Publications

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 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.

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.

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.

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.

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.

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 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 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.

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.

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.

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.

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.

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.

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.

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.

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.

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 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.

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.

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.

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.

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

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.

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.

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.

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].

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.

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.

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.

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.

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.

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.

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.

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].

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.

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.

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 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.

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.

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.

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.

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].

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.

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 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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.