Publications
2019
2018
2017
Using several metals with different work functions as solar cell back contact we identify majority carrier type inversion in methylammonium lead bromide (MAPbBr3, without intentional doping) as the basis for the formation of a p-n junction. MAPbBr3 films deposited on TiO2 are slightly n-type, whereas in a full device they are strongly p-type. The charge transfer between the metal electrode and the halide perovskite (HaP) film is shown to determine the dominant charge carrier type of the HaP and, thus, also of the final cells. Usage of Pt, Au and Pb as metal electrodes shows the effects of metal work function on minority carrier diffusion length and majority carrier concentration in the HaP, as well as on built-in voltage, band bending, and open circuit voltage (V-OC) within a solar cell. V-OC > 1.5 V is demonstrated. The higher the metal WF, the higher the carrier concentration induced in the HaP, as indicated by a narrower space charge region and a smaller minority carrier diffusion length. From the analysis of bias-dependent electron beam-induced currents, the HaP carrier concentrations are estimated to be similar to 1 x 10(17) cm(-3) with Au and 2-3 x 10(18) cm(-3) with Pt. A model in which type-inversion stretches across the entire film width implies formation of the p-n junction away from the interface, near the back-contact metal electrode. This work highlights the importance of the contact metal on device performance in that contact engineering can also serve to control the carrier concentration in HaP.
We present a measurement of the energies and capture cross-sections of defect states in methylammonium lead bromide (MAPbBr(3)) single crystals. Using Laplace current deep level transient spectroscopy (I-DLTS), two prominent defects were observed with energies 0.17 eV and 0.20 eV from the band edges, and further I-DLTS measurements confirmed that these two defects are bulk defects. These results show qualitative agreement with theoretical predictions, whereby all of the observed defects behave as traps rather than as generation-recombination centers. These results provide one explanation for the high efficiencies and open-circuit voltages obtained from devices made with lead halide perovskites. Published by AIP Publishing.
Recent studies showed that positron annihilation methods can provide key insights into the nanostructure and electronic structure of thin film solar cells. In this study, positron annihilation lifetime spectroscopy (PALS) is applied to investigate CdSe quantum dot (QD) light absorbing layers, providing evidence of positron trapping at the surfaces of the QDs. This enables one to monitor their surface composition and electronic structure. Further, 2D-Angular Correlation of Annihilation Radiation (2D-ACAR) is used to investigate the nanostructure of divacancies in photovoltaic-high-quality a-Si: H films. The collected momentum distributions were converted by Fourier transformation to the direct space representation of the electron-positron autocorrelation function. The evolution of the size of the divacancies as a function of hydrogen dilution during deposition of a-Si: H thin films was examined. Finally, we present a first positron Doppler Broadening of Annihilation Radiation (DBAR) study of the emerging class of highly efficient thin film solar cells based on perovskites.
Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI(3)). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI(3) is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI(3) (unlike MAPbBr(3)) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material's relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity's hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI(3), we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material's noncentrosymmetry. We note that the material's ferroelectric nature, can, but need not be important in a PV cell at room temperature.
Doped ceria is known for decades as an excellent ionic conductor used ubiquitously in fuel cells and other devices. Recent discovery of a giant electrostriction effect has brought world-wide interest to this class of materials for actuation applications in micromechanical systems. From this aspect, the electromechanical response has to be studied as a function of external parameters, such as frequency, temperature, and electrode material. In this work, we fabricated circular membranes based on Gd-doped ceria (CGO) with Ti electrodes and studied their electromechanical response using a sensitive interferometric technique. The self-supported membranes are flat at room temperature and reversibly buckle upon heating, indicating that the membranes are under in-plane tensile strain. We have found that the electromechanical response is strongly frequency dependent. Significant hysteresis is observed in the displacement-vs.-voltage curves, which is deleterious for micromechanical applications but can be eliminated by tuning the phase of the excitation voltage. The electromechanical response of the system increases with temperature. Finite Element Modeling is applied to evaluate the electrostriction coefficient of the CGO material. At low frequencies, the M-12 electrostriction coefficient is about 5 x 10(-18) m(2)/V-2, which is in line with the previous reports. Published by AIP Publishing.
Materials are central to our way of life and future. Energy and materials as resources are connected, and the obvious connections between them are the energy cost of materials and the materials cost of energy. For both of these, resilience of the materials is critical; thus, a major goal of future chemistry should be to find materials for energy that can last longer, that is, design principles for self-repair in these.
Negative capacitance in photovoltaic devices has been observed and reported in several cases, but its origin, at low or intermediate frequencies, is under debate. Here we unambiguously demonstrate a direct correlation between the observation of this capacitance and a corresponding decrease in performance of a halide perovskite (HaP; CsPbBr3)-based device, expressed as reduction of open-circuit voltage and fill factor. We have prepared highly stable CsPbBr3 HaPs that do not exhibit any degradation over the duration of the impedance spectroscopy measurements, ruling out degradation as the origin of the observed phenomena. Reconstruction of current voltage curves from the impedance spectroscopy provided further evidence of the deleterious role of negative capacitance on photoconversion performance.
Halide perovskite film-based devices (e.g., solar cells and LEDs) have shown unique device performance. These films are commonly prepared from toxic solutions of metal salts (e.g., Pb2+ in DMF or DMSO). We describe a method to form halide perovskite films by simply reacting metal (Pb or Sn) films with alcoholic solutions of monovalent alkali metal or alkyl ammonium halides, which avoids the use of toxic Pb2+ solutions in the manufacturing step. We show how the morphology of the films can be controlled by variation in reaction parameters and also how mixed halide perovskite films can be prepared. A mechanism for the metal-to-perovskite conversion is suggested. We further show how electrochemically assisted conversion can allow control over the oxidation state of the metal and increase the reaction rate greatly.
The inorganic lead halide perovskite CsPbBr3 promises similar solar cell efficiency to its hybrid organic-inorganic counterpart CH3NH3PbBr3 but shows greater stability. Here, we exploit this stability for the study of band alignment between perovskites and carrier selective interlayers. Using ultraviolet, X-ray, and inverse photoemission spectroscopies, we measure the ionization energy and electron affinities of CsPbBr3 and the hole transport polymer polytriarylamine (PTAA). We find that undoped PTAA introduces a barrier to hole extraction of 0.2-0.5 eV, due to band bending in the PTAA and/or a dipole at the interface. p-doping the PTAA eliminates this barrier, raising PTAA's highest occupied molecular orbital to 0.2 eV above the CsPbBr3 valence band maximum and improving hole transport. However, IPES reveals the presence of states below the PTAA lowest unoccupied molecular level. If present at the CsPbBr3/PTAA interface, these states may limit the polymer's efficacy at blocking electrons in solar cells with wide band gap materials like CsPbBr3 and CH3NH3PbBr3. Published by AIP Publishing.
We review charge transport across molecular monolayers, which is central to molecular electronics (MolEl), using large-area junctions (NmJ). We strive to provide a wide conceptual overview of three main subtopics. First, a broad introduction places NmJ in perspective to related fields of research and to single-molecule junctions (imp in addition to a brief historical account. As charge transport presents an ultrasensitive probe for the electronic perfection of interfaces, in the second part ways to form both the monolayer and the contacts are described to construct reliable, defect-free interfaces. The last part is dedicated to understanding and analyses of current-voltage (I-V) traces across molecular junctions. Notwithstanding the original motivation of MolEl, I-V traces are often not very sensitive to molecular details and then provide a poor probe for chemical information. Instead, we focus on how to analyze the net electrical performance of molecular junctions, from a functional device perspective. Finally, we point to creation of a built-in electric field as a key to achieve functionality, including nonlinear current-voltage characteristics that originate in the molecules or their contacts to the electrodes. This review is complemented by a another review that covers metal-molecule-semiconductor junctions and their unique hybrid effects.
Inserting molecular monolayers within metal/semiconductor interfaces provides one of the most powerful expressions of how minute chemical modifications can affect electronic devices. This topic also has direct importance for technology as it can help improve the efficiency of a variety of electronic devices such as solar cells, LEDs, sensors, and possible future bioelectronic ones. The review covers the main aspects of using chemistry to control the various aspects of interface electrostatics, such as passivation of interface states and alignment of energy levels by intrinsic molecular polarization, as well as charge rearrangement with the adjacent metal and semiconducting contacts. One of the greatest merits of molecular monolayers is their capability to form excellent thin dielectrics, yielding rich and unique current voltage characteristics for transport across metal/molecular monolayer/semiconductor interfaces. We explain the interplay between the monolayer as tunneling barrier on the one hand, and the electrostatic barrier within the semiconductor, due to its space-charge region, on the other hand, as well as how different monolayer chemistries control each of these barriers. Practical tools to experimentally identify these two barriers and distinguish between them are given, followed by a short look to the future. This review is accompanied by another one, concerning the formation of large-area molecular junctions and charge transport that is dominated solely by molecules.
2016
Direct comparison between perovskite-structured hybrid organic-inorganic methylammonium lead bromide (MAPbBr3) and all-inorganic cesium lead bromide (CsPbBr3), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr3 demonstrates a higher thermal stability than MAPbBr3. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr3 or CsPbBr3, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of 6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15-20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.
Halide perovskite-based solar cells still have limited reproducibility, stability, and incomplete understanding of how they work. We track electronic processes in [CH3NH3]PbI3(Cl) ("perovskite") films in vacuo, and in N2, air, and O2, using impedance spectroscopy (IS), contact potential difference, and surface photovoltage measurements, providing direct evidence for perovskite sensitivity to the ambient environment. Two major characteristics of the perovskite IS response change with ambient environment, viz. -1- appearance of negative capacitance in vacuo or post-vacuo N2 exposure, indicating for the first time an electrochemical process in the perovskite, and -2- orders of magnitude decrease in the film resistance upon transferring the film from O2-rich ambient atmosphere to vacuum. The same change in ambient conditions also results in a 0.5 V decrease in the material work function. We suggest that facile adsorption of oxygen onto the film dedopes it from n-type toward intrinsic. These effects influence any material characterization, i.e., results may be ambient-dependent due to changes in the material's electrical properties and electrochemical reactivity, which can also affect material stability.
CONSPECTUS: Hybrid alkylammonium lead halide perovskite solar cells have, in a very few years of research, exceeded a light-to-electricity conversion efficiency of 20%, not far behind crystalline silicon cells. These perovskites do not contain any rare element, the amount of toxic lead used is very small, and the cells can be made with a low energy input. They therefore already conform to two of the three requirements for viable, commercial solar cells efficient and cheap. The potential deal-breaker is their long-term stability. While reasonable short-term (hours) and even medium term (months) stability has been demonstrated, there is concern whether they will be stable for the two decades or more expected from commercial cells in view of the intrinsically unstable nature of these materials. In particular, they have a tendency to be sensitive to various types of irradiation, including sunlight, under certain conditions. This Account focuses on the effect of irradiation on the hybrid (and to a small degree, all-inorganic) lead halide perovskites and their solar cells. It is split up into two main sections. First, we look at the effect of electron beams on the materials. This is important, since such beams are used for characterization of both the perovskites themselves and cells made from them (electron microscopy for morphological and compositional characterization; electron beam-induced current to study cell operation mechanism; cathodoluminescence for charge carrier recombination studies). Since the perovskites are sensitive to electron beam irradiation, it is important to minimize beam damage to draw valid conclusions from such measurements. The second section treats the effect of visible and solar UV irradiation on the perovskites and their cells. As we show, there are many such effects. However, those affecting the perovskite directly need not necessarily always be detrimental to the cells, while those affecting the solar cells, which are composed of several
A vertical nanogap device (VND) structure comprising all-silicon contacts as electrodes for the investigation of electronic transport processes in bioelectronic systems is reported. Devices were fabricated from silicon-on-insulator substrates whose buried oxide (SiO2) layer of a few nanometers in thickness is embedded within two highly doped single crystalline silicon layers. Individual VNDs were fabricated by standard photolithography and a combination of anisotropic and selective wet etching techniques, resulting in p(+) silicon contacts, vertically separated by 4 or 8 nm, depending on the chosen buried oxide thickness. The buried oxide was selectively recessetched with buffered hydrofluoric acid, exposing a nanogap. For verification of the devices' electrical functionality, gold nanoparticles were successfully trapped onto the nanogap electrodes' edges using AC dielectrophoresis. Subsequently, the suitability of the VND structures for transport measurements on proteins was investigated by functionalizing the devices with cytochrome c protein from solution, thereby providing non-destructive, permanent semiconducting contacts to the proteins. Current-voltage measurements performed after protein deposition exhibited an increase in the junctions' conductance of up to several orders of magnitude relative to that measured prior to cytochrome c immobilization. This increase in conductance was lost upon heating the functionalized device to above the protein's denaturation temperature (80 degrees C). Thus, the VND junctions allow conductance measurements which reflect the averaged electronic transport through a large number of protein molecules, contacted in parallel with permanent contacts and, for the first time, in a symmetrical Si-protein-Si configuration.
To experimentally (dis)prove ferroelectric effects on the properties of lead-halide perovskites and of solar cells, based on them, we used second-harmonic-generation spectroscopy and the periodic temperature change (Chynoweth) technique to detect the polar nature of methylammonium lead bromide (MAPbBr 3). We find that MAPbBr 3 is probably centrosymmetric and definitely non-polar; thus, it cannot be ferroelectric. Whenever pyroelectric-like signals were detected, they could be shown to be due to trapped charges, likely at the interface between the metal electrode and the MAPbBr 3 semiconductor. These results indicate that the ferroelectric effects do not affect steady-state performance of MAPbBr 3 solar cells.
Solution-processed hybrid organic-inorganic perovskites (HOIPs) exhibit long electronic carrier diffusion lengths, high optical absorption coefficients and impressive photovoltaic device performance. Recent results allow us to compare and contrast HOIP charge-transport characteristics to those of III-V semiconductors - benchmarks of photovoltaic (and light-emitting and laser diode) performance. In this Review, we summarize what is known and unknown about charge transport in HOIPs, with particular emphasis on their advantages as photovoltaic materials. Experimental and theoretical findings are integrated into one narrative, in which we highlight the fundamental questions that need to be addressed regarding the charge-transport properties of these materials and suggest future research directions.
We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI(3), MAPbBr(3), CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites.
Electron transport properties via a photochromic biological photoreceptor have been studied in junctions of monolayer assemblies in solid-state configurations. The photoreceptor studied was a member of the LOV domain protein family with a bound flavin chromophore, and its photochemically inactive mutant due to change of a crucial cysteine residue by a serine. The photochemical properties of the protein were maintained in dry, solid state conditions, indicating that the proteins in the junctions were assembled in native state-like conditions. Significant current magnitudes (>20 mu A at 1.0 V applied bias) were observed with a mechanically deposited gold pad (area similar to 0.002 cm(2)) as top electrode. The current magnitudes are ascribed to electrode-cofactor coupling originating from the apparent perpendicular orientation of the protein's cofactor embedded between the electrodes, and its proximity to the electrodes. Temperature independent electron transport across the protein monolayers demonstrated that solid-state electron transport is dominated by tunneling. Modulation of the observed current by illumination of the wildtype protein suggested conformation-dependent electron conduction efficiency across the solid-state protein junctions.
The realization of high-quality optoelectronic properties in halide perovskite semiconductors through low-temperature, low energy processing is unprecedented. Understanding the unique aspects of the formation chemistry of these semiconductors is a critical step toward understanding the genesis of high quality material via simple preparation procedures. The toolbox of preparation procedures for halide perovskites grows rapidly. The prototypical reaction is that between lead iodide (PbI2) and methylammonium iodide (CH3NH3I, abbr. MAI) to form the perovskite CH3NH3PbI3 (MAPbI(3)), which we discuss in this work. We investigate the conversion of small, single-crystalline PbI2 crystallites to MAPbI(3) by two commonly used synthesis processes: reaction with MAI in solution or as a vapor. The single crystal nature of the PbI2 precursor allows definitive conclusions to be made about the relationship between the precursors and the final product, illuminating previously unobserved aspects of the reaction process. From in situ photoluminescence microscopy, we find that the reaction in solution begins via isolated nucleation events followed by growth from the nuclei. We observe via X-ray diffraction and morphological characterization that there is a strong orientational and structural relationship between the final stage of the solution-reacted MAPbI(3) product and the initial PbI2 crystallite. In all these measurements, we find that the reaction does not proceed below a certain MAI threshold concentration, which allows the first experimental determination of a free energy of formation for a widely used synthetic procedure of similar to 0.1 eV. From these conclusions, we present a more detailed hypothesis about the reaction pathway than has yet been proposed: Our results suggest that the reaction in solution begins with a topotactic nucleation event followed by grain growth by dissolution-reconstruction. By similar techniques, we find the reaction via vapor phase produces
Photovoltaic solar cells operate under steady-state conditions that are established during the charge carrier excitation and recombination. However, to date no model of the steady-state recombination scenario in halide perovskites has been proposed. In this Letter we present such a model that is based on a single type of recombination center, which is deduced from our measurements of the illumination intensity dependence of the photoconductivity and the ambipolar diffusion length in those materials. The relation between the present results and those from time-resolved measurements, such as photoluminescence that are commonly reported in the literature, is discussed.
Solar cells based on "halide perovskites" (HaPs) have demonstrated unprecedented high power conversion efficiencies in recent years. However, the well-known toxicity of lead (Pb), which is used in the most studied cells, may affect its widespread use. We explored an all-inorganic lead-free perovskite option, cesium tin bromide (CsSnBr3), for optoelectronic applications. CsSnBr3-based solar cells exhibited photoconversion efficiencies (PCEs) of 2.1%, with a short-circuit current (J(sc)) of similar to 9 mA cm(-2), an open circuit potential (V-oc) of 0.41 V, and a fill factor (FF) of 58% under 1 sun (100 mW cm(-2)) illumination, which, even though meager compared to the Pb analogue-based cells, are among the best reported until now. As reported earlier, addition of tin fluoride (SnF2) was found to be beneficial for obtaining good device performance, possibly due to reduction of the background carrier density by neutralizing traps, possibly via filling of cation vacancies. The roles of SnF2 on the properties of the CsSnBr3 were investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) analysis.
Simple organic salts are used as a cheap alternative for hole-conducting materials in methylammonium lead bromide perovskite solar cells and obtaining power conversion efficiency of 4.4%. The findings suggest that the polar organic salts interact with the perovskite surface, leading to formation of a surface dipole or change of an existing one on the perovskites that changes its effective work function.
We investigate the effect of high work function contacts in halide perovskite absorber-based photovoltaic devices. Photoemission spectroscopy measurements reveal that band bending is induced in the absorber by the deposition of the high work function molybdenum trioxide (MoO3). We find that direct contact between MoO3 and the perovskite leads to a chemical reaction, which diminishes device functionality. Introducing an ultrathin spiro-MeOTAD buffer layer prevents the reaction, yet the altered evolution of the energy levels in the methylammonium lead iodide (MAPbI(3)) layer at the interface still negatively impacts device performance.
2015
Surprisingly efficient solid-state electron transport has recently been demonstrated through "dry" proteins (with only structural, tightly bound H2O left), suggesting proteins as promising candidates for molecular (bio)electronics. Using inelastic electron tunneling spectroscopy (IETS), we explored electron-phonon interaction in metal/protein/metal junctions, to help understand solid-state electronic transport across the redox protein azurin. To that end an oriented azurin monolayer on Au is contacted by soft Au electrodes. Characteristic vibrational modes of amide and amino acid side groups as well as of the azurin electrode contact were observed, revealing the azurin native conformation in the junction and the critical role of side groups in the charge transport. The lack of abrupt changes in the conductance and the line shape of IETS point to far off-resonance tunneling as the dominant transport mechanism across azurin, in line with previously reported (and herein confirmed) azurin junctions. The inelastic current and hence electron-phonon interaction appear to be rather weak and comparable in magnitude with the inelastic fraction of tunneling current via alkyl chains, which may reflect the known structural rigidity of azurin.
Electron transfer (ET) proteins are biomolecules with specific functions, selected by evolution. As such they are attractive candidates for use in potential bioelectronic devices. The blue copper protein azurin (Az) is one of the most-studied ET proteins. Traditional spectroscopic, electrochemical, and kinetic methods employed for studying ET to/from the protein's Cu ion have been complemented more recently by studies of electrical conduction through a monolayer of Az in the solid-state, sandwiched between electrodes. As the latter type of measurement does not require involvement of a redox process, it also allows monitoring electronic transport (ETp) via redox-inactive Az-derivatives. Here, results of macroscopic ETp via redox-active and -inactive Az derivatives, i.e., Cu(II) and Cu(I)-Az, apo-Az, Co(II)-Az, Ni(II)-Az, and Zn(II)Az are reported and compared. It is found that earlier reported temperature independence of ETp via Cu(II)-Az (from 20 K until denaturation) is unique, as ETp via all other derivatives is thermally activated at temperatures >approximate to 200 K. Conduction via Cu(I)-Az shows unexpected temperature dependence >approximate to 200 K, with currents decreasing at positive and increasing at negative bias. Taking all the data together we find a clear compensation effect of Az conduction around the Az denaturation temperature. This compensation can be understood by viewing the Az binding site as an electron trap, unless occupied by Cu(II), as in the native protein, with conduction of the native protein setting the upper transport efficiency limit.
The great promise of hybrid organic inorganic lead halide perovskite (HOIP)-based solar cells is being challenged by its Pb content and its sensitivity to water. Here, the impact of rain on methylammonium lead iodide perovskite films was investigated by exposing such films to water of varying pH values, simulating exposure of the films to rain. The amount of Pb loss was determined using both gravimetric and inductively coupled plasma mass spectrometry measurements. Using our results, the extent of Pb loss to the environment, in the case of catastrophic module failure, was evaluated. Although very dependent on module siting, even total destruction of a large solar electrical power generating plant, based on HOIPs, while obviously highly undesirable, is estimated to be far from catastrophic for the environment.
Using ultrafast visible/IR pulse-sequence spectroscopy combined with electric current detection, we engage vibronic and charge-delocalization phenomena to control the performance of optoelectronic devices base on organic semiconductors, colloidal quantum dots and conductive oxides.
Hybrid organic-inorganic lead halide perovskite photovoltaic cells have already surpassed 20% conversion efficiency in the few years that they have been seriously studied. However, many fundamental questions still remain unanswered as to why they are so good. One of these is "Is the organic cation really necessary to obtain high quality cells?" In this study, we show that an all-inorganic version of the lead bromide perovslcite material works equally well as the organic one, in particular generating the high open circuit voltages that are an important feature of these cells.
High band gap, high open-circuit voltage solar cells with methylammonium lead tribromide (MAPbBr(3)) perovskite absorbers are of interest for spectral splitting and photoelectrochemical applications, because of their good performance and ease of processing. The physical origin of high performance in these and similar perovskite-based devices remains only partially understood. Using cross-sectional electron-beam-induced current (EBIC) measurements, we find an increase in carrier diffusion length in MAPbBr(3)(Cl)-based solar cells upon low intensity (a few percent of 1 sun intensity) blue laser illumination. Comparing dark and illuminated conditions, the minority carrier (electron) diffusion length increases about 3.5 times from L-n = 100 +/- 50 nm to 360 +/- 22 nm. The EBIC cross section profile indicates a p-n structure between the n-FTO/TiO, and p-perovskite, rather than the p-i-n structure, reported for the iodide derivative. On the basis of the variation in space-charge region width with varying bias, measured by EBIC and capacitance-voltage measurements, we estimate the net-doping concentration in MAPbBr(3)(Cl) to be 3-6 x 10(17) cm(-3).
The conclusions reached by a diverse group of scientists who attended an intense 2-day workshop on hybrid organic-inorganic perovskites are presented, including their thoughts on the most burning fundamental and practical questions regarding this unique class of materials, and their suggestions on various approaches to resolve these issues.
The soft character of organic materials leads to strong coupling between molecular, nuclear and electronic dynamics. This coupling opens the way to influence charge transport in organic electronic devices by exciting molecular vibrational motions. However, despite encouraging theoretical predictions, experimental realization of such approach has remained elusive. Here we demonstrate experimentally that photoconductivity in a model organic optoelectronic device can be modulated by the selective excitation of molecular vibrations. Using an ultrafast infrared laser source to create a coherent superposition of vibrational motions in a pentacene/C-60 photoresistor, we observe that excitation of certain modes in the 1,500-1,700 cm(-1) region leads to photocurrent enhancement. Excited vibrations affect predominantly trapped carriers. The effect depends on the nature of the vibration and its mode-specific character can be well described by the vibrational modulation of intermolecular electronic couplings. This presents a new tool for studying electron-phonon coupling and charge dynamics in (bio) molecular materials.
We observe temperature-independent electron transport, characteristic of tunneling across a approximately 6 nm thick Halorhodopsin (phR) monolayer. phR contains both retinal and a carotenoid, bacterioruberin, as cofactors, in a trimeric protein-chromophore complex. This finding is unusual because for conjugated oligo-imine molecular wires a transition from temperature-independent to -dependent electron transport, ETp, was reported at approximately 4 nm wire length. In the approximately 6 nm long phR, the approximately 4 nm 50-carbon conjugated bacterioruberin is bound parallel to the alpha-helices of the peptide backbone. This places bacterioruberin's ends proximal to the two electrodes that contact the protein; thus, coupling to these electrodes may facilitate the activation-less current across the contacts. Oxidation of bacterioruberin eliminates its conjugation, causing the ETp to become temperature dependent (>180 K). Remarkably, even elimination of the retinal-protein covalent bond, with the fully conjugated bacterioruberin still present, leads to temperature-dependent ETp (>180 K). These results suggest that ETp via phR is cooperatively affected by both retinal and bacterioruberin cofactors.
2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Electron transport (ETp) across met-myoglobin (m-Mb), as measured in a solid-state-like configuration between two electronic contacts, increases by up to 20 fold if Mb is covalently bound to one of the contacts, a Si electrode, in an oriented manner by its hemin (ferric) group, rather than in a non-oriented manner. Oriented binding of Mb is achieved by covalently binding hemin molecules to form a monolayer on the Si electrode, followed by reconstitution with apo-Mb. We found that the ETp temperature dependence (>120?K) of non-oriented m-Mb virtually disappears when bound in an oriented manner by the hemin group. Our results highlight that combining direct chemical coupling of the protein to one of the electrodes with uniform protein orientation strongly improves the efficiency of ET across the protein. We hypothesize that the behavior of reconstituted m-Mb is due to both strong protein-substrate electronic coupling (which is likely greater than in non-oriented m-Mb) and direct access to a highly efficient transport path provided by the hemin group in this configuration.
We report a combined ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) study of the electronic structure of aromatic self-assembled monolayers covalently bound to Si, using several different aromatic groups (phenyl, biphenyl, and fluorene) and binding groups (O, NH, and CH2). We obtain excellent agreement between theory and experiment, which allows for a detailed interpretation of the experimental results. Our analysis reveals a significant effect of the binding group on state hybridization at the organic/inorganic interface. Specifically, it highlights that lone-pair electrons in the binding atom facilitate hybridization between the aromatic system and the Si substrate, resulting in a significant induced density of interface states (IDIS). These interface states are manifested as a broadened HOMO peak in the experimental UPS data and are clearly observed in a theoretical spatially-resolved density of states map. This provides means to control the degree of coupling between substrate and molecule, which may prove useful in the design of transport across organic/inorganic interfaces. 2015 Elsevier B.V.
A small molecule based on N,N'-dialkyl perylenediimide (PDI) as core derivatized with thiophene moieties (Th-PDI) was synthesized. Its HOMO (highest occupied molecular orbital) level was measured to be between 5.7 and 6.3 eV vs. local vacuum level depending on doping and measurement method. Th-PDI was successfully applied as hole-transporting material (HTM) in CH3NH3PbBr3 hybrid perovskite solar cells. Three different cell architectures, each with a different mode of operation, were tested: (1) using a mesoporous (mp) TiO2 substrate; (2) mp-Al2O3 substrate; (3) planar dense TiO2 substrate. The first gave the best overall efficiency of 5.6% while the mp-Al2O3 gave higher open-circuit photovoltage (VOC) but lower efficiency (2.2%). The cells exhibited good reproducibility with very little J-V hysteresis (the mp-Al2O3 showed a more appreciable hysteresis of individual photovoltaic parameters but little dependence of efficiency on scan direction). Storage of unencapsulated cells in 25-30% relative humidity demonstrated fairly good stability with
2014
Direct and inverse photoemission spectroscopies are used to determine materials electronic structure and energy level alignment in hybrid organic-inorganic perovskite layers grown on TiO2. The results provide a quantitative basis for the analysis of perovskite-based solar cell performance and choice of an optimal hole-extraction layer.
Reproducible molecular junctions can be integrated within standard CMOS technology. Metal-molecule-semiconductor junctions are fabricated by direct Si-C binding of hexadecane or methyl-styrene onto oxide-free H-Si(111) surfaces, with the lateral size of the junctions defined by an etched SiO2 well and with evaporated Pb as the top contact. The current density, J, is highly reproducible with a standard deviation in log(J) of 0.2 over a junction diameter change from 3 to 100 mu m. Reproducibility over such a large range indicates that transport is truly across the molecules and does not result from artifacts like edge effects or defects in the molecular monolayer. Device fabrication is tested for two n-Si doping levels. With highly doped Si, transport is dominated by tunneling and reveals sharp conductance onsets at room temperature. Using the temperature dependence of current across medium-doped n-Si, the molecular tunneling barrier can be separated from the Si-Schottky one, which is a 0.47 eV, in agreement with the molecular-modified surface dipole and quite different from the bare Si-H junction. This indicates that Pb evaporation does not cause significant chemical changes to the molecules. The ability to manufacture reliable devices constitutes important progress toward possible future hybrid Si-based molecular electronics.
Conducting Probe AFM. CP-AFM, was used to follow how chemical etching, oxidation, and sulfurization affect the surface nanoscale electrical characteristics of polycrystalline Cu(In,Ga)Se-2 (CIGS) thin films. Band bending at grain boundaries (GBs) on the surface was studied and analyzed by CP-AFM - measured photocurrents. We find that both oxidation and sulfurization can passivate the GBs of the CIGS films; oxidation increases n-type band bending, which impedes the transport of photogenerated electrons, while sulfurization increases p-type band bending at GBs, which helps this transport. Differences in effects between surface terminations by sulfide, selenide and oxide were analyzed. The effects of these treatments on the electrical activity of the GBs of the films, as well as the importance of the use of chemical bath deposition of the CdS buffer, are explained within a defect surface chemistry model. (C) 2013 Elsevier B.V. All rights reserved.
A distinct odd even effect on the electrical properties, induced by monolayers of alkyl-phenyl molecules directly bound to Si(111), is reported. Monomers of H2C=CH- Even (CH2) phenyl, with n = 2-5, were adsorbed onto Si I-I and formed high-quality monolayers with a binding density of 50-60% Si(111) surface atoms. Molecular dynamics simulations suggest that the binding proximity is close enough to allow efficient /r,r interactions and therefore distinctly different packing and ring orientations for monomers with odd or even numbers of rnethylenes in their alkyl spacers. The odd even alternation in molecular tilt was experimentally confirmed by con. tact ellipsometry, and XPS with a close quantitative matc,t to the simulation results. The orientation. an even s of bot h ring ng p ane and the long axis f the alkyl spacer are more perpendicular pi-pi the with substrate lane for molecules number of niethylenes than for those with an odd number ofi7rriethilYlenesd. with Interestingly! those th an even number conduct better than the effectively thinner mono.laYers Of the Plialeatrin_s le with respect odd number of inethylenes. We attribute this to a change in the orientation of the electron density,on the aromatic to the shortest tunneling path, which increases the harrier for electron transport through the Odd monolaye,rsof,The hig h sensitivity of molecular charge transport o orientation t the oentation of an aromatic moiety might be relevant to better control over th electronic properties of interfaces n organic electronics.
CH3NH3PbI3-based solar cells were characterized with electron beam-induced current (EBIC) and compared to CH3NH3PbI3-xClx ones. A spatial map of charge separation efficiency in working cells shows p-i-n structures for both thin film cells. Effective diffusion lengths, L-D, (from EBIC profile) show that holes are extracted significantly more efficiently than electrons in CH3NH3PbI3, explaining why CH3NH3PbI3-based cells require mesoporous electron conductors, while CH3NH3PbI3-xClx ones, where L-D values are comparable for both charge types, do not.
Low-cost solar cells with high V-OC, relatively small (E-G - qV(OC)), and high qV(OC)/E-G ratio, where E-G is the absorber band gap, are long sought after, especially for use in tandem cells or other systems with spectral splitting. We report a significant improvement in CH3NH3PbBr3-based cells, using CH(3)NH(3)PbBr(3-)xCl(x), with E-G = 2.3 eV, as the absorber in a mesoporous p-i-n device configuration. By p-doping an organic hole transport material with a deep HOMO level and wide band gap to reduce recombination, the cell's V-OC increased to 1.5 V, a 0.2 V increase from our earlier results with the pristine Br analogue with an identical band gap. At the same time, in the most efficient devices, the current density increased from similar to 1 to 4 mA/cm(2).
The work function (WF) of ZnO is modified by two types of dipole-bearing phenylphosphonate layers, yielding a maximum WF span of 1.2 eV. H3CO-phenyl phosphonate, with a positive dipole (positive pole pointing outwards from the surface), lowers the WF by similar to 350 meV. NC-phenyl phosphonate, with a negative dipole, increases the WF by similar to 750 meV. The WF shift is found to be independent of the type of ZnO surface. XPS data show strong molecular dipoles between the phenyl and the functionalizing (CN and OMe) tail groups, while an opposite dipole evolves in each molecular layer between the surface and the phenyl rings. The molecular modification is found to be invariant to supra-bandgap illumination, which indicates that the substrate's space charge-induced built-in potential is unlikely to be the reason for the WF difference. ZnO, grown by several different methods, with different degrees of crystalline perfection and various morphologies and crystallite dimensions, could all be modified to the same extent. Furthermore, a mixture of opposite dipoles allows gradual and continuous tuning of the WF, varying linearly with the partial concentration of the CN-terminated phosphonate in the solution. Exposure to the phosphonic acids during the molecular layer deposition process erodes a few atomic layers of the ZnO. The general validity of the treatment and the fine-tuning of the WF of treated interfaces are of interest for solar cells and LED applications.
The field of organo-lead perovskite absorbers for solar cells is developing rapidly, with open-circuit voltage of reported devices already approaching the maximal theoretical voltage. Obtaining such high voltages on spun-cast or evaporated thin films is intriguing and calls for detailed investigation of the source of photovoltage in those devices. We present here a study of the roles of the selective contacts to methylammonium lead iodide chloride (MAPbI(3-x)Cl(x)) using surface photovoltage spectroscopy. By depositing and characterizing each layer at a time, we show that the electron-extracting interface is more than twice as effective as the hole-extracting interface in generating photovoltage, for several combinations of electrode materials. We further observe the existence of an electron-injection related spectral feature at 1.1 eV, which might bear significance for the cell's operation. Our results illustrate the usefulness of SPV spectroscopy in highlighting gaps in cells efficiency and for deepening the understanding of charge injection processes in perovskite-based photovoltaics.
Potential future use of bacteriorhodopsin (bR) as a solid-state electron transport (ETp) material requires the highest possible active protein concentration. To that end we prepared stable monolayers of protein enriched bR on a conducting HOPG substrate by lipid depletion of the native bR. The ETp properties of this construct were then investigated using conducting probe atomic force microscopy at low bias, both in the ground dark state and in the M-like intermediate configuration, formed upon excitation by green light Photoconductance modulation was observed upon green and blue light excitation, demonstrating the potential of these monolayers as optoelectronic building blocks. To correlate protein structural changes with the observed behavior, measurements were made as a function of pressure under the AFM tip, as well as humidity. The junction conductance is reversible under pressure changes up to similar to 300 MPa, but above this pressure the conductance drops irreversibly. ETp efficiency is enhanced significantly at >60% relative humidity, without changing the relative photoactivity significantly. These observations are ascribed to changes in protein conformation and flexibility and suggest that improved electron transport pathways can be generated through formation of a hydrogen-bonding network.
Organometallic lead-halide perovskite-based solar cells now approach 18% efficiency. Introducing a mixture of bromide and iodide in the halide composition allows tuning of the optical bandgap. We prepare mixed bromide-iodide lead perovskite films CH3NH3Pb(I1-xBrx)(3) (0
Hybrid organic/lead halide perovskites are promising materials for solar cell fabrication, resulting in efficiencies up to 18%. The most commonly studied perovskites are CH3NH3PbI3 and CH3NH3PbI3-xClx where x is small. Importantly, in the latter system, the presence of chloride ion source in the starting solutions used for the perovskite deposition results in a strong increase in the overall charge diffusion length. In this work we investigate the crystallization parameters relevant to fabrication of perovskite materials based on CH(3)NH(3)Pbl(3) and CH3NH3PbBr3. We find that the addition of PbCl2 to the solutions used in the perovskite synthesis has a remarkable effect on the end product, because PbCl2 nanocrystals are present during the fabrication process, acting as heterogeneous nucleation sites for the formation of perovskite crystals in solution. We base this conclusion on SEM studies, synthesis of perovskite single crystals, and on cryo-TEM imaging of the frozen mother liquid. Our studies also included the effect of different substrates and substrate temperatures on the perovskite nucleation efficiency. In view of our findings, we optimized the procedures for solar cells based on lead bromide perovsldte, resulting in 5.4% efficiency and V-oc of 1.24 V, improving the performance in this class of devices. Insights gained from understanding the hybrid perovskite crystallization process can aid in rational design of the polycrystalline absorber films, leading to their enhanced performance.
The alignment between the energy levels of the constituents of an organic solar cell plays a central role in determining the open-circuit voltage. However, tuning the energy levels of electrodes and/or active components via molecular modifiers placed at interfaces is not straightforward. The morphology of organic materials is commonly controlled by the substrate onto which they are deposited, and differences in morphology often lead to differences in energetics. Such a change in morphology may reduce the effect of surface modifications, as the modified surface is part of an interface with the organic material. Here we show, in an experimental model system, that by using binary molecular monolayers, in which dipolar molecules are buried in a protective nonpolar matrix, we can transform changes in the electrode surface dipole into interface dipole changes without significantly affecting the growth of pentacene onto the molecular layer, thus enabling the use of the full range of dipolar-induced open-circuit-voltage tuning.
Developments in organic-inorganic lead halide-based perovskite solar cells have been meteoric over the last 2 years, with small-area efficiencies surpassing 15%. We address the fundamental issue of how these cells work by applying a scanning electron microscopy-based technique to cell cross-sections. By mapping the variation in efficiency of charge separation and collection in the cross-sections, we show the presence of two prime high efficiency locations, one at/near the absorber/hole-blocking-layer, and the second at/near the absorber/electron-blocking-layer interfaces, with the former more pronounced. This 'twin-peaks' profile is characteristic of a p-i-n solar cell, with a layer of low-doped, high electronic quality semiconductor, between a p-and an n-layer. If the electron blocker is replaced by a gold contact, only a heterojunction at the absorber/hole-blocking interface remains.
The remarkable advances over the past few years in performance of photovoltaic cells, including the advent of new absorber materials, call for an update to the previous assessment of prospects for future progress. The same simple criteria with some refinements, based on cell and module performance data, serve to evaluate and compare most types of solar cells. Apart from Si and InP, for all types the best cells have improved in conversion performances (and crystalline Si modules have made major strides in cost reduction). New cell types, such as perovskite, sustainable chalcogenide, and quantum dot cells, are included. CdTe results bring those cells in line with other well-developed ones, lending some credence to the idea that the criteria provide the reader with knowledge, useful for gauging possible future technological developments. Additionally, the developments of the past few years show that, while the advent of more new cell types cannot be predicted, it can be aided and stimulated by innovative, daring, and creative new materials research.
2013
The quinhydrone/methanol treatment has been reported to yield outstanding passivation of the H-terminated Si(100) surface. Here, we report on the mechanism of this process by comparing the resulting surface to that of freshly etched H-terminated Si, of Si with chemically grown oxide, and of Si treated with hydroquinone/methanol solution of the same concentration. We find that the benzoquinone moieties of the quinhydrone react with the surface to yield a Si-hydroquinone surface termination, while the methanol molecules bind as well to form methoxy-terminated Si. The slightly negative-charged benzene ring of the hydroquinone acts to repel majority carrier electrons from the surface and inhabits the surface recombination. The higher the ratio of surface-bound hydroquinone to surface-bound methoxy species, the larger the minority carrier life-time measured by microwave photoconductivity. Thus, our results lead us to conclude that this treatment results in field effect passivation; remarkably, this effect is caused by a molecular monolayer alone. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4793497]
Mesoscopic solar cells, based on solution-processed organic-inorganic perovskite absorbers, are a promising avenue for converting solar to electrical energy. We used solution-processed organic-inorganic lead halide perovskite absorbers, in conjunction with organic hole conductors, to form high voltage solar cells. There is a dire need for low-cost cells of this type, to drive electrochemical reactions or as the high photon energy cell in a system with spectral splitting. These perovskite materials, although spin-coated from solution, form highly crystalline materials. Their simple synthesis, along with high chemical versatility, allows tuning their electronic and optical properties. By judicious selection of the perovskite lead halide-based absorber, matching organic hole conductor, and contacts, a cell with a similar to 1.3 V open circuit voltage was made. While further study is needed, this achievement provides a general guideline for additional improvement of cell performance.
Integrating proteins in molecular electronic devices requires control over their solid-state electronic transport behavior. Unlike `` traditional'' electron transfer (ET) measurements of proteins that involve liquid environments and a redox cycle, no redox cofactor is needed for solid-state electron transport (ETp) across the protein. Here we show the fundamental difference between these two approaches by macroscopic area measurements, which allow measuring ETp temperature dependence down to cryogenic temperatures, via cytochrome C (Cyt C), an ET protein with a heme (Fe-porphyrin) prosthetic group as a redox centre. We compare the ETp to electrochemical ET measurements, and do so also for the protein without the Fe (with metal-free porphyrin) and without porphyrin. As removing the porphyrin irreversibly alters the protein's conformation, we repeat these measurements with human serum albumin (HSA), 'doped' (by non-covalent binding) with a single hemin equivalent, i.e., these natural and artificial proteins share a common prosthetic group. ETp via Cyt C and HSA-hemin are very similar in terms of current magnitude and temperature dependence, which suggests similar ETp mechanisms via these two systems, thermally activated hopping (with similar to 0.1 eV activation energy) > 190 K and tunneling by superexchange o190 K. Also, ET rates to and from the Fe redox centres (Fe2+reversible arrow Fe3+ + e(-)), measured by electrochemistry of HSA-hemin are only 4 times lower than those for Cyt C. However, while removing the Fe redox centre from the porphyrin ring markedly affects the ET rate, it hardly changes the ETp currents through these proteins, while removing the macrocycle (from HSA, which retains its conformation) significantly reduces ETp efficiency. These results show that solid-state ETp across proteins does not require the presence of a redox cofactor, and that while for ET the Fe ion is the main electron mediator, for ETp the porphyrin ring has this function.
To understand the title topic a model system of single crystal SiC, modified with an interfacial molecular monolayer of alkyl siloxane molecules, with polycrystalline pentacene deposited on it, was fabricated. In this way a change in the length of the alkyl chain could change the structural order of the pentacene film by changing the surface's hydrophobicity, while no significant variation was found in the surface potential, and, thus, in the surface dipole. The pentacene film grown on top of the monolayers showed, with increasing alkyl chain length, increased lateral order and decreased band gap state density, as observed by X-ray diffraction and surface photovoltage spectroscopy. The V-oc, J(sc) and fill factor of solar cells, made with these material combinations, improved with increasing alkyl chain length. We explain this as a result of increased 2D film growth with increasing alkyl chain length of the monolayer, as the surface becomes more hydrophobic, which increases ordering of the pentacene film. Thus, this model system illustrates the role of ordering in charge separation and recombination.
Organic monolayers derived from omega-fluoro-1-alkynes of varying carbon chain lengths (C-10-C-18) were prepared on Si(111) surfaces, resulting in changes of the physical and electronic properties of the surface. Analysis of the monolayers using XPS, Infrared Reflection Absorption Spectroscopy, ellipsometry and static water contact angle measurements provided information regarding the monolayer thickness, the tilt angle, and the surface coverage. Additionally, PCFF molecular mechanics studies were used to obtain information on the optimal packing density and the layer thickness, which were compared to the experimentally found data. From the results, it can be concluded that the monolayers derived from longer chain lengths are more ordered, possess a lower tilt angle, and have a higher surface coverage than monolayers derived from shorter chains. We also demonstrate that by substitution of an H by F atom in the terminal group, it is possible to controllably modify the surface potential and energy barrier for charge transport in a full metal/monolayer-semiconductor (MOMS) junction.
Monolayers of the redox protein Cytochrome C (CytC) can be electrostatically formed on an H-terminated Si substrate, if the protein- and Si-surface are prepared so as to carry opposite charges. With such monolayers we study electron transport (ETp) via CytC, using a solid-state approach with macroscopic electrodes. We have revealed that currents via holo-CytC are almost 3 orders of magnitude higher than via the heme-depleted protein (-> apo-CytC). This large difference in currents is attributed to loss of the proteins' secondary structure upon heme removal. While removal of only the Fe ion (-> porphyrin-CytC) does not significantly change the currents via this protein at room temperature, the 30-335 K temperature dependence suggests opening of a new ETp pathway, which dominates at high temperatures (>285 K). These results suggest that the cofactor plays a major role in determining the ETp pathway(s) within CytC.
Measuring solid-state electron transport (ETp) across proteins allows studying electron transfer (ET) mechanism(s), while minimizing solvation effects on the process. ETp is, however, sensitive to any static (conformational) or dynamic (vibrational) changes in the protein. Our macroscopic measurements allow extending ETp studies to low temperatures, with the concomitant resolution of lower current densities, because of the larger electrode contact areas. Thus, earlier we reported temperature-independent ETp via the copper protein azurin (Az), from 80 K until denaturation, whereas for apo-Az ETp was temperature dependent above 180 K. Deuteration (H/D substitution) may provide mechanistic information on the question of whether the ETp involves H-bonds in the solid state. Here we report results of kinetic deuterium isotope effect (KIE) measurements on ETp through holo-Az as a function of temperature (30-340 K). Strikingly, deuteration changed ETp from temperature independent to temperature dependent above 180 K. This H/D effect is expressed in KIE values between 1.8 (340 K) and 9.1 (
Charge separation at organic-organic (O-O) interfaces is crucial to how many organic-based optoelectronic devices function. However, the mechanism of formation of spatially separated charge carriers and the role of geminate recombination remain topics of discussion and research. We review critically the contributions of the various factors, including electric fields, long-range order, and excess energy (beyond the minimum needed for photoexcitation), to the probability that photogenerated charge carriers will be separated. Understanding the processes occurring at the O/O interface and their relative importance for effective charge separation is crucial to design efficient solar cells and photodetectors. We stress that electron and hole delocalization after photoinduced charge transfer at the interface is important for efficient free carrier generation. Fewer defects at the interface and long-range order in the materials also improve overall current efficiency in solar cells. In efficient organic cells, external electric fields play only a small role for charge separation.
Thermally evaporated Pb preserves the electronic properties of an organic monolayer (ML) on Si and surface passivation of the Si surface itself. The obtained current-voltage characteristics of Pb/ML/Si junctions agree with results obtained with the well-established Hg contact and preserve both the molecule-induced dipole effect on, and length-attenuation of, the current. We rationalize our findings by the lack of interaction between the Pb and the Si substrate. This method is fast, scalable, and compatible with standard semiconductor processing, results in close to 100% yield, and can help the development of large-scale utilization of silicon-organic hybrid electronics. Our experimental data show a dependence of the transport across the molecules on the substrate orientation, expressed in the smaller distance decay parameter with Si(100) than that with Si(111).
We report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (S-N) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors.
Contact potential difference (CPD) measurements of the relative work functions of a range of organic semiconductor thin films show that oxygen causes effective p-type doping (with work functions increasing 0.1-0.3 eV). This doping effect is found to be reversible by exposure to high vacuum or heating in inert atmosphere. The mechanism of doping is explained by a model, based on a reversible formation of an O-substrate charge transfer state. Conductivity measurements of p-phthalocyanine films at variable temperatures support this doping model. The oxygen doping effect is consistent with filling of tail states in the gap, as shown by the increase of activation energy of hole transport with decreased O-doping, and by the good fit between experimental data and simulations of the in-gap density of states. A model hybrid solar cell configuration also shows the effect of doping by O-2 and corroborates the fact that O-doping fills the tail states in the system. (C) 2013 Elsevier B.V. All rights reserved.
Transition voltage spectroscopy (TVS) has become an accepted quantification tool for molecular transport characteristics, due to its simplicity and reproducibility. Alternatively, the Taylor expansion view, TyEx, of transport by tunneling suggests that conductance-voltage curves have approximately a generic parabolic shape, regardless of whether the tunneling model is derived from an average medium view (e.g., WKB) or from a scattering view (e.g., Landauer). Comparing TVS and TyEx approaches reveals that TVS is closely related to a bias-scaling factor, V-0, which is directly derived from the third coefficient of TyEx, namely, the second derivative of the conductance with respect to bias at 0 V. This interpretation of TVS leads to simple expressions that can be compared easily across primarily different tunneling models. Because the basic curve shape is mostly generic, the quality of model fitting is not informative on the actual tunneling model. However internal correlation between the conductance near 0 V and V-0 (TVS) provides genuine indication on fundamental tunneling features. Furthermore, we show that the prevailing concept that V-0 is proportional to the barrier height holds only in the case of resonant tunneling, while for off-resonant or deep tunneling, V-0 is proportional to the ratio of barrier height to barrier width. Finally, considering TVS as a measure of conductance nonlinearity, rather than as an indicator for energy level spectroscopy, explains the very low TVS values observed with a semiconducting (instead of metal) electrode, where transport is highly nonlinear due to the relatively small, bias-dependent density of states of the semiconducting electrode.
The interface level alignment of alkyl and alkenyl monolayers, covalently bound to oxide-free Si substrates of various doping levels, is studied using X-ray photoelectron spectroscopy. Using shifts in the C 1s and Si 2p photoelectron peaks as a sensitive probe, we find that charge distribution around the covalent Si-C bond dipole changes according to the initial position of the Fermi level within the Si substrate. This shows that the interface dipole is not fixed but rather changes with the doping level. These results set limits to the applicability of simple models to describe level alignment at interfaces and show that the interface bond and dipole may change according to the electrostatic potential at the interface.
We report a method for preparing electrode-molecule-electrode junctions that incorporate nonsymmetrical azobenzene dithiols. Our approach is based on sequential deprotection of thiol moieties originally carrying two different protecting groups. The azobenzene derivatives retained their switching properties within monolayers and permitted the photocontrol of electrical conductance.
In recent years, conducting and semiconducting polymers such as PEDOT:PSS and P3HT have become commercially available, and as a result, a new type of polymer/Si heterostructure solar cell is emerging. With a conducting polymer (a degenerate semiconductor) as emitter, such an organic/inorganic hybrid heterojunction is likely to achieve high conversion efficiencies only if the inorganic semiconductor is pushed into strong inversion to reduce dramatically the space-charge recombination and to mitigate the poor lateral conductance of the polymeric layer. We explain this notion through a review of the types of solar cells based on an inversion layer, induced in the semiconductor absorber by a metal, by a dielectricmaterial with fixed charges, or by another semiconductor. In these types, which include the metal-insulator-semiconductor (MIS), semiconductor-insulator-semiconductor, and MIS inversion layer solar cells, interfaces play a crucial role, even more so than in other forms of solid-state photovoltaics. We also point out the strategy by which atomic-layer-deposited Al2O3 can be used to form an inversion layer solar cell on an n-Si emitter.
2012
A combined electronic transport-structure characterization of self-assembled monolayers (MLs) of alkyl-phosphonate (AP) chains on Al-AlOx substrates indicates a strong molecular structural effect on charge transport. On the basis of X-ray reflectivity, XPS, and FTIR data, we conclude that "long" APs (C14 and C16) form much denser MLs than do "short" APs (C8, C10, C12). While current through all junctions showed a tunneling-like exponential length-attenuation, junctions with sparsely packed "short" AP MLs attenuate the current relatively more efficiently than those with densely packed, "long" ones. Furthermore, "long" AP ML junctions showed strong bias variation of the length decay coefficient, beta, while for "short" AP ML junctions beta is nearly independent of bias. Therefore, even for these simple molecular systems made up of what are considered to be inert molecules, the tunneling distance cannot be varied independently of other electrical properties, as is commonly assumed.
Compositional uniformity of Cu(In,Ga)Se-2 (CIGS) solar cells was studied, using thin cross sections of complete cells prepared by focused ion beam (FIB) and examined in the transmission electron microscope (TEM). This methodology revealed the compositional variations at the nm-scale. The Ga and In compositions vary not only between neighboring grains, but also inside individual single crystal grains along their growth direction, which explains the electrical non-uniformity seen in electron beam-induced current (EBIC) measurements. The improved compositional uniformity with increase in sample preparation temperature correlates with higher solar cell efficiency. (C) 2011 Elsevier B.V. All rights reserved.
Electrical transport studies across nm-thick dielectric films can be complicated, and datasets compromised, by local electrical breakdown enhanced by nm-sized features. To avoid this problem we need to know the minimal voltage that causes the enhanced electrical breakdown, a task that usually requires numerous measurements and simulation of which is not trivial. Here we describe and use a model system, using a "floating'' gold pad to contact Au nanoparticles, NPs, to simultaneously measure numerous junctions with high aspect ratio NP contacts, with a dielectric film, thus revealing the lowest electrical breakdown voltage of a specific dielectric-nanocontact combination. For a 48 +/- 1.5 angstrom SiO2 layer and a similar to 7 angstrom monolayer of organic molecules (to link the Au NPs) we show how the breakdown voltage decreases from 4.5 +/- 0.4 V for a flat contact, to 2.4 +/- 0.4 V if 5 nm Au NPs are introduced on the surface. The fact that larger Au NPs on the surface do not necessarily result in significantly higher breakdown voltages illustrates the need for combining experiments with model calculations. This combination shows two opposite effects of increasing the particle size, i.e., increase in defect density in the insulator and decrease in electric field strength. Understanding the process then explains why these systems are vulnerable to electrical breakdown as a result of spikes in regular electrical grids. Finally we use XPS-based chemically resolved electrical measurements to confirm that breakdown occurs indeed right below the nm-sized features.
We report near-perfect transfer of the electrical properties of oxide-free Si surface, modified by a molecular monolayer, to the interface of a junction made with that modified Si surface. Such behavior is highly unusual for a covalent, narrow bandgap semiconductor, such as Si. Short, ambient atmosphere, room temperature treatment of oxide-free Si(100) in hydroquinone (HQ)/alkyl alcohol solutions, fully passivates the Si surface, while allowing controlled change of the resulting surface potential. The junctions formed, upon contacting such surfaces with Hg, a metal that does not chemically interact with Si, follow the Schottky-Mott model formetal-semiconductor junctions closer than ever for Si-based junctions. Two examples of such ideal behavior are demonstrated: a) Tuning the molecular surface dipole over 400 mV, with only negligible band bending, by changing the alkyl chain length. Because of the excellent passivation this yields junctions with Hg with barrier heights that follow the change in the Si effective electron affinity nearly ideally. b) HQ/methanol passivation of Si is accompanied by a large surface dipole, which suffices, as interface dipole, to drive the Si into strong inversion as shown experimentally via its photovoltaic effect. With only similar to 0.3 nm molecular interlayer between the metal and the Si, our results proves that it is passivation and prevention of metal-semiconductor interactions that allow ideal metal-semiconductor junction behavior, rather than an insulating transport barrier. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.3694140]
The photovoltaic performance of solar cells, based on a Cu(In1-x Ga-x)Se-2 (CIGS) absorber layer, is directly correlated with Ga composition. We have used scanning capacitance microscopy and conducting probe atomic force microscopy (CP-AFM) to provide microscopic electrical characterization of CIGS films with different Ga content. We found p- to n-type inversion at grain boundaries of the polycrystalline CIGS film, especially for Ga-poor compositions. The fraction of grain boundaries undergoing inversion dramatically decreased for Ga compositions above x = 0.32, the composition corresponding to a sharp efficiency drop of the complete cells. CP-AFM measurements showed a marked current drop at grain boundaries as the Ga composition rose above x = 0.32.
Solid-state electron transport (ETp) via a monolayer of immobilized azurin (Az) was examined by conducting probe atomic force microscopy (CP-AFM), as a function of both temperature (248-373K) and applied tip force (6-15 nN). At low forces, Lip via holo-Az (with Cu2+) is temperature-independent, but thermally activated via the Cu-depleted form of Az, apo-Az. While this observation agrees with those of macroscopic-scale measurements, we find that for holo-Az the mechanism of Lip at high temperatures changes upon an increase in the force applied by the tip to the proteins; namely, above 310 K and forces >6 nN ETp becomes thermally activated. This is in contrast to apo-Az, where increasing applied force causes only small monotonic increases in currents due to decreased electrode separation. The distinct ETp temperature dependence of holo- and apo-Az is assigned to a difference in structural response to pressure between the two protein forms. An important implication of these CP-AFM results (of measurements over a significant temperature range) is that for reliable ETp measurements on flexible macromolecules, such as proteins, the pressure applied during the measurements should be controlled or at least monitored.
Electrons can migrate via proteins over distances that are considered long for nonconjugated systems. The nanoscale dimensions of proteins and their enormous structural and chemical flexibility makes them fascinating subjects for exploring their electron transport (ETp) capacity. One particularly attractive direction is that of tuning their ETp efficiency by "doping" them with small molecules. Here we report that binding of retinoate (RA) to human serum albumin (HSA) increases the solid-state electronic conductance of a monolayer of the protein by >2 orders of magnitude for RA/HSA >= 3. Temperature-dependent ETp measurements show the following with increasing RA/HSA: (a) The temperature-independent current magnitude of the low-temperature (300-fold), suggesting a decrease in the distance-decay constant of the process. (b) The activation energy of the thermally activated regime (>190 K) decreases from 220 meV (RA/HSA = 0) to 70 meV (RA/HSA >= 3).
Since the first report of Si-C bound organic monolayers on oxide-free Si almost two decades ago, a substantial amount of research has focused on studying the fundamental mechanical and electronic properties of these Si/molecule surfaces and interfaces. This feature article covers three closely related topics, including recent advances in achieving high-density organic monolayers (i.e., atomic coverage >55%) on oxide-free Si(111) substrates, an overview of progress in the fundamental understanding of the energetics and electronic properties of hybrid Si/molecule systems, and a brief summary of recent examples of subsequent functionalization on these high-density monolayers, which can significantly expand the range of applicability. Taken together, these topics provide an overview of the present status of this active area of research.
Solar cells based on crystalline semiconductors such as Si and GaAs provide nowadays the highest performance, but photovoltaic (PV) cells based on less pure materials, such as poly-or nano-crystalline or amorphous inorganic or organic materials, or a combination of these, should relax production requirements and lower the cost towards reliable, sustainable and economic electrical power from sunlight. So as to be able to compare the operation of different classes of solar cells we first summarize general photovoltaic principles and then consider implications of using less than ideal materials. In general, lower material purity means more disorder, which introduces a broad distribution of energy states of the electronic carriers that affects all the aspects of PV performance, from light absorption to the generation of voltage and current. Specifically, disorder penalizes energy output by enhanced recombination, with respect to the radiative limit, and also imposes a lowering of quasi-Fermi levels into the gap, which decreases their separation, i.e., reduces the photovoltage. In solar cells based on organic absorbers, such as dye-sensitized or bulk heterojunction solar cells, vibronic effects cause relaxation of carriers in the absorber, which implies an energy price in terms of obtainable output.
Freezing out of molecular motion and increased molecular tilt enhance the efficiency of electron transport through alkyl chain monolayers that are directly chemically bound to oxide-free Si. As a result, the current across such monolayers increases as the temperature decreases from room temperature to similar to 80 K, i.e., opposite to thermally activated transport such as hopping or semiconductor transport. The 30-fold change for transport through an 18-carbon long alkyl monolayer is several times the resistance change for actual metals over this range. FTIR vibrational spectroscopic measurements indicate that cooling increases the packing density and reduces the motional freedom of the alkyl chains by first stretching the chains and then gradually tilting the adsorbed molecules away from the surface normal. Ultraviolet photoelectron spectroscopy shows drastic sharpening of the valence band structure as the temperature decreases, which we ascribe to decreased electron-phonon coupling. Although conformational changes are typical in soft molecular systems, in molecular electronics they are rarely observed experimentally or considered theoretically. Our findings, though, indicate that the molecular conformational changes are a prominent feature, which imply behavior that differs qualitatively from that described by models of electronic transport through inorganic mesoscopic solids.
We compare the charge transport characteristics of heavy-doped p(++)- and n(++)-Si-alkyl chain/Hg junctions. Based on negative differential resistance in an analogous semiconductor-inorganic insulator/metal junction we suggest that for both p(++)- and n(++)-type junctions, the energy difference between the Fermi level and lowest unoccupied molecular orbital (LUMO), i.e., electron tunneling, controls charge transport. This conclusion is supported by results from photoelectron spectroscopy (ultraviolet photoemission spectroscopy, inverse photoelectron spectroscopy, and x-ray photoemission spectroscopy) for the molecule-Si band alignment at equilibrium, which clearly indicate that the energy difference between the Fermi level and the LUMO is much smaller than that between the Fermi level and the highest occupied molecular orbital (HOMO). Furthermore, the experimentally determined Fermi level - LUMO energy difference, agrees with the non-resonant tunneling barrier height, deduced from the exponential length attenuation of the current.
We demonstrate a solar cell that uses fixed negative charges formed at the interface of n-Si with Al2O3 to generate strong inversion at the surface of n-Si by electrostatic repulsion. Built-in voltages of up to 755mV are found at this interface. In order to harness this large built-in voltage, we present a photovoltaic device where the photocurrent generated in this inversion layer is extracted via an inversion layer induced by a high work function transparent organic top contact, deposited on top of a passivating and dipole-inducing molecular monolayer. Results of the effect of the molecular monolayer on device performance yield open-circuit voltages of up to 550mV for moderately doped Si, demonstrating the effectiveness of this contact structure in removing the Fermi level pinning that has hindered past efforts in developing this type of solar cell with n-type Si. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4769041]
Rapid changes in energy availability lead to the question of whether the sustainable availability of energy implies the sustainable availability of materials and vice versa. In particular, many researchers assume that materials can be produced from any resource type, irrespective of scarcity, by providing enough energy. We revisit this issue here for two reasons: (1) To avoid significant disruptions in daily life, no more than a few percent of total energy production and materials usage can be diverted to support a transition to new energy sources. (2) Such a transition could also be problematic if it requires large quantities of materials that are byproducts of other large-scale production cycles, as any increase in the production of a byproduct typically requires an almost proportional increase in the production of the primary product. In turn, increased production of the primary product could require materials and energy expenditures that are too large to be practical. Both limitations have to be taken into account in future energy planning.
Electron transport (ETp) across bacteriorhodopsin (bR), a natural proton pump protein, in the solid state (dry) monolayer configuration, was studied as a function of temperature. Transport changes from thermally activated at T > 200 K to temperature independent at
Good passivation of Si, both electrically and chemically, is achieved by monolayers of 1,9-decadiene, directly bound to an oxide-free Si surface. The terminal C=C bond of the decadiene serves for further in situ reaction, without harming the surface passivation, to -OH- or -Br-terminated monolayers that have different dipole moments. Such a two-step procedure meets the conflicting requirements of binding mutually repelling dipolar groups to a surface, while chemically blocking all surface reactive sites. We demonstrate a change of 0.15 eV in the Si surface potential, which translates into a 0.4 eV variation in the Schottky barrier height of a Hg junction to those molecularly modified n-Si surfaces. Charge transport across such junctions is controlled both by tunneling across the molecular monolayer and by the Si space charge. For reliable insight into transport details, we resorted to detailed numerical simulations, which reveal that the Si space charge and the molecular tunneling barriers are coupled. As a result, attenuation due to the molecular tunneling is much weaker than in metal/molecule/metal molecular junctions. Simulation shows also that some interface states are present but that they have a negligible effect on Fermi level pinning. These states are efficiently decoupled from the metal (Hg) and interact mostly with the Si.
Despite the rapid increase in solar cell manufacturing capacity (similar to 50 GW(p) in 2011), maintaining this continued expansion will require resolving some major fabrication issues. Crystalline Si, the most common type of cell, requires a large energy input in the manufacturing process, which results in an energy payback time of years. CdTe/CdS thin film cells, which have captured around 10% of the global market, may not be sustainable for very large-scale use because of limited Te availability. Thus, research in this field is emphasizing cells that are energy efficient and inexpensive and use readily available materials. The extremely thin absorber (ETA) cell, the subject of this Account, is one of these new generation cells. Since the active light absorber in an ETA cell is no more than tens of nanometers thick, the direct recombination of photogenerated electrons and holes in the absorber should not compete as much with charge removal in the form of photocurrent as in thicker absorber materials. As a result, researchers expect that poorer quality semiconductors can be used in an ETA cell, which would expand the choice of semiconductors over those currently in use. We first describe the ETA cell, comparing and contrasting it to the dye-sensitized cell (DSC) from which it developed and describing its potential advantages and disadvantages. We then explain the mechanism(s) of operation of the ETA cell, which remain controversial: different ETA cells most likely operate by different mechanisms, particularly in their photovoltage generation. We then present a general description of how we prepare ETA cells in our laboratory, emphasizing solution methods to form the various layers and solution treatments of these layers to minimize manufacturing costs. This is followed by a more specific discussion of the various layers and treatments used to make and complete a cell with emphasis on solution treatments that are important in optimizing cell performance and expla
2011
Understanding how quantum dot (QD)-sensitized solar cells operate requires accurate determination of the offset between the lowest-unoccupied molecular orbital (LUMO) of the sensitizer quantum dot and the conduction band of the metal oxide electrode. We present detailed optical spectroscopy, low-energy photoelectron spectroscopy, and two-photon photoemission studies of the energetics of size-selected CdSe colloidal QDs deposited on TiO2 electrodes. Our experimental findings show that in contrast to the prediction of simplified models based on bulk band offsets and effective mass considerations, band alignment in this system is strongly modified by the interaction between the QDs and the electrode. In particular, we find relatively small conduction band-LUMO offsets, and near "pinning" of the QD LUMO relative to the conduction band of the TiO2 electrode, which is explained by the strong QD-electrode interaction. That interaction is the origin for the highly efficient QD to electrode charge transfer, and it also bears on the possibility of hot carrier injection in these types of cells.
What are the solar cell effi ciencies that we can strive towards? We show here that several simple criteria, based on cell and module performance data, serve to evaluate and compare all types of today's solar cells. Analyzing these data allows to gauge in how far signifi cant progress can be expected for the various cell types and, most importantly from both the science and technology points of view, if basic bounds, beyond those known today, may exist, that can limit such progress. This is important, because half a century after Shockley and Queisser (SQ) presented limits, based on detailed balance calculations for single absorber solar cells, those are still held to be the only ones, we need to consider; most efforts to go beyond SQ are directed towards attempts to circumvent them, primarily via smart optics, or optoelectronics. After formulating the criteria and analyzing known loss mechanisms, use of such criteria suggests-additional limits for newer types of cells, Organic and Dye-Sensitized ones, and their siblings,-prospects for progress and-further characterization needs, all of which should help focusing research and predictions for the future.
Despite many recent research efforts, the influence of grain boundaries (GBs) on device properties of CuIn1-xGaxSe2 solar cells is still not fully understood Here, we present a microscopic approach to characterizing GBs in polycrystalline CuIn1-xGaxSe2 films with x = 0.33. On samples from the same deposition process we applied methods giving complementary information, i.e., electron backscatter diffraction (EBSD), electron-beam induced current measurements (EBIC), conductive atomic force microscopy (c-AFM), variable-temperature Kelvin probe force microscopy (KPFM), and scanning capacitance microscopy (SCM). By combining EBIC with EBSD, we find a decrease in charge-carrier collection for non-Sigma 3 GBs, while Sigma 3 GBs exhibit no variation with respect to grain interiors. In contrast, a higher conductance of GBs compared to grain interiors was found by c-AFM at low bias and under illumination. By KPFM, we directly measured the band bending at GBs, finding a variation from -80 up to +115 mV. Depletion and even inversion at GBs was confirmed by SCM. We comparatively discuss the apparent differences between the results obtained by various microscopic techniques. (C) 2011 Elsevier B.V. All rights reserved.
The electronic structure of the prototypical self-assembled monolayer (SAM) system, i.e. alkanethiol molecules on Au, is investigated via ultraviolet and inverse photoemission spectroscopy measurements. The determination of the density of filled and empty states of the system reveals that the metal Fermi level is significantly closer to the lowest unoccupied molecular orbital (LUMO) of the molecules than to their highest occupied molecular orbital (HOMO). The results suggest that charge carrier tunneling is controlled by the LUMO, rather than by the HOMO, in contrast to what is commonly assumed. (C) 2011 Elsevier B.V. All rights reserved.
We show that electronic transport quality alkyl chain monolayers can be prepared from dilute solution, rather than from neat alkanes, and on Si (100) instead of (111) surfaces. High monolayer quality was deduced from XPS and from comparing current-voltage curves of Hg/alkyl/Si junctions with those for junctions with monolayers made from neat alkanes. XPS shows that limited surface oxidation does not harm the integrity of the monolayer. Solution preparation significantly widens the range of molecules that can be used for transport studies.
The temperature dependence of current-voltage values of electron transport through proteins integrated into a solid-state junction has been investigated. These measurements were performed from 80 up to 400 K [above the denaturation temperature of azurin (Az)] using Si/Az/Au junctions that we have described previously. The current across the similar to 3.5 nm thick Az junction was temperature-independent over the complete range. In marked contrast, for both Zn-substituted and apo-Az (i.e., Cu-depleted Az), thermally activated behavior was observed. These striking temperature-dependence differences are ascribed to the pivotal function of the Cu ion as a redox center in the solid-state electron transport process. Thus, while Cu enabled temperature-independent electron transport, upon its removal the polypeptide was capable only of supporting thermally activated transport.
2010
Electron transfer (ET) through proteins, a fundamental element of many biochemical reactions, is studied intensively in aqueous solutions. Over the past decade, attempts were made to integrate proteins into solid-state junctions in order to study their electronic conductance properties. Most such studies to date were conducted with one or very few molecules in the junction, using scanning probe techniques. Here we present the high-yield, reproducible preparation of large-area monolayer junctions, assembled on a Si platform, of proteins of three different families: azurin (Az), a blue-copper ET protein, bacteriorhodopsin (bR), a membrane protein-chromophore complex with a proton pumping function, and bovine serum albumin (BSA). We achieve highly reproducible electrical current measurements with these three types of monolayers using appropriate top electrodes. Notably, the current-voltage (I-V) measurements on such junctions show relatively minor differences between Az and bR, even though the latter lacks any known ET function. Electron Transport (ETp) across both Az and bR is much more efficient than across BSA, but even for the latter the measured currents are higher than those through a monolayer of organic, C18 alkyl chains that is about half as wide, therefore suggesting transport mechanism(s) different from the often considered coherent mechanism. Our results show that the employed proteins maintain their conformation under these conditions. The relatively efficient ETp through these proteins opens up possibilities for using such biomolecules as current-carrying elements in solid-state electronic devices.
Using a semiconductor as the substrate to a molecular organic layer, penetration of metal contacts can be clearly identified by the study of electronic charge transport through the layer. A series of monolayers of saturated hydrocarbon molecules with varying lengths is assembled on Si or GaAs and the junctions resulting after further electronic contact is made by liquid Hg, indirect metal evaporation, and a "ready-made" metal pad are measured. In contrast to tunneling characteristics, which are ambiguous regarding contact penetration, the semiconductor surface barrier is very sensitive to any direct contact with a metal. With the organic monolayer intact, a metal insulator semiconductor (MIS) structure results. If metal penetrated the monolayer, the junction behaves as a metal semiconductor (MS) structure. By comparing a molecule-free interface (MS junction) with a molecularly modified one (presumably MIS), possible metal penetration is identified. The major indicators are the semiconductor electronic transport barrier height, extracted from the junction transport characteristics, and the photovoltage. The approach does not require a series of different monolayers and data analysis is quite straightforward, helping to identify non-invasive ways to make electronic contact to soft matter.
Molecular electronics is a flourishing area of nano-science and -technology, with a promise for cheap electronics of novel functionality. Here we outline the major challenges for molecular electronics becoming an established scientific discipline, including models with predictive power.
Molecular electronics is a flourishing area of nano-science and -technology, with a promise for cheap electronics of novel functionality. Here we outline the major challenges for molecular electronics becoming an established scientific discipline, including models with predictive power.
One of the major problems in molecular electronics is how to make electronically conducting contact to the "soft" organic and biomolecules without altering the molecules. As a result, only a small number of metals can be applied, mostly by special deposition methods with severe limitations. Transferring a predefined thin metal leaf onto a molecular layer provides a nondestructive, noninvasive contacting method that is, in principle, applicable to many types of metal and a variety of metal/molecules combinations. Here we report a modification of our earlier lift-off, float-on (LOFO) method, using as a basis its offspring, the polymer-assisted lift-off (PALO) method, where a backing polymer enables simultaneous deposition of multiple contacts as well as reduces wrinkles in the thin metal leaf. The modified PALO (MoPALO) method, reported here, adds lithography steps to obviate the need to punch through the polymer, as is done to complete PALO contacts. Morphological characterization of the electrodes indicates highly uniform, wrinkle-free contacts of negligible roughness. The good electrical performance of the MoPALO contacts was proven with metal/organic-monolayer/semiconductor (MOMS) junctions, which are known to be very sensitive to molecular degradation and metal penetration. We also show how MoPALO contacts enabled us to compare the effect of varying the metal work function and contact area on the current-voltage characteristics of MOMS devices.
Metal-organic molecule-semiconductor junctions are controlled not only by the molecular properties, as in metal-organic molecule-metal junctions, but also by effects of the molecular dipole, the dipolar molecule-semiconductor link, and molecule-semiconductor charge transfer, and by the effects of all these on the semiconductor depletion layer (i.e., on the internal semiconductor barrier to charge transport). Here, we report on and compare the electrical properties (current-voltage, capacitance-voltage, and work function) of large area Hg/organic monolayer-Si junctions with alkyl and alkenyl monolayers on moderately and highly doped n-Si, and combine the experimental data with simulations of charge transport and electronic structure calculations. We show that, for moderately doped Si, the internal semiconductor barrier completely controls transport and the attached molecules influence the transport of such junctions only in that they drive the Si into inversion. The resulting minority carrier-controlled junction is not sensitive to molecular changes in the organic monolayer at reverse and low forward bias and is controlled by series resistance at higher forward bias. However, in the case of highly doped Si, the internal barrier is smaller, and as a result, the charge transport properties of the junction are affected by changing from an alkyl to an alkenyl monolayer. We propose that the double bond near the surface primarily increases the coupling between the organic monolayer and the Si, which increases the current density at a given bias by increasing the contact conductance.
Basic scientific interest in using a semiconducting electrode in molecule- based electronics arises from the rich electrostatic landscape presented by semiconductor interfaces. Technological interest rests on the promise that combining existing semiconductor (primarily Si) electronics with (mostly organic) molecules will result in a whole that is larger than the sum of its parts. Such a hybrid approach appears presently particularly relevant for sensors and photovoltaics. Semiconductors, especially Si, present an important experimental test-bed for assessing electronic transport behavior of molecules, because they allow varying the critical interface energetics without out, to a first approximation, altering the interfacial chemistry. To investigate semiconductor-molecule electronics we need reproducible, high-yield preparations of samples that allow reliable and reproducible data collection. Only in that way can we explore how the molecule/electrode interfaces affect or even dictate charge transport, which may then provide a basis for models with predictive power. To consider these issues and questions we will, in this Progress Report, review junctions based on direct bonding of molecules to oxide-free Si. describe the possible charge transport mechanisms across such interfaces and evaluate in how far they can be quantified. investigate to what extent imperfections in the monolayer are important for transport across the monolayer. revisit the concept of energy levels in such hybrid systems.
Studying solid-state electronic conductance of biological molecules requires interfacing the biomolecules with electronic conductors without altering the molecules. To this end, we developed and present here a simple, solution-based approach of conjugating Bacteriorhodopsin (bR)-containing membranes with metallic clusters. Our approach is based on selective electroless deposition of Pt nanoparticles on suspended membrane fragments through chemical interaction of the Pt precursor with the protein's residues. Optical absorption measurements show that the membranes retain their photoactivity after this procedure. The result of the Pt deposition is best shown by conductive probe atomic force microscopy mapping of electronic current transport across such soft biological layers, which allows reproducible microscopic electrical characterization of the electronic conductance of the resulting junctions. The maps show that chemical contact between the protein and the deposited electrode yields better electronic coupling than a physical contact, demonstrating that also with biomolecules, the type and method of deposition of the electrical contact are critical to the behavior of the resulting junctions.
Protein structures can facilitate long-range electron transfer in solution. But a fundamental question remains: can these structures also serve as solid-state electronic conductors? Answering this question requires methods for studying conductivity of the "dry" protein (which only contains tightly bound structured water molecules) sandwiched between two electronic conductors in a solid-state type configuration. If successful, such systems could serve as the basis for future, bioinspired electronic device technology. In this Account, we survey, analyze, and compare macroscopic and nanoscopic (scanning probe) solid-state conductivities of proteins, noting the inherent constraints of each of these, and provide the first status report on this research area. This analysis shows convincing evidence that "dry" proteins pass orders of magnitude higher currents than saturated molecules with comparable thickness and that proteins with known electrical activity show electronic conductivity, nearly comparable to that of conjugated molecules ("wires"). These findings suggest that the structural features of proteins must have elements that facilitate electronic conductivity, even if they do not have a known electron transfer function. As a result, proteins could serve not only as sensing, polar,or photoactive elements in devices (such as field-effect transistor configurations) but also as electronic conductors. Current knowledge of peptide synthesis and protein modification paves the way toward a greater understanding of how changes in a protein's structure affect its conductivity. Such an approach could minimize the need for biochemical cascades in systems such as enzyme-based circuits, which transduce the protein's response to electronic current. In addition, as precision and sensitivity of solid-state measurements increase, and as knowledge of the structure and function of "dry" proteins grows, electronic conductivity may become an additional approach to study electron tran
2009
Alkyl chain molecules on n-Si were used to test the concept of hybrid metal-organic insulator-semiconductor (MOIS) solar cells. Test structures were made by binding alkyl chain molecules via Si-O-C bonds to oxide-free n-Si surfaces, using self-assembly. With thiol groups at the terminals away from the Si, binding of Au nanoparticles, followed by electroless Au plating yields semitransparent top contacts. First cells give, under 25 mW/cm(2) white light illumination, open-circuit voltage V(oc)=0.48 V and fill factor FF=0.58. Because with sulfur termination the molecules have a dipole that limits inversion of the Si, we also used methyl-terminated monolayers. Even though then we can work, at this point, only with a Hg top contact, without chemical bond to the molecules, we get, using only radiation (similar to AM 1.5) collected around the contact, the expected higher V(oc)=0.54 V, and respectable 0.8 FF, justifying further MOIS cell development.
Bromine-terminated alkyl-chain monolayers, bound to oxide-free Si substrates, were prepared by self-assembly. Infrared spectroscopy and atomic force microscopy imply that monolayer packing density improves after hydrolysis, despite an increase in the presence of oxide. The probable reason is that OH-mediated intermolecular H-bonding along the monolayer emerges after hydrolysis and rearranges the molecular components of the insulating layer. Current-voltage and differential capacitance measurements show that also the interfacial electronic properties of these junctions are changed by hydrolysis of the Br groups. This is expressed in an increased effective Schottky barrier height and a decreased junction ideality factor. We correlate the proposed structural changes of the monolayer with the change in the interfacial electronic properties, with the help of the inhomogeneous Schottky barrier height model. The role of oxide in the charge transport through the monolayer is discussed, as well.
A low-cost dichroic mirror can be used successfully for solar spectrum splitting to enhance solar to electrical energy conversion. The mirror is optimized for use with a polycrystalline silicon photovoltaic cell (pc-Si). With the dichroic mirror simultaneous excitation of a medium-efficient (11.1%) commercial pc-Si and a custom-made high band gap GaInP cell (12.3%), yields 16.8% efficiency, with both cells operating at maximum power. Our results clearly show that what is missing for this simple low-cost enhancement of Si solar cell efficiency are low-cost high band gap cells. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3081510]
We report on electronic transport measurements through dense monolayers of CH(3)(CH(2))(n)PO(3)H(2) molecules of varying chain lengths, with a strong and stable bond through the phosphonic acid end group to a <100 > GaAs surface and a Hg top contact. The monolayers maintain their high quality during and after the electrical measurements. Analyses of the electronic transport measurements of junctions, and of UV and inverse photoemission spectroscopy data on band alignments of free surfaces, yield insight about the electrical transport mechanism. Transport characteristics for n-GaAs junctions at low forward bias are identical for different chain lengths, a strong indication of high-quality monolayers. Tunneling barrier and carrier effective mass values for n- and p-GaAs samples were deduced from the transport data. In this way we find a tunneling barrier for n-GaAs of 1.3 eV, while UPS data for the lowest unoccupied system orbital (LUSO) point to a 2.4 eV barrier. This discrepancy can be understood by invoking states, closer to the Fermi level than the LUSO state, that contribute to charge transport. Such states lead to a manifold of transitions, each having a different probability, both because of differences in the tunnel barrier and because of differences in density of these interface-induced states; i.e., the single barrier, deduced from J-V measurements, is an effective value only.
Electronic transport across n-Si-alkyl monolayer/Hg junctions is, at reverse and low forward bias, independent of alkyl chain length from 18 down to 1 or 2 carbons! This and further recent results indicate that electron transport is minority, rather than majority carrier dominated, occurs via generation and recombination, rather than (the earlier assumed) thermionic emission, and, as such, is rather insensitive to interface properties. The (m)ethyl results show that binding organic molecules directly to semiconductors provides semiconductor/metal interface control options, not accessible otherwise.
We demonstrate an extremely thin absorber (ETA) solar cell using a copper sulfide (Cu(2-x)S) light absorber. We compare the cell performance with that of a CdS absorber, to demonstrate the potential and the challenges associated with using low-cost, low-band gap absorber materials to fully exploit the thin-absorber concept.
The electronic band structure of different alkyl/Si(111) self-assembled monolayers (SAMs) was investigated using photoelectron spectroscopy (PES) with variable photon energy. We observe a significant dispersion in the valence-band spectra and a large density-of-states (DOS) effect. The dispersion can be described by quantum well states, which depend only on the local properties of the alkanes with a dispersion relation similar to polyethylene and without any significant influence of the Si/molecule interface. Furthermore, the DOS effect is due to averaging over molecules with different tilt angles and thus can be considered as indicator for the degree of orientational order within the SAM. Finally we present a structural model for a description of the PES data, which takes both aspects into account.
2008
After some definitions to establish common ground and illustrate the issues in terms of orders of magnitude, we note that meeting the Energy challenge will require suitable materials. Luckily, we can count on the availability of natural resources for most materials. We briefly illustrate the connection between materials and energy and review the past and the present situations, to focus on the future. We wrap up by arguing that more than bare economics is required to use the fruits of science and technology towards a world order, built an sustainable energy band materials resources.
Using a dense organic monolayer, self-assembled and directly bount to n-Si, as high quality insulator with a thickness that can be varied from 1.5-2.5 nm, we construct a Metal-organic Insulator-Semiconductor (MOIS) structure, which, if fabricated with semi-transparent top electrode, performs as ahybrid organic-inorganic photovoltaic device. The feasibility of the concept and the electrical properties of the insulating layer were first shown with a Hg top electrode, allowing use of prior know-how from electron transport through molecular monolayers, but with photon collection only from around the electrode. We then used another bottom-up fabrication technique, in addition to molecular self-deposition yields an electrically continuous, porous and semi-transparent top electrode, improving photon harvesting. Aside form being a nearly ideal insulator, the monolayer acts to passivate and protect the interfacial Si layer from defects and to decrease the surface state density. In addition the cell, like any MIS solar cell, benefits from that the light needs only to cross a few thin transparent layers (anti-reflective coating, organic insulator) to reach the photovoltaically active cell part. This helps to generate carriers close to the junction area, even by short wavelength photons, and, thus, to increase light collection, compared to p-n junction solar cells. While probably the most important use of MOIS cells will be to allow systematic exploration of directions for general MIS solar cell optimization, low temperature cell fabrication without high vaccum steps, may make this approach also interesting for low cost solar cells.
Photon up-conversion (UC) and photon-induced multiple-exciton generation (MEG) are proposed directions that are of increasing interest for improving photovoltaic (PV) conversion efficiencies via "photon (or light) management". Straightforward analysis of these approaches for non-concentrated single-junction cells in the detailed balance limit yields a theoretical PV conversion limit of 49%, instead of 31% without UC and MEG. With what we estimate to be optimistic, maximal realistic efficiencies (25% for UC; 70% for MEG) this limit becomes
Can we put organic molecules to use as electronic components? The answer to this question is to no small degree limited by the ability to contact them electrically without damaging the molecules. In this Account, we present some of the methods for contacting molecules that do not 14 or minimally damage them and that allow formation of electronic junctions that can become compatible with electronics from the submicrometer to the macroscale. In "Linnaean" fashion, we have grouped contacting methods according to the following main criteria: (a) is a chemical bond is required between contact and molecule, and (b) is the contact "ready-made", that is, preformed, or prepared in situ? Contacting methods that, so far, seem to require a chemical bond include spin-coating a conductive polymer and transfer printing. In the latter, a metallic pattern on an elastomeric polymer is mechanically transferred to molecules with an exposed terminal group that can react chemically with the metal. These methods allow one to define structures from several tens of nanometers size upwards and to fabricate devices on flexible substrates, which is very difficult by conventional techniques. However, the requirement for bifunctionality severely restricts the type of molecules that can be used and can complicate their self-assembly into monolayers. Methods that rely on prior formation of the contact pad are represented. by two approaches: (a) use of a liquid metal as electrode (e.g., Hg, Ga, various alloys), where molecules can be adsorbed on the liquid metal and the molecularly modified drop is brought into contact with the second electrode, the molecules can be adsorbed on the second electrode and then the liquid metal brought into contact with them, or bilayers are used, with a layer on both the metal and the second electrode and (b) use of preformed metal pads from a solid substrate and subsequent pad deposition on the molecules with the help of a liquid. These methods allow formation of
Introducing organic molecules in electronics, in general, and as active electronic transport components, in particular, is to no small degree limited by the ability to connect them electrically to the outside world. Making useful electrical contacts to them requires achieving this either without altering the molecules, or if they are affected, then in a controlled fashion. This is not a trivial task because most known methods to make such contacts are likely to damage the molecules. In this progress report we review many of the various ways that have been devised to make electrical contacts to molecules with minimal or no damage. These approaches include depositing the electronic conducting contact material directly on the molecules, relying on physical interactions, requiring chemical bond formation between molecule and electrode materials, "ready-made" contacts (i.e., contact structures that are prepared in advance), and contacts that are prepared in situ. Advantages and disadvantages of each approach, as well as the possibilities that they can be used practically, are discussed in terms of molecular reactivity, surface and interfacial science. (C) 2008 Elsevier Ltd. All rights reserved.
n-Si/C,,H2n + /Hg junctions (n = 12, 14, 16 and 18) can be prepared with sufficient quality to assure that the transport characteristics are not anymore dominated by defects in the molecular monolayers. With such organic monolayers we can, using electron, UV and X-ray irradiation, alter the charge transport through the molecular junctions on n- as well as on p-type Si. Remarkably, the quality of the self-assembled molecular monolayers following irradiation remains sufficiently high to provide the same very good protection of Si from oxidation in ambient atmosphere as provided by the pristine films. Combining spectroscopic (UV photoemission spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), Auger, near edge-X-ray absorption fine structure (NEXAFS)) and electrical transport measurements, we show that irradiation induces defects in the alkyl films, most likely C=C bonds and C-C crosslinks, and that the density of defects can be controlled by irradiation dose. These altered intra- and intermolecular bonds introduce new electronic states in the highest occupied molecular orbital (HOMO)lowest unoccupied molecular orbital (LUNIO) gap of the alkyl chains and, in the process, dope the organic film. We demonstrate an enhancement of 1-2 orders of magnitude in current. This change is clearly distinguishable from the previous observed difference between transport through high quality and defective monolayers. A detailed analysis of the electrical transport at different temperatures shows that the dopants modify the transport mechanism from tunnelling to hopping. This study suggests a way to extend significantly the use of monolayers in molecular electronics.
Molecular electronics is very much about contacts, and thus understanding of any generic contact effect is essential to its advance. For example, it is still not obvious in how far variations in electrode roughness of macroscopic contacts can lead to rectification. Here we report an investigation of this contact effect on electronic transport properties using metal-insulator-metal planar junctions with a 5 nm thick bacteriorhodopsin-based insulator as model system. We demonstrate that the experimentally observed rectifying behavior is not an intrinsic property of the molecules used, but rather of the local contact quality. Even a slight increase in surface roughness of the bottom electrode gives rise to distinct rectifying behavior in. these and, by extrapolation, possibly other molecular junctions.
Temperature-depen dent transport measurements through alkyl chain monolayers that are directly chemically bound to Si, show that the currents decrease as the temperature increases. We relate this temperature dependence primarily to a gradual un-tilting of the adsorbed molecules, which leads to increasing of the film thickness, resulting in a wider tunnel barrier. Following that, we conclude that a significant part of transport through these alkyl chain monolayers occurs "through space". The experimental finding and its interpretation result from the high reproducibility and accuracy of the transport results for the semiconductor/alkyl chain/ metal junctions that we study.
Controlling the orientation of bacteriorhodopsin (bR) monolayers is an important step in studying and utilizing such membranes in a solid-state configuration in., for example, photoelectric applications. Macroscopic monolayers of bR have been fabricated in a variety of ways, but characterization of the distribution of the two possible orientations in which the membrane fragments can adsorb has not yet been addressed experimentally. Here, an approach is presented that labels only one of the membrane surfaces by electroless growth of metal nanoparticles on top of the solid-supported membranes. In, this way, it is possible to observe which surface of the membranes is actually adsorbed to the substrate. How this technique serves to interface the membranes with a top metal contact for further electrical measurements is also demonstrated.
Electronic current transport through alkoxy and alkyl monolayer-based junctions is presented. Monolayers are prepared on n-Si(100) with sufficiently high quality to reliably investigate the actual molecular effect of each monolayer on their current-voltage characteristics. The results show that extending the Si-binding chemistry from alkene to alcohol is feasible which should significantly facilitate preparation of monolayers with modified molecules.
The interfacing of functional proteins with solid supports and the study of related protein-adsorption behavior are promising and important for potential device applications. In this study, we describe the preparation of bacteriorhodopsin (bR) monolayers on Br-terminated solid supports through covalent attachment. The bonding, by chemical reaction of the exposed free amine groups of bR with the pendant Br group of the chemically modified solid surface, was confirmed both by negative AFM results obtained when acetylated bR (instead of native bR) was used as a control and by weak bands observed at around 1610 cm(-1) in the FTIR spectrum. The coverage of the resultant bR monolayer was significantly increased by changing the pH of the purple-membrane suspension from 9.2 to 6.8. Although bR, which is an exceptionally stable protein, showed a pronounced loss of its photoactivity in these bR monolayers, it retained full photoactivity after covalent binding to Br-terminated alkyls in solution. Several characterization methods, including atomic force microscopy (AFM), contact potential difference (CPD) measurements, and UV/Vis and Fourier transform infrared (FTIR) spectroscopy, verified that these bR monolayers behaved significantly different from native bR. Current-voltage (I-V) measurements (and optical absorption spectroscopy) suggest that the retinal chromophore is probably still present in the protein, whereas the UV/Vis spectrum suggests that it lacks the characteristic covalent protonated Schiff base linkage. This finding sheds light on the unique interactions of biomolecules with solid surfaces and may be significant for the design of protein-containing device structures.
Interfacing functional proteins with solid supports for device applications is a promising route to possible applications in bio-electronics, -sensors, and -optics. Various possible applications of bacteriorhodopsin (bR) have been explored and reviewed since the discovery of bR. This tutorial review discusses bR as a medium for biomolecular optoelectronics, emphasizing ways in which it can be interfaced, especially as a thin film, solid-state current-carrying electronic element.
2007
Electron irradiation can alter electronic charge transport through Si-CH2(CH2)(12)-CH3//Hg molecular junctions. Applying UPS, XPS, Auger, NEXAFS, and electrical transport measurements, we show that irradiation induces defects, most likely CC bonds and C-C cross-links, which introduce new electronic states into the HOMO-LUMO gap of the alkyl chains, and, hence, effectively dope these layers. We demonstrate a 1-2 order of magnitude enhancement in current, clearly distinguishable from that of defects in as-prepared layers.
How alkyl chain molecules are bound chemically to GaAs directly affects current transport through GaAs/Alkyl/Hg junctions. We used two different binding groups, thiols that form an As-S bond and phosphonates with the much stronger Ga-O (actually Ga-O-P) bond. Analyzing transport through the junctions as tunneling through a dielectric medium of defined thickness, characterized by one barrier and the effective mass of the electronic carrier, we find the main difference in the electronic properties between the two systems to be the effective mass, 1.5-1.6 m(e) with thiols and 0.3 m(e) with phosphonates. The latter value is similar to that found with, or predicted for, other systems. We ascribe this difference primarily to less scattering of carriers by the Ga-O than by the As-S interface.
By combining experimental electron-transport results through an alkane monolayer sandwiched between Si and a metal, photoemission data from the monolayer-on-Si, and theoretical calculations, we show that transport is dominated by a distribution of mixed Si molecular levels, rather than a single molecular level, as shown schematically in the figure.
We show that electron beam evaporation of metal onto a monolayer of organic molecules can yield reproducible electrical contacts, if evaporation is indirect and the sample is on a cooled substrate. The metal contact forms without damaging even the molecules' outermost groups. In contrast, direct evaporation seriously damages the molecules. By comparing molecular effects on metal/molecular layer/GaAs junctions, prepared by indirect evaporation and by other soft contacting methods, we confirm experimentally that An is not an optimal choice as an evaporated contact metal. We ascribe this to the ease by which Au can diffuse between molecules, something that can, apart from direct contact- substrate connections, lead to undesired and uncontrollable interfacial interactions. Such phenomena are largely absent with Pd as evaporated contact.
A reliable and reproducible method for preparing bacteriorhodopsin (bR)-containing metal-biomolecule-monolayer-metal planar junctions via vesicle fusion tactics and soft deposition of Au top electrodes is reported. Optimum monolayer and junction preparations, including contact effects, are discussed. The electron-transport characteristics of bR-containing membranes are studied systematically by incorporating native bR or artificial bR pigments derived from synthetic retinal analogues, into single solid-supported lipid bilayers. Current-voltage (I-V) measurements at ambient conditions show that a single layer of such bR-containing artificial lipid bilayers pass current in solid electrode/bilayer/solid electrode structures. The current is passed only if retinal or its analogue is present in the protein. Furthermore, the preparations show photoconductivity as long as the retinal can isomerize following light absorption. Optical characterization suggests that the junction photocurrents might be associated with a photochemically induced M-like intermediate of bR. I-V measurements along with theoretical estimates reveal that electron transfer through the protein is over four orders of magnitude more efficient than what would be estimated for direct tunneling through 5 nm of water-free peptides. Our results furthermore suggest that the light-driven proton-pumping activity of the sandwiched solid-state bR monolayer contributes negligibly to the steady-state light currents that are observed, and that the orientation of bR does not significantly affect the observed I-V characteristics.
Local electrical transport measurements with scanning probe microscopy on polycrystalline (PX) p-CuInSe2 and p-Cu(In,Ga)Se-2 films show that the photovoltaic and dark currents for bias voltages smaller than 1 V flow mainly through grain boundaries (GBs), indicating inversion at the GBs. Photocurrent for higher bias flows mainly via the grains. Based on these results and our finding of similar to 100 meV GB band bending we deduce the potential landscape around the GBs. We suggest that high grain material quality, leading to large carrier mobilities, and electron-hole separation at the GBs, by chemical and electrical potential gradients, result in the high performance of these PX solar cells. (c) 2006 Elsevier B.V. All rights reserved.
Self-assembled monolayers formed by thermal hydrosilylation of a trifluoroacetyl-protected alkenylthiol on Si-H surfaces, followed by removal of the protecting groups, yield essentially oxide-free monolayers suitable for the formation of Si-C11H22-S-Hg and Si-C11H22-S-Au junctions in which the alkyl chains are chemically bound to the silicon surface (via Si-C bonds) and the metal electrode (via Hg-S or Au-S bonds). Two barriers to charge transport are present in the system: at low bias the current is temperature activated and hence limited by thermionic emission over the Schottky barrier in the silicon, whereas as at high bias transport is limited by tunneling through the organic monolayer. The thiol-terminated monolayer on oxide-free silicon provides a well-characterized system allowing a careful study of the importance of the interfacial bond to the metal electrode for current transport through saturated molecules.
2006
We study how partial monolayers of molecular dipoles at semiconductor/metal interfaces can affect electrical transport across these interfaces, using a series of molecules with systematically varying dipole moment, adsorbed on n-GaAs, prior to Au or Pd metal contact deposition, by indirect evaporation or as "ready-made" pads. From analyses of the molecularly modified surfaces, we find that molecular coverage is poorer on low-than on high-doped n-GaAs. Electrical charge transport across the resulting interfaces was studied by current-voltage-temperature, internal photoemission, and capacitance-voltage measurements. The data were analyzed and compared with numerical simulations of interfaces that present inhomogeneous barriers for electron transport across them. For high-doped GaAs, we confirm that only the former, molecular dipole-dependent barrier is found. Although no clear molecular effects appear to exist with low-doped n-GaAs, those data are well explained by two coexisting barriers for electron transport, one with clear systematic dependence on molecular dipole (molecule-controlled regions) and a constant one (molecule-free regions, pinholes). This explains why directly observable molecular control over the barrier height is found with high-doped GaAs: there, the monolayer pinholes are small enough for their electronic effect not to be felt (they are "pinched off"). We conclude that molecules can control and tailor electronic devices need not form high-quality monolayers, bind chemically to both electrodes, or form multilayers to achieve complete surface coverage. Furthermore, the problem of stability during electron transport is significantly alleviated with molecular control via partial molecule coverage, as most current flows now between, rather than via, the molecules.
We elucidate the electronic structure of both filled and empty states of ordered alkyl chains bound to the Si(111) surface by combining direct and inverse photoemission spectroscopy with first principles calculations based on density functional theory. We identify both filled and empty interface-induced gap states, distinguish between those and states extending throughout the monolayer, and discuss the importance of these findings for interpreting transport experiments through such monolayers.
We study the effect of monolayer quality on the electrical transport through n-Si/CnH2n+1/Hg junctions ( n = 12, 14, and 18) and find that truly high quality layers and only they, yield the type of data, reported by us in Phys. ReV. Lett. 2005, 95, 266807, data that are consistent with the theoretically predicted behavior of a Schottky barrier coupled to a tunnel barrier. By using that agreement as our starting point, we can assess the effects of changing the quality of the alkyl monolayers, as judged from ellipsometer, contact angle, XPS, and ATR-FTIR measurements, on the electrical transport. Although low monolayer quality layers are easily identified by one or more of those characterization tools, as well as from the current-voltage measurements, even a combination of characterization techniques may not suffice to distinguish between monolayers with minor differences in quality, which, nevertheless, are evident in the transport measurement. The thermionic emission mechanism, which in these systems dominates at low forward bias, is the one that is most sensitive to monolayer quality. It serves thus as the best quality control. This is important because, even where tunneling characteristics appear rather insensitive to slightly diminished quality, their correct analysis will be affected, especially if layers of different lengths are also of different quality.
Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO(2), are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation-or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi* resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.
We show that the electrode/molecule chemical bond does not change the tunneling barrier for charge transport through alkyl chain monolayers sandwiched between Si and Hg electrodes. This observation can be understood if the interfacial bond mainly governs the monolayer's structure, while the electronic states due to molecule-electrode bonding do not contribute significantly to tunneling. Yet, the nature of the bond affects the Schottky barrier inside the semiconductor due to changes in the interface dipole.
Acetylation of purple membranes ( PM) significantly enhances the surface photovoltage that they exhibit, if adsorbed as a monolayer on a solid surface; we suggest that this increase is due to the improved orientation of the PM on the surface.
CdSe is homogeneously deposited into nanoporous TiO2 films and used in liquid junction photoelectrochemical solar cells. The effect of the deposition parameters on the cell are studied, in particular differences between ion-by-ion and cluster deposition mechanisms. CdSe deposition on a Cd-rich US film that was deposited first into the TiO2 film, or selenization of the Cd-rich CdS layer with selenosulphate solution improves the cell parameters. Photocurrent spectral response measurements indicate photocurrent losses due to poor collection efficiencies, as shown by the strong spectral dependence on illumination intensity. Cell efficiencies up to 2.8% under solar conditions have been obtained. (c) 2006 Elsevier B.V. All rights reserved.
A series of p- and n- GaAs- S- C(n)H(2)n(+1) vertical bar vertical bar Hg junctions are prepared, and the electronic transport through them is measured. From current-voltage measurements, we find that, for n- GaAs, transport occurs by both thermionic emission and tunneling, with the former dominating at low forward bias and the latter dominating at higher forward bias. For p- GaAs, tunneling dominates at all bias voltages. By combining the analysis of the transport data with results from direct and inverse photoemission spectroscopy, we deduce an energy band diagram of the system, including the tunnel barrier and, with this barrier and within the Simmons tunneling model, extract an effective mass value of 1.5 - 1.6me for the electronic carriers that cross the junctions. We find that transport is well- described by lowest unoccupied and highest occupied states at 1.3 - 1.4 eV above and 2.0 - 2.2 eV below the Fermi level. At the same time, the photoemission data indicate that there are continua of states from the conduction band minimum and the valence band maximum, the density of which varies with energy. On the basis of our results, it appears likely that, for both types of junctions, electrons are the main carrier type, although holes may contribute significantly to the transport in the p- GaAs system.
A dipole-layer approach is adapted to describe the electrostatic potential and electronic transport through metal/semiconductor junctions with a discontinuous monolayer of polar molecules at the metal/semiconductor interface. The effective barrier height of those junctions, which have small pinholes, embedded in a molecular layer, which introduces a negative {positive} dipole (i.e., a dipole whose negative {positive} pole is the one that is closest to the semiconductor surface) on an n-type {p-type} semiconductor, is often "tunable" by the magnitude and density of the dipoles. If the lateral dimensions of a molecule-free pinhole at the interface exceed the semiconductor depletion width, carrier transport is not influenced by the molecular layer and the "effective" barrier height is the nominal metal/semiconductor barrier height. If the molecular layer introduces a positive {negative) dipole on an n-type {p-type) semiconductor, enhanced field emission at edges of small pinholes might lead to a leakage- and/or an edge-current component resulting in an effective barrier height lower than the nominal one. We support these conclusions by direct measurements of the nm-scale electronic behaviour of a Au/n-GaAs diode with a discontinuous monolayer of dicarboxylic acids at the interface, using Ballistic Electron Emission Microscopy (BEEM). (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Studying electron transport (ET) through proteins is hampered by achieving reproducible experimental configurations, particularly electronic contacts to the proteins. The transmembrane protein bacteriorhoclopsin (bR), a natural light-activated proton pump in purple membranes of Halobacterium salinarum, is well studied for biomolecular electronics because of its sturdiness over a wide range of conditions. To date, related studies of dry bR systems focused on photovoltage generation and photoconduction with multilayers, rather than on the ET ability of bR, which is understandable because ET across 5-nm-thick, apparently insulating membranes is not obvious. Here we show that electronic current passes through bR-containing artificial lipid bilayers in solid "electrode-bilayer-electrode" structures and that the current through the protein is more than four orders of magnitude higher than would be estimated for direct tunneling through 5-nm, water-free peptides. We find that ET occurs only if retinal or a close analogue is present in the protein. As long as the retinal can isomerize after light absorption, there is a photo-ET effect. The contribution of light-driven proton pumping to the steady-state photocurrents is negligible. Possible implications in view of the suggested early evolutionary origin of halobacteria are noted.
The superior performance of certain polycrystalline (PX) solar cells compared to that of corresponding single-crystal ones has been an enigma until recently. Conventional knowledge predicted that grain boundaries serve as traps and recombination centers for the photogenerated carriers, which should decrease cell performance. To understand if cell performance is limited by grain bulk, grain surface, and/or grain boundaries (GBs), we performed high-resolution mapping of electronic properties of single GBs and grain surfaces in PX p-CdTe/n-CdS solar cells. Combining results from scanning electron and scanning probe microscopies, viz., capacitance, Kelvin probe, and conductive probe atomic force microscopies, and comparing images taken under varying conditions, allowed elimination of topography-related artifacts and verification of the measured properties. Our experimental results led to several interesting conclusions: 1) current is depleted near GBs, while photocurrents are enhanced along the GB cores; 2) GB cores are inverted, which explains GB core conduction. Conclusions (1) and (2) imply that the regions around the GBs function as an extension of the carrier-collection volume, i.e., they participate actively in the photovoltaic conversion process, while conclusion (2) implies minimal recombination at the GB cores, 3) the surface potential is diminished near the GBs; and 4) the photovoltaic and metallurgical junction in the n-CdS/p-CdTe devices coincide. These conclusions, taken together with gettering of defects and impurities from the bulk into the GBs, explain the good photovoltaic performance of these PX cells (at the expense of some voltage loss, as is indeed observed). We show that these CdTe GB features are induced by the CdCl2 heat treatment used to optimize these cells in the production process.
2005
The effect of surface treatments on p-CdTe/n-CdS solar cell performance was examined. Adsorption of organic molecules with various magnitudes and directions of the dipole moment on p-CdTe resulted in controlled changes in electron affinity and surface bond bending. Similar adsorption on CdTe in state-of-the-art p-CdTe/n-CdS solar cells changes the cell performance, and we explain this by a combination of increased series resistance and changes in light absorption and in cell photovoltoge. While at this stage no improvement in performance has been found with these cell structures, which are the result of years of empirical optimization, the molecular effect on the photovoltoge shows that it is possible in this way to control the photovoltaic effect at this junction. Separate optimization may well lead to improvement by inserting a dipole layer near the photovoltaic interface. Our results also show that this is even possible when dipole adsorption is performed on the complete polycrystalline thin-film cell.
Molecular modification of dye-sensitized, mesoporous TiO2 electrodes changes their electronic properties. We show that the open-circuit voltage (V-oc) of dye-sensitized solar cells varies linearly with the dipole moment of coadsorbed phosphonic, benzoic, and dicarboxylic acid derivatives. A similar dependence is observed for the short-circuit current density (I-sc). Photovoltage spectroscopy measurements show a shift of the signal onset as a function of dipole moment. We explain the dipole dependence of the V-oc in terms of a TiO2 conduction band shift with respect to the redox potential of the electrolyte, which is partially followed by the energy level of the dye. The I-sc shift is explained by a dipole-dependent driving force for the electron current and a dipole-dependent recombination current.
Well-oriented monolayers of bacteriorhodopsin(bR)-containing purple-membrane patches are prepared on solid substrates (see Figure). Green-light illumination completely converts wild-type bR to the blue-light-absorbing M state, even at high humidity and pH 7. The possibility of bR-based optoelectronic devices is significantly enhanced by systems comprised of the long-lived M state, thus underlying the importance of this work.
Indirect e-beam evaporation of metal on a cooled substrate that allows making reproducible and gentle electrical contact to molecular films of organic molecules yields strikingly different results with Pd and Au. This is attributed to different growth modes of the metals, which lead to different molecule/metal interactions and to Au penetration in between the molecules. These differences can radically change the effect of the molecules on the resulting junctions. (C) 2005 American Institute of Physics.
Transport of charge carriers through interfaces is crucial to all electronic and optoelectronic devices, in particular devices based on organic molecular films and, especially, monomolecular layers and single molecules. The energetics of molecular interfaces are exceedingly important, therefore, and must be understood in detail so that we can model and control their behavior. This knowledge, however, is not always sufficient, as the very physics of charge carrier transport through molecular interfaces remains, at times, unclear. This article provides an overview of the main issues being researched actively in the field of interfaces involving organic molecules, and points out areas where progress has been made and where basic questions remain unanswered.
Electron transport through Si-C bound alkyl chains, sandwiched between n-Si and Hg, is characterized by two distinct types of barriers, each dominating in a different voltage range. At low voltage, the current depends strongly on temperature but not on molecular length, suggesting transport by thermionic emission over a barrier in the Si. At higher voltage, the current decreases exponentially with molecular length, suggesting transport limited by tunneling through the molecules. The tunnel barrier is estimated, from transport and photoemission data, to be similar to 1.5 eV with a 0.25m(e) effective mass.
Diodes made by (indirectly) evaporating An on a monolayer of molecules that are adsorbed chemically onto GaAs, via either disulfide or dicarboxylate groups, show roughly linear but opposite dependence of their effective barrier height on the dipole moment of the molecules. We explain this by Au-molecule (electrical) interactions not only with the exposed end groups of the molecule but also with its binding groups. We arrive at this conclusion by characterizing the interface by in situ UPS-XPS, ex situ XPS, TOF-SIMS, and Kelvin probe measurements, by scanning microscopy of the surfaces, and by current-voltage measurements of the devices. While there is a very limited interaction of Au with the dicarboxylic binding groups, there is a much stronger interaction with the disulfide groups. We suggest that these very different interactions lead to different (growth) morphologies of the evaporated gold layer, resulting in opposite effects of the molecular dipole on the junction barrier height.
Two-dimensional arrangements of molecules can show remarkable cooperative electronic 1771 effects. Such effects can serve to achieve direct electronic sensing of chemical and physical processes via electrostatic effects, i.e., without transfer of charge or matter between the locus of sensing and that of detection.
2004
A contact-free method to measure the photovoltage that can be generated by an absorber, upon illumination, is presented. The measurement is based on Kelvin's well-known capacitor method which measures the contact potential difference that builds up between two sufficiently conducting materials of different work function that are electrically connected. We show that the photovoltage of an absorber, which is introduced into the Kelvin capacitor, can be measured accurately, even though it is not in electrical contact to any of the capacitor plates. Comparative measurements of the surface photovoltage of an n-type Si semiconductor surface in grounded and nongrounded mode as well as the interface photovoltage of mesoporous TiO2, deposited onto a conducting substrate, are presented to demonstrate the feasibility of the concept. This approach enables to measure the photovoltage of complete solar cells and also its single components (absorber, absorber + buffer layer, absorber + buffer layer + electron and/or hole conductor), a matter that is of particular importance for a better understanding of photovoltaic devices such as extreme thin absorber cells, dye sensitized solar cells, or organic (so-called plastic) solar cells. (C) 2004 American Institute of Physics.
The electric potential distribution in dye-sensitized solar cells plays a major role in the operation of such cells. Models based on a built-in electric field which sets the upper limit for the open circuit voltage (V-oc) and/or the possibility of a Schottky barrier at the interface between the mesoporous wide band gap semiconductor and the transparent conducting substrate have been presented. We show that I-V characteristics in the dark and upon illumination are very well explained by electron tunneling, rather than transport over a Schottky barrier, at this interface. Our calculations, based on tunnel currents, show that a discontinuity of the conduction band at the TiO2/FTO interface, rather than a built-in electric field, suffices for efficient electron transfer through this interface, and, thus, for efficient operation of this type of solar cell. Clearly, this will hold only if the photoinduced electrostatic potential barrier between the transparent conducting substrate and the mesoporous wide band gap semiconductor drops over a region that is sufficiently narrow to allow efficient tunneling through it.
Reproducible electrical contacts to organic molecules are created non-destructively by indirect electron beam evaporation of Pd onto molecular films on cooled substrates. In contrast, directly evaporated contacts damage the molecules seriously. Our conclusions are based on correlating trends in properties of a series of molecules with systematically varying, exposed functional groups, with trends in the electrical behaviour of Pd/molecule/GaAs junctions, where these same molecules are part of the junctions.
Molecular control over charge transport across a metal/semiconductor interface persists even if there is only a partial monolayer of polar molecules at the interface. This is because the long-range electrostatic effect of the dipole layer also affects the semiconductor regions under the film's pinholes. Thus, all types of polar molecules that show average order at the interface can be used.
We show reproducible, stable negative differential resistance (NDR) at room temperature in molecule-controlled, solvent-free devices, based on reversible changes in molecule-electrode interface properties. The active component is the cyclic disulfide end of a series of molecules adsorbed onto mercury. As this active component is reduced, the Hg-molecule contact is broken, and an insulating barrier at the molecule-electrode interface is formed. Therefore, the alignment of the molecular energy levels, relative to the Fermi levels of the electrodes, is changed. This effect results in a decrease in the current with voltage increase as the reduction process progresses, leading to the so-called NDR behavior. The effect is reproducible and repeatable over more than 50 scans without any reduction in the current. The stability of the system, which is in the "solid state" except for the Hg, is due to the molecular design where long alkyl chains keep the molecules aligned with respect to the Hg electrode, even when they are not bound to it any longer.
We review the status of the understanding of dye-sensitized solar cells (DSSC), emphasizing clear physical models with predictive power, and discuss them in terms of the chemical and electrical potential distributions in the device. Before doing so, we place the DSSC in the overall picture of photovoltaic energy converters, reiterating the fundamental common basis of all photovoltaic systems as well as their most important differences.
We use the adsorption of systematically substituted silanes with either simple alkyl or alkyl phenyl ether chains onto oxidized Si to study the electronic effects of such molecular monolayers on Si. While there is no significant effect of distance of the substituents from the surface, a strong effect of what we interpret as depolarization is found for layers made up of molecules with high (>5 D) free molecule dipole moment. This is also apparent from differences in UV-visible and Fourier transform infrared (FTIR) spectral features, suggesting changes in molecular conformation, and, especially, from the measured contact potential differences. These reflect the modified surface's electron affinity and, thus, the effective dipole moment of the monolayer. The effect is ascribed to the system's response to the energetic price of dipole-dipole repulsion.
2003
CdTe/CdS solar cells were subjected to heat stress at 200 degreesC in the dark under different environments (in N-2 and in air), and under illumination (in N-2). We postulate that two independent mechanisms can explain degradation phenomena in these cells: i) Excessive Cu doping of CdS: Accumulation of Cu in the CdS with stress, in the presence of Cl, will increase the photoconductivity of CdS. With limited amounts of Cu in CdS, this does NOT affect the photovoltaic behavior, but explains the crossover of light/dark current-voltage (J-V) curves. Overdoping of CdS with Cu can be detrimental to cell performance by creating deep acceptor states, acting as recombination centers, and compensating donor states. Under illumination, the barrier to Cu cations at the cell junction is reduced, and, therefore, Cu accumulation in the CdS is enhanced. Recovery of light-stress induced degradation in CdTe/CdS cells in the dark is explained by dissociation of the acceptor defects. ii) Back contact barrier: Oxidation of the CdTe back surface in O-2/H2O-containing environment to form an insulating oxide results in a back-contact barrier. This barrier is expressed by a rollover in the J-V curve. Humidity is an important factor in air-induced degradation, as it accelerates the oxide formation. Heat treatment in the dark in inert atmosphere can stabilize the cells against certain causes of degradation, by completing the back contact anneal.
We use scanning probe microscopy-based methods for direct characterization of a single grain boundary and a single grain surface in solar cell-quality CdTe, deposited by closed-space vapor transport. We find that scanning capacitance microscopy can serve to study polycrystalline electronic materials, notwithstanding the strong topographical variations. In this way, we find a barrier for hole transport across grain boundaries, a conclusion supported by the much more topography-sensitive scanning kelvin probe microscopy, with some variation in barrier height between different boundaries. (C) 2003 American Institute of Physics.
Differences between junctions of metals on ionic or covalent semiconductors persist for junctions, prepared by wet solution methods with a molecular layer at the junctions' interface. A series of molecules that controls the junction of Au with n-GaAs, does so even stronger with ZnO (300 instead of similar to100 mV barrier height change). With ZnO the interface behavior index is found to be 0.55, five times that with GaAs. This agrees remarkably well with results for junctions of these materials with different metals, prepared in ultrahigh vacuum. Thus, the free semiconductor surface, e.g., surface state density, rather than direct metal-semiconductor interactions, appears to dominate junction behavior. (C) 2003 American Institute of Physics.
Epitaxial films of CuInSe2 on Si(1 1 1) were modified by the application of an electric field through a movable tip. The electric field induces stable junction regions which are identified by separation and collection of electron beam-induced charge carriers. The movable tip allows scribing of these junction regions and one-sided connection to a contact pad. The junction formation is mainly due to electric field application and, in contrast to what was found to be the case for bulk samples, is not accompanied by a significant temperature rise. The junctions can be explained by symmetrical p/p(+)/n/p(+)/p regions formed within the CuInSe2 epilayers. The reported method presents a new way for junction patterning in two dimensions. (C) 2003 Elsevier Science B.V. All rights reserved.
Metal/organic monolayer/GaAs junctions, prepared by adsorbing a set of dicarboxylic ligands, with systematic change of ligand substituents, on GaAs, are measured and characterized electrically. The molecules are chemically bound to the semiconductor surface under ambient conditions and form roughly a monolayer (MoL), with average order in the direction perpendicular to the semiconductor surface. This suffices to yield systematic changes in electron affinity and work function of the modified GaAs. Junctions are made by a soft metal deposition method, used here for Au and Al. Experimentally, we find strong molecular effects, reaching differences in current at a given voltage of up to 6 orders of magnitude, depending on the substituent on the molecules making up the monolayer. These and the changes in the effective barrier height of the metal/MoL/GaAs junctions, extracted by analyses of their current-voltage characteristics, can be explained by electrostatic effects of the molecular layer, rather than by electrodynamic ones (current flow through the molecular film). This can be understood by realizing that the samples are relatively large area devices with extremely narrow (similar to1 nm) films of organic molecules, showing only average order, which makes dominance of tunneling effects very unlikely. We show that not only the molecule's electronic and electrical properties but also the way the metals contact the molecules, as well as the doping type of the semiconductor, can determine the direction of the molecular effect. Also the type of metal governs the effect that we identify as being due to interfacial dipoles formed as a result of triple metal/organic molecule/semiconductor interaction.
We compile, compare, and discuss experimental results on low-bias, room-temperature currents through organic molecules obtained in different electrode-molecule-electrode test-beds. Currents are normalized to single-molecule values for comparison and are quoted at 0.2 and 0.5 V junction bias. Emphasis is on currents through saturated alkane chains where many comparable measurements have been reported, but comparison to conjugated molecules is also made. We discuss factors that affect the magnitude of the measured current, such as tunneling attenuation factor, molecular energy gap and conformation, molecule/electrode contacts, and electrode material.
Electronic mapping of cross sections of a polycrystalline device, the n-CdS/p-CdTe solar cell, show that the photovoltaic and metallurgical junctions coincide to within experimental resolution (50 nm), which rules out both type conversion of CdS and buried homojunctions. Compositional analysis of the CdS supports this. Mapping was done using scanning capacitance, complemented by scanning Kelvin probe microscopy. Our results explain why a high-resistance transparent conducting oxide layer is needed as contact to the CdS for successful device operation. They define limits on inputs for modeling performance of these devices. (C) 2003 American Institute of Physics.
We present a concise, although admittedly nonexhaustive, but hopefully didactic review and discussion of some of the central and basic concepts related to the energetics of surfaces and interfaces of solids. this is of particular importance for surfaces and interfaces that involve organic molecules and molecular films. It attempts to pull together different views and terminologies used in the solid state, electrochemistry, and electronic device communities, regarding key concepts of local and absolute vacuum level, surface dipole, work function, electron affinity, and ionization energy. Finally, it describes how standard techniques like photoemission spectroscopy can be used to measure such quantities.
2002
An information transfer mechanism through a molecular bilayer, which does not involve charge/mass transfer or conformational changes of membrane-spanning molecular structures, is proposed. We tested this proposal by measuring changes in the electric potential at a Si/SiOx surface, onto which an artificial bilayer had been constructed, in response to exposure of the adsorbed bilayer to different ambient. The bilayer was comprised of an OctadecylTrichloroSilane (OTS) monolayer, adsorbed onto the Si/SiOx surface and a second layer of stearic acid, deposited on the OTS monolayer by the Langmuir-Blodgett technique. Changes of the band bending (1313) at the Si/SiOx surface in response to exposing the bilayer to different solutions were measured by Kelvin Probe. These changes indicate that external stimuli at the bilayer's exterior induce a change in the electric potential at the bilayer's interior, a change that is sensed at the surface of the Si/SiOx. The mechanism proposed to explain the results is based on electrostatic interactions at the bilayer's exterior with dipole- or monopole-carrying molecules. (C) 2002 Elsevier Science B.V. All rights reserved.
This article examines a somewhat counter-intuitive approach to molecular-based electronic devices. Control over the electronic energy levels at the surfaces of conventional semiconductors and metals is achieved by assembling on the solid surfaces, poorly organized, partial monolayers (MLs) of molecules instead of the more commonly used ideal ones. Once those surfaces become interfaces, these layers exert electrostatic rather than electrodynamic control over the resulting devices, based on both electrical monopole and dipole effects of the molecules. Thus electronic transport devices, incorporating molecules, can be constructed without current flow through the molecules. This is illustrated for a gallium arsenide (GaAs) sensor as well as for gold-silicon (Au-Si) and Au-GaAs diodes. Incorporating molecules into solid interfaces becomes possible, using a 'soft' electrical contacting procedure, so as not to damage the molecules. Because there are only a few molecular restrictions, this approach opens up possibilities for the use of more complex (including biologically active) molecules as it circumvents requirements for ideal MLs and for molecules that can tolerate actual electron transport through them.
The mechanism by which dicarboxylic acid molecules adsorb onto ambient-exposed GaAs (10 0) surfaces is studied by combining infrared spectroscopy and measurements that are sensitive to changes of the electric potential on the surface. For the latter we used the recently developed molecular controlled semiconductor resistor. By comparing the time dependences of the two measurements we conclude that adsorption proceeds sequentially, with virtually all of the rearrangement of electrical charge in the adsorbates taking place when the first carboxylic group, in each molecule, binds to the surface. This can be understood if charge rearrangement is necessary for forming a close-packed adsorbed layer. Since creation of such a layer, that is made up of molecules with significant molecular dipoles, requires some degree of depolarization of the molecules. (C) 2002 Published by Elsevier Science B.V.
We describe and analyze a process to position a similar to1 nm thick molecular layer between two solid surfaces without damage to the molecules. The method is used to deposit a metal film in a soft, gentle manner on a semiconductor, yielding functional semiconductor/molecule/metal junctions. It is a combination of the lift-off procedure, known from, for example, lithography, and the bonding process, known from, for example, wafer bonding. The combined method may find application also outside the area described here. We point out its major difficulties as well as solutions to overcome them. For this we rely on concepts from the physics of liquid and solid surfaces and interfaces. Conditions are found, in terms of choice of solvents, under which the method will be effective. The efficacy of floatation as a soft contacting procedure is demonstrated by the preparation of Au and Al contacts on GaAs single crystal surface, modified by a self-assembled monolayer of small organic molecules. The resulting electrical properties of the contacts depend crucially on how the molecular interface with the contacting metal is formed. This type of wet contacting procedure to make dry devices may be advantageous especially if biomolecules are used.
Progress reports are a new type of article in Advanced Materials, dealing with the hottest current topics, and providing readers with a critically selected overview of important progress in these fields. It is not intended that the articles be comprehensive, but rather insightful, selective, critical, opinionated, and even visionary. We have approached scientists we believe are at the very forefront of these fields to contribute the articles, which will appear on an annual basis. The article below describes the latest advances in molecular electronics.
The effect of the presence or absence of chemical bonds between alkyl chain monolayers and the contacts in metal/molecule/semiconductor junctions on the current-voltage characteristics was studied. Three types of junctions were used: Hg/alkylthiols/SiO2/p-Si, Hg/alkylthiolsip-Si-H, and Hg/alkylsilaneS/SiO2/p-Si. While in the first two junctions current is attenuated exponentially as a function of the length of the alkyl chain, a characteristic behavior of tunneling, the current through the third junction does not reveal such behavior, suggesting that current transport is different in this case. We postulate that this is because in the first two junctions the monolayers are covalently bound to the Hg, while in the third junction, the alkysilanes are anchored to the Si surface only at a few points and are best viewed as not bonded to either side of the junction. The mechanism of cur-rent flow through the first two junctions is thought to be through-bond tunneling, and our results indicate that a chemical bond to at least one of the electrode surfaces is essential for this mechanism to operate. Electrostriction causes changes in the current-voltage characteristics,of the first two junctions. Evidence is presented suggesting that electrostriction tilts short chains (less than or equal toC(12)), resulting in an additional route to charge transport by tunneling through space. In contrast, long chains (greater than or equal toC(14)) do not tilt under pressure; instead, gauche defects are formed in their initial all-trans configuration decreasing the efficiency of electronic coupling through them. The use of p-type Si in this study ensures that at low bias voltages holes are the dominant charge carriers. Holes are found to tunnel more efficiently than electrons in agreement with theoretical predictions.
Grafting organic molecules onto solid surfaces can transfer molecular properties to the solid. We describe how modifications of semiconductor or metal surfaces by molecules with systematically varying properties can lead to corresponding trends in the (electronic) properties of the resulting hybrid (molecule + solid) materials and devices made with them. Examples include molecule-controlled diodes and sensors, where the electrons need not to go through the molecules (action at a distance), suggesting a new approach to molecule-based electronics.
The effect of sodium on the performance of CuInSe2-based solar cells has been under discussion for already a decade. We present experimental evidence using secondary ion mass spectroscopy, x-ray photoelectron spectroscopy (XPS) and other, complementary physical characterization methods, which indicate that, after exposure to an external Na source, no significant amounts of sodium, beyond the residual amount, found in as-grown samples, enter intact crystals, except via defects such as grain boundaries. However, after such exposure, sodium is found in significant concentrations on crystal surfaces, something that is accompanied by an increase in oxygen concentration, as judged by XPS. As expected metallic Na attacks the crystals and can destroy them or at least introduce significant defect densities. Adding Se-0 is found, via Na2Se formation, to temper Na activity specifically its effects on crystal disintegration. This is different from the effect of Se-0 along where annealing (of n-type) crystals results in n to p type conversion by Cu outdiffusion. (C) 2002 American Institute of Physics.
2001
High efficiency CdTe/CdS thin-film solar cells require low resistance contacts to p-CdTe, which is frequently achieved by addition of Cu. Decreases in cell efficiency over time. however. have been associated with Cu from the contact. The question that is considered here is if Cu is really detrimental to cell performance? By performing a series of thermal stress tests the authors reach a far more optimistic conclusion than what has hitherto been assumed. The Figure shows the proposed model for action of Cu (and Cl) in the CdTe/CdS cell.
Nitric oxide (NO) acts as a signal molecule in the nervous system, as a defense against infections, as a regulator of blood pressure, and as a gate keeper of blood flow to different organs. In vivo, it is thought to have a lifetime of a few seconds. Therefore, its direct detection at low concentrations is difficult. Mie report on a new type of hybrid, organic-semiconductor, electronic sen-sor that makes detection of nitric oxide in physiological solution possible. The mode of action of the device is described to explain how its electrical resistivity changes as a result of NO binding to a layer of native hemin molecules. These molecules are self-assembled on a GaAs surface to which they are attached through a carboxylate binding group. The new sensor provides a fast and simple method for directly detecting NO at concentrations down to 1 muM in physiological aqueous (pH=7.4) solution at room temperature.
Epitaxial films of CuInSe2 on Si(111) were modified by the application of an electric field through a movable tip. The electric field induces stable junction regions which are identified by efficient separation and collection of electron beam-induced charge carriers. The movable tip allows for scribing of these junction regions. The junctions can be explained by symmetrical p/p(+)/n/p(+)/p regions formed within the CuInSe2 epilayers. The reported method presents an alternate way for junction patterning in two dimensions. (C) 2001 American Institute of Physics.
Bifunctional conjugated molecules, consisting of electron donating or accepting groups that are connected, via a conjugated bridge, to a carboxylic acid group, were adsorbed as monomolecular carboxylate films on n-GaAs (100) and characterized by reflection FTIR, ellipsometry, and contact angle techniques. The way the donors and acceptors affected the electronic properties of the semiconductor was investigated. In agreement with theory, we find a linear relation between the calculated dipole moment of the molecules and the change in electron affinity of the moleculary modified surface, as well as between the barrier height of Au/molecule on n-GaAs junctions, extracted from their current-voltage characteristics and the dipole moment. The experimental results show little effect of the nature of the conjugated bridge in the molecules. Comparison with earlier work shows a clear decrease in the effect of the dipole of the free molecule on the semiconductor surface and interface behavior, notwithstanding the strongly conjugated link between the donor or acceptor groups of the molecule and the semiconductor surface. The simplest way to understand this is to consider the higher polarizability of the intervening bonds. Such effect needs to be considered in designing molecules for molecular control over devices.
The electron affinity of semiconductors and the work function of metals can be systematically varied by the adsorption of a series of organic molecules with varying dipole moment. This effect can be used to induce molecular control over the electrical characteristics of some metal/semiconductor diodes. The variety of molecules that can be bonded to metals, together with those that are available for bonding to semiconductors, makes the method quite flexible and may enable the build up of more sophisticated interfacial structures.
A semiconductor that contains dopants can be considered as a mixed electronic-ionic conductor, with the dopants as mobile ions. The temperature range in which this normally becomes true is far from where the opto-electronic properties of the material are of interest. However, exceptions exist. In this chapter we consider several important cases. Dopant diffusion and drift are relevant not only for materials such as Si:Li, used in radiation detectors, but also for other semiconductors, ranging from II-VIs and related compounds, such as CdTe, (Hg,Cd)Te and CuInSe2, to III-Vs, including GaN, and potential high temperature semiconductors, such as SiC. Better understanding of the phenomena is important also because of the implications that it has for device miniaturization. as dopant diffusion and drift put chemical limits to device stability. Such understanding can also make dopant electromigration useful for loci-temperature doping.
We suggest an alternative technique for electroluminescent device fabrication, based on our earlier findings of electric field (E-field)-induced bipolar transistor creation in Si, doped with Li. An external electric field served to induce Irm sized electroluminescent device structures in Si, that had been doped prior to E-field application, with Li, and Er via thermal in-diffusion. Such devices exhibit low temperature, near infrared (IR) electroluminescence at similar to 1.16 and 1.55 mum, corresponding to transitions associated with Li and Er levels, respectively, in the forbidden gap. While Li also creates radiative recombination centers in Si, the Er-based IR radiation is the most desirable one. At the same time Li-doping is what makes E-field-induced p-n junction fabrication possible. (C) 2001 Elsevier Science B.V. All rights reserved.
A semiconductor that contains dopants can be considered as a mixed electronic-ionic conductor, with the dopants as mobile ions. The temperature range in which this normally becomes true is far from where the opto-electronic properties of the material are of interest. However, exceptions exist. In this chapter we consider several important cases. Dopant diffusion and drift are relevant not only for materials such as Si:Li, used in radiation detectors, but also for other semiconductors, ranging from II-VIs and related compounds, such as CdTe, (Hg,Cd)Te and CuInSe(2), to III-Vs, including GaN, and potential high temperature semiconductors, such as SiC. Better understanding of the phenomena is important also because of the implications that it has for device miniaturization. as dopant diffusion and drift put chemical limits to device stability. Such understanding can also make dopant electromigration useful for loci-temperature doping.
The onset wavelengths of the surface photovoltage (SPV) in dye-sensitized solar cells (DSSCs) with different mesoporous, wide-band gap electron conductor anode materials, viz., TiO2 (anatase), Nb2O5 (amorphous and crystalline), and SrTiO3 using the same Ru bis-bipyridyl dye for all experiments, are different. We find a clear dependence of these onset wavelengths on the conduction band edge energies (E-CB) Of these oxides. This is manifested in a blue-shift for cells with Nb2O5 and SrTiO3 compared to those with TiO2. The ECB levels of Nb2O5 and SrTiO3 are known to be some 200-250 meV closer to the vacuum level than that of our anatase films, while there is no significant difference between the optical absorption spectra of the dye on the various films. We, therefore, suggest that the blue shift is due to electron injection from excited-state dye levels above the LUMO into Nb2O5 and SrTiO3. Such injection comes about because, in contrast to what is the case for anatase, the LUMO of the adsorbed dye in the solution is below the ECB Of these semiconductors, necessitating the involvement of higher vibrational and/or electronic levels of the dye, with the former being more likely than the latter. While for Nb2O5 hot electron injection has been proposed earlier, on the basis of flash photolysis experiments, this is the first evidence for such ballistic electron-transfer involving SrTiO3 a material very similar to anatase but with a significantly smaller electron affinity. Additional features in the SPV spectra of SrTiO3 and amorphous Nb2O5 (but not in those of crystalline Nb2O5) can be understood in terms of hole injection from the dye into the oxide via intraband gap surface states.
2000
Stability aspects of the Mo/Cu(In,Ga)Se-2/CdS/ZnO solar cell are reviewed and assessed. These include (i) the chemical stability of the various interfaces present in the device, (ii) the long-term behavior of metastable defects found in the Cu(In,Ga)Se-2 (CIGS) compound, and (iii) the impact of Cu migration on device performance and lifetime. We find that (i) all interfaces within the structure are chemically stable, (ii) metastable defects have a beneficial effect on performance, and (iii) Cu migration effects are reversible and their possible detrimental effects are eclipsed by the beneficial effect of the metastable states. Moreover, Cu out-diffusion from the CIGS layer is absent in photovoltaic-quality CIGS. Finally, we propose a model that explains the exceptional radiation hardness and impurity tolerance of CIGS-based devices, based on the synergetic effect of copper migration and point defect reactions.
The recent literature regarding the stability of CdTe/CdS photovoltaic cells las distinguished from modules) is reviewed. Particular emphasis is given to the role of Cu as a major factor that can limit the stability of these devices. Cu is often added to improve the ohmic contact to p-CdTe and the overall cell photovoltaic performance. This may be due to the formation of a Cu2Te/CdTe back contact. Excess Cu also enhances the instability of devices when under stress. The Cu, as Cu+, from either Cu2Te or other sources, diffuses via grain boundaries to the CdTe/CdS active junction. Recent experimental data indicate that Cu, Cl and other diffusing species reach (and accumulate at) the CdS layer, which may not be expected on the basis of bulk diffusion. These observations may be factors in cell behavior and degradation, for which new mechanisms are suggested and areas for future study are highlighted. Other possible Cu-related degradation mechanisms, as well as some non-Cu-related issues for cell stability are discussed. (C) 2000 Elsevier Science B.V. All rights reserved.
CuInSe2 is a semiconductor used in solar cells that has appreciable Cu ion conductivity. These authors have used 0.25 Angstrom synchrotron X-radiation to analyze its structure. It is shown that the application of a strong electric field leads to a decrease in electron density on the Cu sites, which sheds light on the role of Cu electromigration in transistor formation (see Figure) and in the photovoltaic activity of CuInSe2.
A new generic transducer has been developed, based on a Molecular Controlled Semiconductor Resistor (MOCSER). It is based on a GaAs/(AI, Ga)As structure, to the surface of which the specially designed bifunctional organic molecules are covalently bound The electrical current through the device is very sensitive to the surface polential. Therefore, it changes when metal ions bind to the receptor site of the organic molecule. The new sensor has high sensitivity over a wide dynamic range, high selectivity, short measurement time and it is inexpensive to produce.
Semiconductor surface states can affect the performance of many electronic devices, because of the significant role they have in electron transport across device interfaces. These authors use a series of dicarboxylic acids on GaAs surfaces to show that the effect is due to a HOMO-LUMO type of interaction between the frontier orbitals of the molecules and the semiconductor surface states.
Numerical simulations of the defect distribution of CuInSe2 were carried out as a function of the stoichiometry. The simulations are based on a new calculation of the intrinsic defects in this material. The results of the calculations were compared with earlier electrical and positron lifetime measurements. This leads to the assumption, that the single defects V-Se, V-Cu, Cu-1n and the defect pair (2V(Cu)-In-Cu) occur in the investigated specimens in considerable concentrations. (C) 2000 Elsevier Science S.A. All rights reserved.
The chemical effects of oxygenation of Cu(In,Ga)Se-2 (CIGS) interfaces are analyzed and are shown to involve passivation of Se deficiencies and Cu removal. The former effect is beneficial at grain boundaries, but detrimental at the CdS/CIGS interface. The latter effect is purely detrimental. Na and chemical bath deposition (CBD) treatments are shown to isolate the 'good' oxygenation effect from the 'bad' ones. Na is shown to promote oxygenation already before the deposition of the buffer and window layers, which allows a maximization of the benefits of Se deficiency passivation and a minimization of Cu removal. Next, the CBD of the CdS buffer layer restores the interface charge, due to creation of Cd-Cu interface donors and possibly a removal of O-Se interface accepters. This highlights the crucial role that interface redox engineering plays in optimizing the performance of CIGS-based solar cells. (C) 2000 Elsevier Science S.A. All rights reserved.
We explore chemical and physical limits to semiconductor device miniaturization. Minimal sizes for space charge-based devices can be estimated from Debye screening lengths of the materials used. Because a doped semiconductor can be viewed as a mixed electronic-ionic conductor, with the dopants as mobile ions, dopant intermixing across a p/n junction presents a chemical limit. Given a desired lifetime, simple relations can be derived between size and dopant intermixing for reverse- or forward-biased devices. Mostly, conditions for significant dopant mobility are far from those where the material is used. Thus, it is generally held that elemental and III-V-based p-n junctions are immune to this problem and persist because of kinetic stability. Indeed, we find this to be so for Si in the foreseeable future, but not for III-V- and II-VI-based ones. The limitation is more severe in structures with very thin undoped layers sandwiched between doped ones or vice versa, where even 1% intermixing can be critical. This decreases lifetime nearly 100 times. For example, for structures containing a 10 nm critical dimension, none of the components can have an average diffusion coefficient higher than 10(-24) cm(2)/s for a 3 year lifetime. Ways to overcome or mitigate this limitation are indicated. (C) 2000 Elsevier Science B.V. All rights reserved.
The use of molecules to control electron transport is an interesting possibility, not least because of the anticipated role of molecules in future electronic devices(1). But physical implementations using discrete molecules are neither conceptually(2,3) simple nor technically straightforward (difficulties arise in connecting the molecules to the macroscopic environment). But the use of molecules in electronic devices is not limited to single molecules, molecular wires or bulk material. Here we demonstrate that molecules can control the electrical characteristics of conventional metal-semiconductor junctions, apparently without the need for electrons to be transferred onto and through the molecules. We modify diodes by adsorbing small molecules onto single crystals of n-type GaAs semiconductor. Gold contacts were deposited onto the modified surface, using a 'soft' method to avoid damaging the molecules(4). By using a series of multifunctional molecules whose dipole is varied systematically, we produce diodes with an effective barrier height that is tuned by the molecule's dipole moment. These barrier heights correlate well with the change in work function of the GaAs surface after molecular modification. This behaviour is consistent with that of unmodified metal-semiconductor diodes, in which the barrier height can depend on the metal's work function.
We explain the cause for the photocurrent and photovoltage in nanocrystalline, mesoporous dye-sensitized solar cells, in terms of the separation, recombination, and transport of electronic charge as well as in terms of electron energetics. On the basis of available experimental data, we confirm that the basic cause for the photovoltage is the change in the electron concentration in the nanocrystalline electron conductor that results from photoinduced charge injection from the dye. The maximum photovoltage is given by the difference in electron energies between the redox level and the bottom of the electron conductor's conduction band, rather than by any difference in electrical potential in the cell, in the dark. Charge separation occurs because of the energetic and entropic driving forces that exist at the dye/electron conductor interface, with charge transport aided by such driving forces at the electron conductor/contact interface. The mesoporosity and nanocrystallinity of the semiconductor are important not only because of the large amount of dye that can be adsorbed on the system's very. large surface, but also for two additional reasons: (1) it allows the semiconductor small particles to become almost totally depleted upon immersion in the electrolyte (allowing for large photovoltages), and (2) the proximity of the electrolyte to all particles makes screening of injected electrons, and thus their transport, possible.
Careful analysis of the Cd-Te P-T-X phase diagram, allows us to prepare conducting p- and n-type CdTe, by manipulating the native defect equilibria only, without resorting to external dopants. Quenching of CdTe, following its annealing in Te atmosphere at 350-550 degrees C, leads to p-type conductivity with hole concentrations of similar to 2 x 10(16) cm(-3) Slow cooling of the samples, after 550 degrees C annealing in Te atmosphere, increases the hole concentration by one order of magnitude, as compared to quenching from the same temperature. We explain this increase by the defect reaction between donors V-Te and Te-i. Annealing in Cd atmosphere in the 350-550 degrees C temperature range leads, in contrast to the annealing in Te atmosphere, to n-type conductivity with electron concentrations of similar to 2 x 10(16) cm(-3). We ascribe this to annihilation of V-Cd as a result of Cd-i diffusion. (C) 2000 Elsevier Science B.V. All rights reserved.
Sequential self-assembly of a two-component system on a solid support is described with respect to structure and function. Two ligands, which bind to the semiconductor surface through one end and axially ligate a heme analogue at the other end, are described. Monolayer assemblies of complexes formed by these ligands and iron-porphyrin perform reversible binding of molecular oxygen. In the manolayer, a metalloporphyrin rin (the sensing unit) is held by the intervening ligand that serves as a "hinge'", away from the solid surface. Sensing events based on porphyrin chemistry are communicated via the ligand to the: Solid support. The transduction manifests itself as a change in the solid's surface electronic properties. Synthesis of the ligands and analysis of its complex formation with Fe-III-porphyrin are described. The anisotropic orientation of the porphyrin ring within the ligand cavity, due to restricted rotation around the Fe-III-N imidazole bonds, was probed by H-I NMR measurements in solution. We show that the porphyrin substituents stand as barriers for the free rotation even at room temperature. Molecular modeling supports the NMR evidence and reveals the stable conformations for the porphyrin's orientation relative to the solid support, The complexes wen assembled as films on the (0001) surface of etched n-CdSe single crystals, and the Films were characterized using transmission Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies. Contact potential difference (CPD) and steady-state photoluminescence (PL) measurements of the derivatized CdSe show that the intervening ligands yield better conjugation and; stronger binding of the sensing unit to the semiconductor surface, relative to direct adsorption of metalloporphyrins. Furthermore, the PL changes in the Cdse: can be used to follow the interaction of the surface-bound Fe-III-porphyrin-ligand complexes with molecular oxygen, A model is proposed to explain the electronic changes r
The use of molecules to control electron transport is an interesting possibility, not least because of the anticipated role of molecules in future electronic devices(1). But physical implementations using discrete molecules are neither conceptually(2,3) simple nor technically straightforward (difficulties arise in connecting the molecules to the macroscopic environment). But the use of molecules in electronic devices is not limited to single molecules, molecular wires or bulk material. Here we demonstrate that molecules can control the electrical characteristics of conventional metal-semiconductor junctions, apparently without the need for electrons to be transferred onto and through the molecules. We modify diodes by adsorbing small molecules onto single crystals of n-type GaAs semiconductor. Gold contacts were deposited onto the modified surface, using a 'soft' method to avoid damaging the molecules(4). By using a series of multifunctional molecules whose dipole is varied systematically, we produce diodes with an effective barrier height that is tuned by the molecule's dipole moment. These barrier heights correlate well with the change in work function of the GaAs surface after molecular modification. This behaviour is consistent with that of unmodified metal-semiconductor diodes, in which the barrier height can depend on the metal's work function.
1999
Single crystals of CuInSe2 were prepared under conditions to suppress the occurrence of twinning. This was accomplished by growth from an In melt by the traveling heater method to keep the growth temperature below that of the sphalerite-chalcopyrite phase transition. The resulting crystals were n-type and could be converted to p-type by a Se anneal. Both n and p-type crystals were characterized structurally by X-ray diffraction, compositionally by microprobe analyses, morphologically by atomic force and scanning electron microscopy, and electrically. They were found to be mostly homogeneous with mirror-like cleavage and without twins. (C) 1999 Elsevier Science B.V. All rights reserved.
We show that percolation can control not only diffusion in solids, but in the case of semiconductors also their electrical activity, via the doping action of the diffusing species. This occurs in (Hg1-xCdx)Te (MCT) when x(Cd) <0.8. The 10(7) times higher diffusivity at x(Cd) <0.8 can be understood by realizing that the percolation threshold for an ideal FCC lattice is at 0.19. While normally Ag is a donor, it can be an acceptor by stabilizing the Hg(I) state. This is possible by interaction with 2 Hg neighbors, a process that will be favorable above the Hg percolation limit. The fast Ag diffusion also holds the clue for the occurrence of ultra-low concentration phase separation in this system, the result of a balance between elastic attraction and Coulombic repulsion between the charged dopants. Prima facie evidence for this phase separation comes from coulometric Ag titration in and out of MCT. (C) 1999 Elsevier Science B.V. All rights reserved.
Communication: Is "self-healing" the source of the stability of Cu(In, Ga)Se-2-based solar modules? The proven remarkable stability and radiation hardness of Cu(In,Ga)Se-2 (CIGS) solar cells stand in apparent contradiction to the fact that CIGS shows both short-range (metastable defect centers) and long-range (significant Cu migration) instabilities. The authors suggest that these instabilities may in fact be a prerequisite for CIGS's stability as they allow a degree of flexibility or "smartness" in accommodating externally imposed changes. Two self-healing cycles are proposed, in which copper species play a particularly important role.
We present "design rules" for the selection of molecules to achieve electronic control over semiconductor surfaces, using a simple molecular orbital model. The performance of most electronic devices depends critically on their surface electronic properties, i.e., surface band-bending and surface recombination velocity. For semiconductors, these properties depend on the density and energy distribution of surface states. The model is based on a surface state-molecule, HOMO-LUMO-Like interaction between molecule and semiconductor. We test it by using a combination of contact potential difference, surface photovoltage spectroscopy, and time- and intensity-resolved photoluminescence measurements. With these, we characterize the interaction of two types of bifunctional dicarboxylic acids, the frontier orbital energy levels of which can be changed systematically, with air-exposed CdTe, CdSe, InP, and GaAs surfaces. The molecules are chemisorbed as monolayers onto the semiconductors. This model explains the widely varying electronic consequences of such interaction and shows them to be determined by the surface state energy position and the strength of the molecule-surface state coupling. The present findings can thus be used as guidelines for molecule-aided surface engineering of semiconductors.
We show that percolation can control not only diffusion in solids, but in the case of semiconductors also their electrical activity, via the doping action of the diffusing species. This occurs in (Hg1-xCdx)Te (MCT) when x(Cd) <0.8. The 10(7) times higher diffusivity at x(Cd) <0.8 can be understood by realizing that the percolation threshold for an ideal FCC lattice is at 0.19. While normally Ag is a donor, it can be an acceptor by stabilizing the Hg(I) state. This is possible by interaction with 2 Hg neighbors, a process that will be favorable above the Hg percolation limit. The fast Ag diffusion also holds the clue for the occurrence of ultra-low concentration phase separation in this system, the result of a balance between elastic attraction and Coulombic repulsion between the charged dopants. Prima facie evidence for this phase separation comes from coulometric Ag titration in and out of MCT. (C) 1999 Elsevier Science B.V. All rights reserved.
A reinvestigation of the phase diagram of the Cu-In-Se system along the quasi-binary cut In2Se3-Cu2Se reveals an existence range of the chalcopyrite alpha-phase that is much narrower than commonly accepted. The presence of 0.1% of Na or replacement of In by Ga at the at.% level widens the existence range of the alpha-phase, towards In- and Ga-rich compositions. We also investigate the interplay between phase segregation and junction formation in polycrystalline Cu(In, Ga)Sen films. Here, we attribute the band bending observed at bare surfaces of the films to a positively charged surface acting as a driving force for the formation of a Cu-poor surface defect layer via Cu-electromigration. The electrical properties of this defect layer are different from those found for the bulk beta-phase. We suggest that Cu-depletion is self-limited at the observed In/(In+Cu) surface composition of 0.75 because further Cu-depletion would require a structural transformation. Capacitance measurements reveal two types of junction metastabilities: one resulting from local defect relaxation, invoked to explain a light-induced increase of the open-circuit voltage of Cu(In, Ga)Se-2 solar cells, and one due to Cu-electromigration.
Nanocrystalline SrTiO3 is synthesized by hydrothermal treatment of nanocrystalline titanium dioxide in the presence of strontium hydroxide. Working photoelectrochemical solar cells are produced using these nanometer-sized semiconductor particles as photoelectrode materials. At AM 1.5, measured open circuit voltages were roughly 100 mV higher than in solar cells produced using nanocrystalline titanium dioxide (anatase), in agreement with a simple relation between semiconductor conduction band edge and open circuit voltage for these cells. Photocurrents measured in the SrTiO3 cells were roughly 1/3 those measured with TiO2 (anatase)-based cells. On the basis of flash laser photolysis and absorptance studies, we suggest that low dye loading and possibly suboptimal dye-oxide interactions can be the cause for the relatively low photocurrents in the SrTiO3 system.
Post-deposition air-annealing effects of Cu(In,Ga)Se-2 based thin films and heterojunction solar cell devices are studied by photoelectron spectroscopy and admittance spectroscopy. Ultraviolet photoelectron spectroscopy reveals type inversion at the surface of the as-prepared films, which is eliminated after exposure of several minutes to air due to the passivation of surface Se deficiencies. X-ray photoelectron spectroscopy demonstrates that air annealing at 200 degrees C leads to a decreased Cu concentration at the film surface. Admittance spectroscopy of complete ZnO/CdS/Cu(In,Ga)Se-2 heterojunction solar cells shows that the Cu(In,Ga)Se-2 surface type inversion is restored by the chemical bath used for CdS deposition. Air annealing of the finished devices at 200 degrees C reduces the type inversion again due to defect passivation. Our results also show that oxygenation leads to a charge redistribution and to a significant compensation of the effective acceptor density in the bulk of the absorber. This is consistent with the release of Cu from the absorber surface and its redistribution in the bulk. (C) 1999 American Institute of Physics. [S0021-8979(99)02813-3].
Dopant flux in a semiconductor junction due to chemical diffusion and drift (electromigration) was analyzed as a possible determining factor for device life expectancy at room temperature. Simple relations are derived and/or recalled to allow estimates of lifetimes. They are shown to be appropriate for III-V heterojunction bipolar transistors. We suggest that this chemical factor must be considered for compound semiconductor devices, as their dimensions shrink. (C) 1999 The Electrochemical Society. S1099-0062(98)10-082-2. All rights reserved.
We show that percolation can control not only diffusion in solids, but in the case of semiconductors also their electrical activity, via the doping action of the diffusing species. This occurs in (Hg1-xCdx)Te (MCT) when x(Cd) <0.8 The 10(7) times higher diffusivity at x(Cd) <0.8 can be understood by realizing that the percolation threshold for an ideal FCC lattice is at 0.19. While normally Ag is a donor, it can be an acceptor by stabilizing the Hg(I) state. This is possible by interaction with 2 Hg neighbors, a process that will be favorable above the Hg percolation limit. The fast Ag diffusion also holds the clue for the occurrence of ultra-low concentration phase separation in this system, the result of a balance between elastic attraction and Coulombic repulsion between the charged dopants. Primafacie evidence for this phase separation comes from coulometric Ag titration in and out of MCT. (C) 1999 Elsevier Science B.V. All rights reserved.
Hemispherical p/n/p transistor structures ranging from 100 mu m down to 0.05 mu m in diameter are fabricated in CuInSe(2), by application of a high electric field between a conducting diamond tip of an atomic force microscope and a CuInSe(2) crystal. This leads to electromigration of Cu ions in the bulk of the material. The results of this thermally assisted process are the transistor structures. These are characterized by scanning spreading resistance microscopy. For large devices these results are compared and found to agree with those of "conventional" electron-beam-induced current ones. Removing several tens of atomic layers from the top surface of a structure does not affect the spreading resistance image of the device. This indicates the three-dimensional hemispherical nature of the structures. [S0163-1829(99)13515-X].
We show how phase separation, in the form of a redistribution of impurities (dopants in a semiconductor), can occur at impurity concentrations that are more than one order of magnitude lower than hitherto observed. This phenomenon results from the balance between long-range electrostatic repulsion and the elastic attraction of the dopants, which deforms the anisotropic host lattice. We observed such a phase separation for Ag in (Cd, Hg)Te at Ag concentrations <0.02 at. %. This also leads to the formation of a thermodynamically (as opposed to kinetically) stable p-n junction in the a-phase region. Searching for phase separation at such low concentrations requires highly sensitive analyses, here made possible because of the difference in conductivity type between the phases.
We present a simple, compact, and robust arrangement for surface photovoltage measurements of free semiconductor surfaces immersed in liquids. It is based on the classical Kelvin probe arrangement, where the semiconductor sample is put in a liquid-containing, electrically insulating vessel, with an optically transparent window, situated between the sample and the Kelvin probe. At the price of permitting relative, rather than absolute, contact potential difference values, this modification enables easy, routine surface photovoltage measurements of semiconductors in any kind of liquid ambient. The validity and efficiency of this approach are demonstrated by surface photovoltage spectra obtained from the p-InP(100) surface in various liquid etchants. (C) 1999 American Institute of Physics. [S0034- 6748(99)03910-6].
We have developed a new, efficient method to dope bulk single crystals of CdTe by In, via gas phase diffusion, using In4Te3 as the source. Doping was carried out on crystals of very high resistivity (>5 M Omega cm), following annealing in the temperature range of 350-1000 degrees C. Resulting crystals showed n-type conductivity with a free carrier concentration in the range: of 10(15)-10(18) cm(-3) and carrier mobility of 100-750 cm(2)/(V s), depending on the annealing temperature and time, and on the cooling conditions. Incorporation of In was found to be a function of annealing time and temperature only. Up to 650 degrees C, the In and the free electron concentrations are roughly the same. (C) 1999 Elsevier Science B.V. All rights reserved.
1998
The structure of CuInSe2 was redetermined, using synchrotron X-radiation with 0.15 Angstrom wavelength, thus eliminating problems of uncertainties introduced by absorption corrections. This allowed us to look at the effect of subjecting crystals to strong electric fields, a process known to be able to type convert the material under relatively mild conditions. Proper refinement became possible after correcting for twinning. The main results are relatively high Cu temperature factors and significant electron density in octahedral interstitial sites. The main results of electric field application are a decrease in structure quality (increased R factor) and a slight increase in electron density on Cu sites. These preliminary results point to the need for further work with twin-free crystals.
In this study we present the determination of the defect chemistry and the electrical properties of CuInSe2 after controlled annealing steps. The samples were investigated with the positron annihilation method and the admittance spectroscopy.
Control over semiconductor surface energetics can be achieved using different chemisorbed organic molecules with diverse electronic properties. We find evidence of such control over CdTe upon adsorption of dicarboxylic acid derivatives with different substituted phenyl rings. FT-IR measurements show that the dicarboxylic acid derivatives bind as carboxylates to form approximately one monolayer. Such chemisorption modifies both the band bending and the electron affinity (up to 500 and 700 mV, respectively), as measured by contact potential difference (CPD). Changes in band bending result from a coupling between molecular orbitals and surface states close to the valence band and depend on the withdrawing character of the phenyl substituent. A model is presented to interpret and explain the data. (C) 1998 Elsevier Science B.V.
We fabricate sub-micron sized diode and transistor structures (down to 100 nm in diameter) inside CuInSe2 crystals by inducing thermally assisted electromigration of mobile dopants. This is achieved by applying an electric field via a small area contact to the crystals, using a conducting Atomic Force Microscope tip. The structures are characterized by nm scale scanning spreading resistance and scanning capacitance measurements to reveal the inhomogeneous doping profiles, that result from the electric field action. Calculations suggest that the smallest of the structures that we made are very close to the lower size limit of possible p/n/p devices.
Thermal diffusion, parallel to the photovoltaic junction and perpendicular to the direction of illumination, can be used to separate the contributions of injected and photogenerated carriers to the generation of heat in a photothermal experiment, and to demonstrate the influence of electronic carrier diffusion on the signal, already at relatively low modulation frequencies. We show this by using an experimental arrangement in which the distance is varied between the illuminated area of the photovoltaic cell and that over which the thermal signal is detected, and the two areas do not overlap. Our results agree with theoretical calculations used to simulate the photothermal responses of solar cells.
In this study we present the determination of the defect chemistry and the electrical properties of CuInSe2 after controlled annealing steps. The samples were investigated with the positron annihilation method and the admittance spectroscopy.
Ion potential diagrams can facilitate the description of systems in which ionic species are mobile. They depict qualitatively the spatial dependence of the potential energy for mobile ions, somewhat akin to band diagrams for electrons. We construct ion potential diagrams for the mixed conducting (oxide), optically active electrodes of five-layer electrochromic devices, based on reversible Li+ intercalation. These serve to analyze stability problems that arise in these systems. We then use them as building blocks to arrive at ion diagrams for complete devices. This allows analyses of (dis)coloration kinetics.
By growing CuInSe(2) with the traveling heater method, from an In melt (at a temperature below that of the sphalerite-chalcopyrite transition), twinning in the resulting single crystals was suppressed. The resulting crystals were n-type and could be converted to p-type by Se anneal. Both types were characterized structurally by X-ray diffraction, for composition by microprobe analyses, morphologically by AFM and SEM, and electrically. They were found to be mostly homogeneous, with mirror-like cleavage and without twins.
The interactions between adsorbed organic molecules and the electronic charge carriers in specially made GaAs structures are studied by time- and wavelength-dependent measurements of the photocurrent. The adsorption of the molecules modifies the photocurrent decay time by orders of magnitude. The effects are molecularly specific, as they depend on the electronic properties and absorption spectrum of the molecules. These observations are rationalized by assuming that new surface states are created upon adsorption of the molecules and that the character of these states is controlled by the relative electronegativity of the substrates and the adsorbed molecules. The relevance for surface passivation and for construction of semiconductor-based sensors is indicated. (C) 1998 Elsevier Science B.V.
We fabricate sub-micron sized diode and transistor structures (down to 100 nm in diameter) inside CuInSe2 crystals by inducing thermally assisted electromigration of mobile dopants. This is achieved by applying an electric field via a small area contact to the crystals, using a conducting Atomic Force Microscope tip. The structures are characterized by nm scale scanning spreading resistance and scanning capacitance measurements to reveal the inhomogeneous doping profiles, that result from the electric field action. Calculations suggest that the smallest of the structures that we made are very close to the lower size limit of possible p/n/p devices.
Thermal diffusion, parallel to the photovoltaic junction and perpendicular to the direction of illumination, can be used to separate the contributions of injected and photogenerated carriers to the generation of heat in a photothermal experiment, and to demonstrate the influence of electronic carrier diffusion on the signal, already at relatively low modulation frequencies. We show this by using an experimental arrangement in which the distance is varied between the illuminated area of the photovoltaic cell and that over which the thermal signal is detected, and the two areas do not overlap. Our results agree with theoretical calculations used to simulate the photothermal responses of solar cells.
The promising new generation of solar cells based on CIGS (Cu(I,Ga)Se-2) exhibits behavior differing from that of earlier cells because of changes in the method of preparation, leading, among other things, to a difference in sodium content. A simple defect chemical model is presented for the effects of sodium on the surface chemistry and electronic properties of CIGS thin films. The model, based on the well-known catalytic effect that alkali metals have on surface oxidation of semiconductors, is shown to be consistent with the experimental data available in the literature.
Control over the surface chemistry and physics of electronic and optical materials is essential for constructing devices and fine-tuning their performance. In the past few years we have started to explore the use of organic molecules for systematic modification of semiconductor surface electronic properties. In this paper, manipulation of silicon surfaces by self-assembly of various quinolinium-based chromophores is reported. The progress of the assembly process is monitored by XPS, UV-Vis, and FTIR spectroscopies as well as with surface wettability. The effect of the monolayer's dipole moment on the Si surface potential and the interaction with surface states is monitored by CPD measurements. A pronounced effect of a sub-nanometer coupling-agent layer alone on the electron affinity and band-bending of Si was observed. We also show a way to modulate the Si work-function by tuning the dipole strength of the chromophore-containing organic, self-assembled monolayer and of its orientation with respect to the silicon surface.
Control over the surface chemistry and physics of electronic and optical materials is essential for constructing devices and fine-tuning their performance. In the past few years we have started to explore the use of organic molecules for systematic modification of semiconductor surface electronic properties. In this paper, manipulation of silicon surfaces by self-assembly of various quinolinium-based chromophores is reported. The progress of the assembly process is monitored by XPS, UV-Vis, and FTIR spectroscopies as well as with surface wettability. The effect of the monolayer's dipole moment on the Si surface potential and the interaction with surface states is monitored by CPD measurements. A pronounced effect of a sub-nanometer coupling-agent layer alone on the electron affinity and band-bending of Si was observed. We also show a way to modulate the Si work-function by tuning the dipole strength of the chromophore-containing organic, self-assembled monolayer and of its orientation with respect to the silicon surface.
We show how sub-mu m sized transistor structures (down to 50 nm cross section) can be fabricated by thermally assisted electromigration of mobile dopants inside the semiconductor CuInSe2. Small device structures are fabricated by application of an electric field to the sample via the contact, defined by a conducting atomic force microscope tip. The structures are characterized by nm scale scanning spreading resistance and scanning capacitance measurements to reveal the inhomogeneous doping profiles created by the electric field. (C) 1998 American Institute of Physics. [S0003-6951(98)03539-6].
The structure of CuInSe2 was redetermined, using synchrotron X-radiation with 0.15 Angstrom wavelength, thus eliminating problems of uncertainties introduced by absorption corrections. This allowed us to look at the effect of subjecting crystals to strong electric fields, a process known to be able to type convert the material under relatively mild conditions. Proper refinement became possible after correcting for twinning. The main results are relatively high Cu temperature factors and significant electron density in octahedral interstitial sites. The main results of electric field application are a decrease in structure quality (increased R factor) and a slight increase in electron density on Cu sites. These preliminary results point to the need for further work with twin-free crystals.
Systematic errors are likely to affect the results of indirect methods used for measuring dopant diffusion in semiconductors, which, for this purpose should be considered as mixed electronic-ionic conductors. The highest contribution to these errors is introduced by the presence of an internal electric field, i.e., by space charge effects. The electric field can be the result either of a dopant concentration gradient or of external bias, applied during the measurement. We consider here three methods in detail, viz. measurement of p-n junction motion, of current or potential decay, and of the time dependence of capacitance (transient ion drift). We show that space charge effects can lead to overestimating diffusion coefficients by a few orders of magnitude. We use the results of our analyses to review and compare the experimental data obtained by different direct and indirect methods, for Cu diffusion in CuInSe2, an issue of considerable current interest for solar cells. (C) 1998 American Institute of Physics.
We show that the chemisorption of dicarboxylic acids on GaAs (100) is described well by a two-site mechanism, in contrast to benzoic acid adsorption which fits to a one-site mechanism. We do so by using a novel electrical method for direct measurement of adsorption kinetics. In the method we measure the current through a GaAs/(Al, Ga)As-based device, where the bare surface between two contacts is used as the adsorption domain. The results, which are in agreement with FTIR absorption equilibrium data, are obtained in ambient notwithstanding the notorious instability of GaAs surfaces under such conditions. We conclude that these acids chemisorb on the GaAs surface and that binding is significantly stronger for the di-than for the monocarboxylic acids.
By growing CuInSe2 with the traveling heater method, from an In melt (at a temperature below that of the sphalerite-chalcopyrite transition), twinning in the resulting single crystals was suppressed. The resulting crystals were n-type and could be converted to p-type by Se anneal. Both types were characterized structurally by X-ray diffraction, for composition by microprobe analyses, morphologically by AFM and SEM, and electrically. They were found to be mostly homogeneous, with mirror-like cleavage and without twins.
A doped semiconductor can be viewed as a mixed electronic-ionic conductor, with the dopants as mobile ions. Normally the temperature range where this becomes true is not even close to that where the (opto)electronic properties of the material are of interest. However notable exceptions exist and some examples of these are reviewed here. We limit ourselves to those cases where semiconductivity is preserved when the (mobile) dopant concentration changes and ambipolar behaviour can be obtained by dopant mobility. Dopant diffusion and drift are of interest not only in materials such as Si:Li, known from its use in radiation detectors, but also in ternary semiconductors, such as (HE,Cd)Te and CuInSe2. Understanding the phenomena is important not only for low-temperature doping, but also because of the implications that it has for device miniaturization, as dopant diffusion and drift impose chemical limits on device stability.
A doped semiconductor can be viewed as a mixed electronic-ionic conductor, with the dopants as mobile ions. Normally the temperature range where this becomes true is not even close to that where the (opto)electronic properties of the material are of interest. However notable exceptions exist and some examples of these are reviewed here. We limit ourselves to those cases where semiconductivity is preserved when the (mobile) dopant concentration changes and ambipolar behaviour can be obtained by dopant mobility. Dopant diffusion and drift are of interest not only in materials such as Si:Li, known from its use in radiation detectors, but also in ternary semiconductors, such as (HE,Cd)Te and CuInSe2. Understanding the phenomena is important not only for low-temperature doping, but also because of the implications that it has for device miniaturization, as dopant diffusion and drift impose chemical limits on device stability.
1997
Homogeneously mixed molecular assemblies of defined stoichiometry were created by adsorption of asymmetric, trifunctional ligands on gold and CuInSe2 (CISe). The ligands rely on cyclic disulfide groups for binding to the substrate and can in addition-possess two different substituents, one polar substituent (p-cyanobenzoyl or anisoyl) and one long-chain, aliphatic residue (palmitoyl). Because the substituents are covalently connected, no phase segregation will occur upon surface binding. Adsorption of these ligands on conducting surfaces changed both the surface potential (because of the polar substituent) and hydrophobicity (because of the aliphatic residue). Larger changes of surface potential were obtained by adsorption of the symmetric, dipolar ligands than by adsorption of the asymmetric ligands, and larger changes occurred on gold than on CuInSe2 (up to 1.2 V between extreme modifications on Au and 0.3 V on CISe). The magnitude and direction of the observed contact potential difference changes were found to depend on the extent of coverage (as derived from electrochemical and contact angle measurements) and on the orientation of the ligands (estimated from ellipsometry and FTIR data) and could also be reconstructed using a simple, electrostatic model. These findings demonstrate that the present methodology enables simultaneous grafting of two desired properties onto solid surfaces and illustrate the predictive power of a simple, electrostatic model for molecule-controlled surface engineering.
The effects of chemisorbed molecules on the electronic transport through an ungated high electron mobility transistor and through an ungated field effect transistor are examined, Current versus voltage measurements in the dark reveal that the adsorbed molecules and their chemical nature have a pronounced effect on the structures' performance, as they reduce the current by up to one order of magnitude. The molecular specificity of the devices is expressed in the wavelength dependence of photo current decay. The decay time, which increases by several orders of magnitude upon adsorption of the molecules, changes drastically when the excitation wavelength matches the absorption of the adsorbed molecules. Effect of Cu ions caught by adsorbed organic molecules on the photo current decay is clearly demonstrated. The observations open new possibilities in constructing semiconductor based light and chemical sensors.
The electronic properties of semiconductor surfaces can be controlled by binding tailor-made ligands to them. Here we demonstrate that deposition of a conducting phase on the treated surface enables control of the performance of the resulting device. We describe the characteristics of the free surface of single crystals and of polycrystalline thin films of semiconductors that serve as absorbers in thin film polycrystalline, heterojunction solar cells, and report first data for actual cell structures obtained by chemical bath deposition of CdS as the window semiconductor. The trend of the characteristics observed by systematically varying the ligands suggests changes in work function rather than in band bending at the free surface, and implies that changes in band line-up, which appear to cause changes in band bending, rather than direct, ligand-induced band bending changes, dominate.
The diffusion and electromigration of Ag in crystals of CdxHg1-x is studied, as a function of original doping level and of the concentration of mercury. In materials with x = 0.55-0.8, Ag dopes p-type, when diffusing in at <125 degrees C. This should be contrasted to what is found in n-CdTe; where in-diffusion of Ag at 200 degrees C increases the net donor density, leaving the material n-type. Our results show that the higher is the mercury content or the hole concentration in CdxHg1-xTe (x = 0.55-0.8), the faster Ag will; diffuse in these materials; We explain our results, building on earlier suggestions made for Hg-rich materials, by assuming that silver diffuses by way of a substitutional-interstitial mechanism; i.e., it is present as two species with opposite charge, one of which : dominates nd is practically immobile, while the minority, species diffuses rapidly These forms equilibrate, at room temperature, within a few seconds, something that can be understood by postulating silver-mercury complex formation. If both forms of silver are bound to mercury, then this hypothesis explains the strong influence of mercury content on the diffusion behavior.
The electronic properties of semiconductor surfaces can be controlled by binding tailor-made ligands to them. Here we demonstrate that deposition of a conducting phase on the treated surface enables control of the performance of the resulting device. We describe the characteristics of the free surface of single crystals and of polycrystalline thin films of semiconductors that serve as absorbers in thin film polycrystalline, heterojunction solar cells, and report first data for actual cell structures obtained by chemical bath deposition of CdS as the window semiconductor. The trend of the characteristics observed by systematically varying the ligands suggests changes in work function rather than in band bending at the free surface, and implies that changes in band line-up, which appear to cause changes in band bending, rather than direct, ligand-induced band bending changes, dominate.
Assembling quinolinium-based chromophores on silicon surfaces provides a new route to electronic control over such semiconducting surfaces. The two-step process by which the molecules are grafted on to the surface involves first coupling the organic functionality to silicon, followed by chromophore anchoring. These synthetic steps are monitored by XPS, UV-Vis and FTIR spectroscopies. Using contact potential difference measurements we found that the electron affinity of the modified silicon is a function of the molecule's dipole moment. The same technique shows a pronounced effect of the sub-nanometer siloxane-based, coupling-agent, layer by itself on the band bending and band-bending modification as function of chromophore adsorption. (C) 1997 Published by Elsevier Science B.V.
Dopant diffusion and drift in semiconductors is reviewed with special emphasis on those materials in which semiconductivity is preserved when the dopant concentration changes and ambipolar behavior can be obtained by dopant mobility. The Figure is a schematic representation of the electromigration process in CuInSe2 upon application of an electric field.
We show that the transient ion drift (TID) method, which is based on recording junction capacitance under constant reverse bias [A. Zamouche, T. Heiser, and A. Mesh, Appl. Phys. Lett. 66, 631 (1995)], can be used not only for measurements of the diffusion coefficient of mobile impurities, but also to estimate the concentration of mobile species as part of the total dopant density. This is illustrated for CdTe, contaminated by Cu, and intentionally doped by Li or Ag and for CuInSe2. We show also that, with some restrictions, the TID method can be used if the mobile ions are major dopants. This is demonstrated using Schottky barriers on CdTe, and p-n junction devices in (Hg,Cd)Te, and CuInSe2. The values that we obtain for the diffusion coefficients (for Li, Ag, and Cu in CdTe and for Cu in CuInSe2) agree well with measured or extrapolated values, obtained by other methods, as reported in the literature. Furthermore, we could distinguish between diffusion and chemical reactions of dopants, as demonstrated for the case of Cu in CdTe and Ag-doped (Hg,Cd)Te. In the former case this allows us to separate copper-free from contaminated CdTe samples. (C) 1997 American Institute of Physics.
The purpose of construction of ion potential diagrams is to facilitate the description of systems in which ionic species are mobile. These diagrams depict qualitatively the spatial dependence of the potential energy for mobile ions in a way similar to band diagrams for electrons. We specify and explain what types of experimental data are needed to construct these diagrams. We construct such diagrams for five layer electrochromic devices in which both optically active electrodes are oxides, capable of reversible lithium ion intercalation. We consider the systems at open circuit and under bias. We compare the behaviour of several electrochromic oxides with respect to intercalation and deintercalation reactions. On the basis of the diagrams we discuss electrode stability and switching time in electrochromic devices. Possible novel electrode materials, in terms of their electrical behaviour, are discussed.
When p-n junctions are formed by doping with a dopant that diffuses via a dissociative diffusion mechanism, dopant diffusion is suppressed and dopants can pile up near the junction, well above their original concentration. Calculations confirm this, if no local neutrality is assumed. The results agree well with published and our own experimental data for Zn diffusion in InP. The increased built-in electric field due to this pileup is expelled nearly completely to the side of the junction without the pileup. This effect has important consequences for devices containing thin and/or small regions doped with such dopants because such regions may be completely depleted. (C) 1997 American Institute of Physics.
Room temperature formation of ohmic contacts by electroplating gold on chemically treated surfaces of p-CuInSe2 and p-CdTe single crystals is reported. The effect of Br-2/methanol and KOH+KCN+H2O treatments prior to plating was analyzed in the case of CuInSe2. It is shown that the former treatment yields better ohmic contacts, with lower contact resistance, than the latter. While annealing these contacts made them highly non-ohmic, the method gives reasonably ohmic contacts on surfaces, that were purposely oxidized prior to contact preparation. In the case of p-CdTe stable, low resistance ohmic contacts were obtained at room temperature by electrochemical diffusion of Hg from solution, prior to gold plating,The treatment forms a highly degenerated p(+)-HgCdTe layer. The contacts, which have a very low contact to bulk resistivity ratio, were further improved by vacuum annealing.
The effects of chemisorbed molecules on the electronic transport through an ungated high electron mobility transistor and through an ungated field effect transistor are examined, Current versus voltage measurements in the dark reveal that the adsorbed molecules and their chemical nature have a pronounced effect on the structures' performance, as they reduce the current by up to one order of magnitude. The molecular specificity of the devices is expressed in the wavelength dependence of photo current decay. The decay time, which increases by several orders of magnitude upon adsorption of the molecules, changes drastically when the excitation wavelength matches the absorption of the adsorbed molecules. Effect of Cu ions caught by adsorbed organic molecules on the photo current decay is clearly demonstrated. The observations open new possibilities in constructing semiconductor based light and chemical sensors.
Cu diffusion in chalcopyrite CuInSe2 was studied directly, using Cu-64 as a radioactive tracer. For diffusion from a thin surface layer, the Cu diffusion coefficients at 380 and 430 degrees C, were found to vary from 10(-8) to 10(-9) cm(2)/s. In case of diffusion from a volume source at 400 degrees C, a value of 10(-10) cm(2)/s was calculated from diffusion profiles. Electromigration of Cu was demonstrated, by applying a strong electric field to a sample and following the redistribution of Cu-64, that had been thermally diffused into the sample, prior to electric field application. (C) 1997 American Institute of Physics. [S0021-8979(97)03321-5].
Polymer electrochemical cells with ion blocking electrodes were reported to emit light under applied voltage. This work analyzes the current-voltage relations, internal electric fields, and point defect distribution in the polymer. The polymer is regarded as a mixed-ionic-electronic conductor. Two relevant defect models are investigated, A goad fit is obtained between experimental data and theory which also takes into consideration electrode over potentials. (C) 1997 American Institute of Physics.
Control of the work function of GaAs single crystals, under ambient conditions, was achieved by chemisorption of a series of benzoic acid derivatives with varying dipole moments. Quantitative Fourier transform infrared spectroscopy shows that the benzoic acid derivatives bind as carboxylates, via coordination to oxidized Ga or As atoms, with a surface coverage of about one layer and a binding constant of 2.1 10(4) M(-1) for benzoic acid. Contact potential difference measurements reveal that molecules affect the work function by changing the electron affinity while band bending is not affected significantly. The direction of the electron affinity changes depends on the direction of the dipole moments, and the extent of the change increases linearly with the dipole's magnitude. Investigation of the surface composition by X-ray photoelectron spectroscopy shows that the etched surface, onto which the molecules adsorb, is covered by an oxide layer. This may prevent the molecules from affecting band bending.
Wavelength-dependent two-photon photoemission (WD-TPPE) spectroscopy was used to investigate the surface state properties of CdTe crystals before and after the adsorption of specially designed organic molecules. One photon was used to modify the population of the surface states and a second photon to eject electrons from the substrate. We measured the dependence of the photoemission signal on the energy of the first photon and on the delay between the two light pulses. The energy of surface states, relative to the bands, was found to correlate with the relaxation time of the semiconductor surface after being photoexcited. This is explained in terms of a simple kinetic model for electron transfer. These findings demonstrate that the properties of surface states of semiconductors can be manipulated by adsorbing suitable organic molecules on the semiconductor surface and that the WD-TPPE method is a useful tool for optoelectronic characterization of semiconductor surfaces, with sensitivity exceeding that of most commonly used techniques.
1996
Micrometer-sized homojunction structures can be formed by applying strong electric pulses, at ambient temperatures, to Li-doped, floating zone n-Si. Two such junctions, arranged back to back, act as a transistor, as evidenced by electron-beam-induced current and current-voltage measurements, The structures are created during a time ranging from similar to 100 ms to a few seconds, depending on the size of the structure. The phenomenon is similar to what was observed earlier in CuInSe2 and was explained there by thermally assisted electromigration of Cu. In the case of Si doped with Li we can use secondary-ion-mass spectrometry to detect the redistribution of Li after electric-field application. Such a redistribution is indeed found and corresponds to an n(+)-p-n structure with the p region extending at least similar to 20 mu m into the bulk of Si. Structures created in Si doped with Li in this way are stable for at least 13 months after their creation. We ascribe this to the large difference between Li diffusivity at the local temperature that is reached during structure formation (similar to 400 degrees C; 10(-8) cm(2)/s) and at room temperature (similar to 10(-15) cm(2)/s). (C) 1996 American Institute of Physics.
Electron transfer (ET) in organic-inorganic hybrid structures is of interest for applications in optoelectronics. The study of these hybrid structures is difficult because contact formation is often destructive. We have experimented with the lift-off/float-on technique to create metal contacts in a gentle manner. We present results of these experiments and initial data on silicon/octadecyl trichlorosilane (OTS)/silver junctions where the metal contact was prepared by evaporation. The presence of the OTS greatly affects the current-voltage characteristics of such a junction.
A number of configurations can be used to form p-n junctions in semiconductors, by applying an electrical potential difference to them under conditions where dopants, native or foreign, show ionic conductivity, In all these cases the electrical potential difference guides the dopants to create compositional inhomogeneities. This can lead to actual type conversion and thus to p-n junction formation, Junction formation can be localized on a scale that is small compared to the sample size, by working under conditions far from equilibrium and by limiting thermal effects.
A p-n junction is a stable situation for electronic carriers, but not for those dopants that are the cause of the junction. Thus the junction is stabilized only kinetically against equilibration of the dopant concentrations due to the electrical and chemical potential gradients that reign in the depletion regions that are associated with the junction. The situation changes, though, when a dopant can be present in two forms, with opposite effective charges, with the majority form being responsible for doping and the minority one for drifting. Then the electrical potential gradient can actually stabilize the junction. Ag, which acts as an acceptor in (Hg,Cd)Te, is an example of such a dopant. Silver creates a p-n junction in Cd-rich n-(Hg,Cd)Te. We show that this junction is capable of restoring itself after being smeared out by small electrical or thermal perturbations. This behaviour suggests that we have a thermodynamically, rather than a kinetically stabilized junction. It indicates that Ag dissolution in MCT strongly deviates from ideal behaviour. Reasons for this non-ideality are suggested.
Silver diffusion in CdxHg1-xTe was investigated as a function of Fermi level position and of mercury content. Silver diffusion increases with increasing mercury content and hole concentration. While in CdTe Ag diffusion at 200 degrees C dopes n-type, in CdxHg1-xTe with x = 0.55-0.8, Ag diffusion below 125 degrees C dopes p-type. We explain these findings by silver-mercury complex formation.
The effect of air annealing on state-of-the-art, solar-cell-quality CdS/Cu(In,Ga)Se-2 heterojunctions has been studied using contact potential difference and surface photovoltage measurements. The annealing treatment is shown to have no significant effect on the band lineup of the heterojunction. However, the surface photovoltage spectral response increases markedly upon air annealing. These results can be reconciled if air annealing of the junctions leads mainly to elimination of recombination centers, rather than to changes in the built-in voltage or in the band lineup. We also show that ZnO deposition has an effect on the surface photovoltage that is similar to that of air annealing.
We have measured the widths of the transition regions at p-n-p junctions that are formed on CuxAg1-xInSe2 by high electric field at room temperature, by using a scanning tunneling microscope with capacity for measuring current-voltage curves on physical contact. We find marked transition regions of low conductivity with widths in the range of 1.3-5 mu m. This shows that the junction created by the electromigration mechanism in this material, while diffuse by the standards of those produced by high-temperature or high-energy methods, are remarkably sharp by solid-state ionic measures. (C) 1996 American Institute of Physics.
Real space, potential energy level diagrams of electrons ("band diagrams") are useful for describing devices, i.e. structures with spatially varying electronic carrier concentration. They help us to visualize situations in semiconductor materials and devices, without the need for calculations. Diagrams with the same function can be conceived of for ions in structures and devices with ionic conductivity. Such diagrams could be especially useful for describing the dynamic behaviour of systems with both ionic and electronic conductivity, such as devices incorporating semionic materials. We show how such diagrams can be constructed and indicate how their use can add to our understanding of the behaviour of mixed conductors through qualitative descriptions of processes that occur in them. We illustrate their use for a few specific cases, such as electrochromic and light emitting devices.
1995
Fourier transform infrared spectroscopy shows that benzoic acid and its derivatives can bind chemically to the surfaces of CdSe. The dipole moment of the adsorbed benzoate correlates linearly with changes in the semiconductor work function, as determined by vibrating capacitor (Kelvin probe) measurements. Because ligand adsorption does not induce significant changes in surface photovoltage, we conclude that changes in work function are due to changes in electron affinity rather than in band bending. This means that ligand adsorption does not induce charge transfer between the surface and the semiconductor but rather adds a surface dipole. Changes in band bending do occur, however, upon conventional etching.
In view of our recent experimental finding of self-restoration of p/n junctions in Ag-doped (Cd,Hg)Te after their electrical or thermal perturbation, we ask the question if, and if so, when can, a mixed electronic semiconductor/ionic conductor support a built-in electric field. The question is of interest because common p/n junctions are merely kinetically stabilized systems. We study the problem by deriving the thermodynamically stable states of mixed conductors. This shows that (1) as long as all components of a multicomponent system behave ideally, no stable concentration gradient and built-in field may exist; (2) a thermodynamically stable concentration gradient and thus a built-in field can exist in a multicomponent system, if at least one of its components behaves nonideally (and thus, from the Gibbs-Duhem relation, at least one additional component must behave nonideally, too); and (3) the likelihood of finding a thermodynamically stable concentration gradient increases with the number of components of the system. While the first of these results is intuitively obvious, the rigorous proof given here is necessary to deduce that actual observation of self-restoration of p/n junctions implies nonideal behavior of at least two of the mobile species in the system. We show that our results can be used to derive the built-in electric field for a given variation of activity coefficients of one or more of the mobile species and vice versa.
While a p-n junction is a stable situation for electronic carriers, it represents an unstable one for the very dopants that create the junction, i.e., the junction is only kinetically stabilized against equilibration of the dopant concentrations in the chemical and electrical potential gradients in the junction region. However, when a dopant migrates with a charge opposite to the effective one that it has as a dopant, the electrical potential gradient, instead of destabilizing, can now help to stabilize the junction. Ag, which acts as an acceptor in (Hg,Cd)Te, is an example of such a dopant. We show here that in Cd-rich n-(Hg,Cd)Te, Ag creates a p-n junction that is capable of restoring itself after being smeared out by small perturbations. This behavior is inconsistent with pure kinetic stabilization of the junction and indicates that AE dissolution in (Hg,Cd)Te strongly deviates from ideal behavior. Reasons for this nonideality are suggested. (C) 1995 American Institute of Physics.
Contact potential difference measurements in the dark and under illumination are used to derive the conduction band offset (Delta E(c)) in a solar cell quality junction formed by chemical bath deposition of CdS on a polycrystalline thin film of Cu(In,Ga)Se-2. Our experimental measurements and the estimates made for dipole contributions show that the junction is of type II, i.e., without a spike in the conduction band (Delta E(c) = 80 meV +/- 100 meV). This is consistent with the high performance of the actual solar cell. However, it differs from most previous results on junctions based on single crystals and/or vacuum deposited CdS, which indicated the existence of a conduction band spike. (C) 1995 American Institute of Physics.
Application of strong electric fields at ambient temperatures to crystals of CuInSe2 and (Cu,Ag)InSe2 semiconductors can create non-equilibrium doping profiles, stable after removal of the electric field, as illustrated by formation of mu m-sized single and multiple diode structures in initially homogeneous and uniformly doped single crystals. Phototransistor action and amplification was obtained, clear evidence for the presence of junctions, resulting from non-equilibrium doping profiles. Electron beam-induced current measurements, combined with current-voltage, capacitance-voltage and time-dependent current measurements, as well as numerical simulations were performed to characterize and understand the phenomena. Control experiments exclude formation of extended defects or the occurrence of contact diffusion. Localized Joule heating that occurs around the contact cannot by itself account for the observed phenomena. Because these chalcopyrites contain relatively mobile components [Cu,Ag], which are also dopants, we interpret these observations as a result of internal dopant redistribution, aided by localized temperature increases and directed by the electric field.
Communication: Light emitting diodes where the efficiency of the junction electroluminescence has been improved over devices fabricated using thermal in-diffusion methods, is demonstrated for structures such as that shown in the figure, which is an electric-field-induced device. As E-field produced transistors are already available, combined monolithic LED/transistor structures produced using E-field-induced doping of semiconductors could be possible.
1994
Controlled surface modification of CdTe single crystals and CdTe and CuInSe2 solar cell quality thin films was achieved by chemisorption of a series of organic ligands with varying dipole moments. Contact potential difference measurements in air showed that adsorption of benzoic or hydroxamic acid derivatives on the thin films or crystals changes the semiconductors' electron affinity without significantly affecting band bending. The magnitude and direction of surface potential changes, which reach 670 mV between extreme modifications, correlate with the ligands' dipole moments. Ligand dipole moments were controlled by varying the substituents of the ligand. Quantitative Fourier transform infrared (FTIR) spectroscopy showed that benzoic acid surface coverage is about one monolayer. Finally, FTIR spectral analysis showed that the benzoic acid derivatives adsorb via coordination to Cd on CdTe and that hydroxamic acids bind to Cd on CdTe and to In on CuInSe2. These phenomena occur in several systems (two semiconductor compounds, two types of binding groups, and two types of surface morphologies were examined) and may prove useful in band edge engineering.
Surface photovoltage spectroscopy has been used as a clear, simple method to identify the two polar faces [(111) and (111BAR)] of undoped CdTe. The difference in electronic structure of the two faces is clearly observed in air on polished untreated samples. The (111BAR)Te surface is characterized by an acceptor level, at an energy 1.17 eV below the conduction-band minimum, which is assumed to result from TeO2-CdTe interaction. The (111)Cd surface is distinguished by two additional donor levels, at 1.11 and 1.33 eV above the valence-band maximum, which seem to be due to Cd surface atom displacements, accompanying the Te oxidation. These assignments are supported by the results obtained after various chemical treatments.
Local p-n and p-n-p junction structures can be formed under room-temperature conditions, in CuInSe2 and related materials solely by applying strong electric fields through small contacts. Electromigration of native Cu ions, which was suggested as the mechanism for type conversion, assumes an enhancement in ion mobility of several orders of magnitude. Electric-field-induced local heating was given as one possible cause for such enhancement [Cahen et al., Science 258, 271 (1992)]. Therefore, we have measured the average temperature of and around the contacts to CuInSe2 and Cu0.95Ag0.05InSe2 crystals, during application of the electric field. The measurements were done as a function of the active power dissipated in the system, using two different techniques, viz. infrared emission and contact melting. We find that the temperature around the contact, during the tens of ms of actual structure formation (210-320-degrees-C), is insufficient for significant thermal diffusion. We conclude that electromigration is the dominant mechanism.
The electron transfer through an organized organic monolayer of alkyl chains adsorbed on a silicon wafer has been studied. The silicon was used as an electrode in a three-electrode electrochemical cell, and the current versus voltage response was measured. The results show that when the chains in the monolayer are in the ''all trans'' configuration, the charge transfer efficiency is higher than when the chains have a ''gauche'' configuration. A mechanism rationalizing all the observations is suggested.
1993
We report here on the optimization of ohmic contacts to p-CuInSe2 (CISe) single crystals. A low resistance ohmic contact is required to minimize current losses due to series resistance; e.g. in Schottky diodes. Both In-Ga (eutectic)/CISe and gold (evaporated)/CISe contacts have been fabricated on crystals with different orientations and bulk properties. Gold contacts were found to have a lower resistance and to be more stable than In-Ga ones, from the slope of the linear current-voltage plot of the junctions. The resistance of the Au/CISe ohmic contact was decreased by etching the CISe crystal surface chemically in a 0.5% solution of Br2 in methanol for 30 sec at room temperature, prior to gold deposition, while that of the In-Ga contact increased by this etch. Wetting experiments and contact angle measurements showed evidence for changes in the polarity of the surface due to chemical etches.
YBa2Cu3O7 (1237) was reduced and reoxidized at room temperature (RT), by using wet electrochemistry to extract, or solid state electrochemistry to re-insert oxygen. With thin films this led to homogeneous products, as judged by X ray diffraction and temperature dependence of electrical resistivity. Because reduction leads to loss of superconductivity and re-oxidation restores it, this method allows room temperature control over superconducting properties of (parts of) films and, thus, can be used for patterning of (1237) thin films. We showed this by preparing SNS-like structures by this method. The method affords control not only over bulk properties, but also over the quality of the intergranular contact, possibly via control of oxygen concentration and ordering in the outermost layers of grains (in films and pellets). The results imply rapid, field-assisted, oxygen motion and this was confirmed by independent measurements.
YBa2Cu3O7 (1237) was reduced and reoxidized at room temperature (RT), by using wet electrochemistry to extract, or solid state electrochemistry to re-insert oxygen. With thin films this led to homogeneous products, as judged by X ray diffraction and temperature dependence of electrical resistivity. Because reduction leads to loss of superconductivity and re-oxidation restores it, this method allows room temperature control over superconducting properties of (parts of) films and, thus, can be used for patterning of (1237) thin films. We showed this by preparing SNS-like structures by this method. The method affords control not only over bulk properties, but also over the quality of the intergranular contact, possibly via control of oxygen concentration and ordering in the outermost layers of grains (in films and pellets). The results imply rapid, field-assisted, oxygen motion and this was confirmed by independent measurements.
YBa2Cu3O7 (1237) was reduced and reoxydated quantitatively, in a controlled manner, at room temperature (RT),by way of extraction or insertion of oxygen, using an electrochemical set-up. RT reduction and reoxygenation of thin films, which led to homogeneous products, as judged by X ray diffraction. Since reduction leads to loss of superconductivity and re-oxidation restores it, this method allows room temperature control over superconducting properties of (parts of) films. This permits patterning of (1237) thin films. SNS-like structures were already prepared by this method. The method affords control not only over n(E(F)) via [oxygen]bulk, but also over the quality of the intergranular contact, possibly via control of [oxygen] in the outermost layers of grains (in films and pellets).
Solar cells based on CuInSe2 polycrystalline thin films (see Figure) are one of the few realistic alternatives to polycrystalline Si for practical conversion of solar energy into electricity. A model explaining the important role of the secondary copper chalcogenide phases in the deposition of the CuInSe2 films by physical vacuum evaporation is presented.
Semionic behaviour is demonstrated in certain ternary and multinary semiconductors, by following the effects of application of external electric fields at ambient temperature. We find that this can lead to stable, local changes in their microchemical composition and, via resulting changes in carrier concentration, in their electronic properties. Thus, actual device structures are embedded in the material. We summarize these results and our understanding of the mechanisms involved.
Impedance measurements were used to evaluate the relative band edge positions of single crystal p-CuInSe2 electrodes in various aqueous electrolytes, by measuring the extrapolated flatband potentials, V(fb). We find that V(fb) can be shifted, depending on the extent of the potential scan and on the pH of the electrolyte used, over a range of up to 1.7 V (between pH 0-pH 14). In the pH range 0-6, V(fb) can be fixed at intermediate values, which, in their turn, are determined by the pH of the electrolyte.
The interaction between a chalcogenide semiconductor surface and a specific chelating ligand was studied by a number of complementary spectroscopic methods (UV/VIS, FTIR, XPS). FTIR suggests that the chelating ligand (diphenyl hydroxamic acid) complexes an In3+ ion in CuInSe2, and a Cd2+ ion in CdTe, accompanied by the loss of a proton. Contact potential measurements showed that the adsorbed ligand changes the semiconductor electron affinity without significantly influencing the band bending. On the basis of these and other results, we suggest that the molecular dipole of the chelating ligand is responsible for the change in surface potential. Because this dipole can be modified without changing the ligand's binding group, this finding opens the way to control surface potential by varying the dipole moment of the adsorbed ligand without changing the binding functional group.
The interaction between a chalcogenide semiconductor surface and a specific chelating ligand was studied by a number of complementary spectroscopic methods (UV/VIS, FTIR, XPS). FTIR suggests that the chelating ligand (diphenyl hydroxamic acid) complexes an In3+ ion in CuInSe2, and a Cd2+ ion in CdTe, accompanied by the loss of a proton. Contact potential measurements showed that the adsorbed ligand changes the semiconductor electron affinity without significantly influencing the band bending. On the basis of these and other results, we suggest that the molecular dipole of the chelating ligand is responsible for the change in surface potential. Because this dipole can be modified without changing the ligand's binding group, this finding opens the way to control surface potential by varying the dipole moment of the adsorbed ligand without changing the binding functional group.
Semionic behaviour is demonstrated in certain ternary and multinary semiconductors, by following the effects of application of external electric fields at ambient temperature. We find that this can lead to stable, local changes in their microchemical composition and, via resulting changes in carrier concentration, in their electronic properties. Thus, actual device structures are embedded in the material. We summarize these results and our understanding of the mechanisms involved.
1992
On the basis of literature data of thermodynamic quantities and functions for species that can be involved in the preparation of thin films of CuInSe2, we calculate free energies for a number of possible reactions. The reactions that are considered are especially relevant for the three-source vacuum evaporation process and for selenization of Culn alloys. Reactions of species that can be present in the gas phase, with oxygen, are also considered. Where possible, free energies of reaction are calculated at temperatures relevant for these preparation processes. In some cases, only enthalpies of reaction could be given. We include a compilation of free energies and enthalpies of formation for I-III-VI2 compounds and related binary chalcogenides. This can help future calculations of the type presented here for other I-III-VI2 compounds.
Quantitative data are presented that show partial ionic conductivity of Cu or Ag in ternary and quaternary electronic semiconductors, with idealized stoichiometry CuxAg1-xInSe2. A trend of increasing facility of ionic motion with increasing Ag content was observed. Ionic transference numbers up to 0.13 and 0.55 were measured for CuInSe2 and AgInSe2, respectively. This trend can be correlated with the degree of compactness of the structure. It is supported by results from measurements of effective values of chemical diffusion coefficients, obtained by a potentiostatic current decay technique. Those results show a generally higher diffusivity in AgInSe2 than in CuInSe2. A clear trend of increasing diffusion coefficient (up to 10(-7) cm2/s) with decreasing concentration of IB metal was observed. No obvious general correlation is seen between net electronic carrier concentration (or resistivity) and diffusion coefficients, except that overall the highest diffusion coefficients are found for Cu-poor (or Ag-poor) samples which are also the most resistive. The effect of temperature (between 20 and 100-degrees-C) on the diffusivity is small. On the basis of our observations we conclude that diffusion occurs predominantly via a vacancy mechanism and suggest that this possibility of coexistence of significant ionic mobility with true semiconductivity can be useful for electronic doping by native defects.
Electronic properties of initially homogeneous (Hg,Cd)Te samples have been modified on a local scale, in a stable manner at room temperature, by reverse biasing of small-area Schottky contacts on them. This was shown, after the bias voltage had been lifted, by current-voltage measurements and by electron beam-induced current scans. The creation of a clear diodelike structure in the vicinity of the Schottky contact on a scale of about hundred mum could be explained by electromigration of electrically active ions and/or by generation of point and line defects. The latter type of defect was revealed by chemical etch after application of the field.
Multiple-junction structures were formed, on a microscopic scale, at room temperature, by the application of a strong electric field across originally homogeneous crystals of the ternary chalcopyrite semiconductor CuInSe2. After removal of the electric field, the structures were examined with electron beam-induced current microscopy and their current-voltage characteristics were measured. Bipolar transistor action was observed, indicating that sharp bulk junctions can form in this way at low ambient temperatures. The devices are stable under normal (low-voltage) operating conditions. Possible causes for this effect, including electromigration and electric field-assisted defect reactions, are suggested.
1991
On the basis of literature data of thermodynamic quantities and functions for species that can be involved in the preparation of thin films of CuInSe2, we calculate free energies for a number of possible reactions. The reactions that are considered are especially relevant for the three-source vacuum evaporation process and for selenization of CuIn alloys. Reactions of species that can be present in the gas phase, with oxygen, are also considered. Where possible, free energies of reaction are calculated at temperatures relevant for these preparation processes. In some cases, only enthalpies of reaction could be given. We include a compilation of free energies and enthalpies of formation for I-III-VI2 compounds and related binary chalcogenides. This can help future calculations of the type presented here for other I-III-VI2 compounds.
We present a summary of our defect chemical microscopic model for the effect that annealing in air or oxygen has on CuInSe2 and CdTe-based polycrystalline thin film solar cells and explain its generalization to other chalcogenide-based semiconductor devices. The summary includes a hypothesis for specific O2 (molecule) and surface interaction From the point of view of device performance, the model provides a specific chemical explanation for the conclusions obtained from device analyses that the performance of the present generation of polycrystalline cells of this type is mainly limited by recombination at grain surfaces and boundaries.
The oxygen content of polycrystalline samples of YBa2Cu3O7-x can be reduced quantitatively, in a controlled fashion, by electrochemical techniques at room temperature in propylene carbonate. Upon reduction, the propylene carbonate undergoes an unusual reaction at the YBa2Cu3O7-x cathode to produce propanal, apparently because of the production of an active oxygen species on the surface. The reduced materials have been characterized by X-ray powder diffraction, electrical resistivity and magnetic susceptibility. The large-grained, reduced pellets are found to be inhomogeneous with respect to x. The reduced materials exhibit a broadened transition to the superconducting state. This effect is ascribed to the formation of metastable phases formed during reduction. After a low-temperature anneal, 80, 60 and 20 K transition temperatures are observed. These results indicate that T(c) is a continuous function of oxygen content, but a discontinuous function of oxygen ordering.
Diffusion of oxygen at room temperature in polycrystalline pellets and thin films of YBa2Cu3O7-x (123) is measured from the current decay at constant potential in an electrochemical cell with a liquid electrolyte, using 123 as the cathode. The effective chemical diffusion coefficient is found to be 10(-11)-10(-12)cm2/s, thus explaining the relatively facile movement of oxygen in such samples.
Energy storage measurements by modulated photothermal radiometry (PTR) were carried out on intact leaves to assess the value of the PTR method for photosynthesis research. In particular, correlations to the redox state of P700 under various conditions were examined. PTR monitors modulated light conversion to heat by sensing the resulting modulated infra-red radiation emitted from the leaf. It is, therefore, a complementary method to photoacoustics for estimating energy storage and its time variation, particularly under controlled leaf atmosphere. With modulated light-1 (lambda > 690 nm) the energy storage approached zero and P700 was maximally oxidized. When background light of shorter wavelength (lambda <690 nm-light-2) was added, energy storage momentarily increased (a manifestation of Emerson enhancement) while P700 was reduced. The values of both parameters varied as a function of the background light intensity, keeping a mutual linear relationship. Following the initial change, there was a slow reversal transient of P700 oxidation with a parallel decrease in energy storage. Temporal correlation to P700 redox state after dark adaptation was observed also for the energy storage measured in modulated light 2 when combined with background actinic light of medium intensity (about 50 W m2). Under these circumstances P700 was almost totally oxidized initially and then gradually reduced while energy storage was initially low and then increased parallel to P700 reduction. A comparison between the maximum energy storage in modulated light 1, enhanced by background light 2, to the energy storage with short wavelength light (where light tends to be more evenly distributed) indicates a comparable contribution to energy storage from each active photosystem. The above experiments indicate that energy storage contribution from PS I is directly related to the extent of openness of its reaction-centers. While some aspects of the data call for more experimentation, these expe