Publications

The fundamental question of \u201cwhat is the transport path of electrons through proteins?\u201d initially introduced while studying long-range electron transfer between localized redox centers in proteins in vivo is also highly relevant to the transport properties of solid-state, dry metalproteinmetal junctions. Here, we report conductance measurements of such junctions, Au-(Azurin monolayer ensemble)-Bismuth (Bi) ones, with well-defined nanopore geometry and ~10³ proteins/pore. Our results can be understood as follows. (1) Transport is via two interacting conducting channels, characterized by different spatial and time scales. The slow and spatially localized channel is associated with the Cu center of Azurin and the fast delocalized one with the proteins polypeptide matrix. Transport via the slow channel is by a sequential (noncoherent) process and in the second one by direct, off-resonant tunneling. (2) The two channels are capacitively coupled. Thus, with a change in charge occupation of the weakly coupled (metal center) channel, the broad energy level manifold, responsible for off-resonance tunneling, shifts, relative to the electrodes Fermi levels. In this process, the off-resonance (fast) channel dominates transport, and the slow (redox) channel, while contributing only negligibly directly, significantly affects transport by intramolecular gating.

The term defect tolerance (DT) is used often to rationalize the exceptional optoelectronic properties of halide perovskites (HaPs) and their devices. Even though DT lacked direct experimental evidence, it became a "fact" in the field. DT in semiconductors implies that structural defects do not translate to electrical and optical effects (e.g., due to charge trapping), associated with such defects. We present pioneering direct experimental evidence for DT in Pb-HaPs by comparing the structural quality of 2-dimensional (2D), 2D-3D, and 3D Pb-iodide HaP crystals with their optoelectronic characteristics using high-sensitivity methods. Importantly, we get information from the materials' bulk because we sample at least a few hundred nanometers, up to several micrometers, from the sample's surface, which allows for assessing intrinsic bulk (and not only surface-) properties of HaPs. The results point to DT in 3D, 2D-3D, and 2D Pb-HaPs. Overall, our data provide an experimental basis to rationalize DT in Pb-HaPs. These experiments and findings will help the search for and design of materials with real DT.

Self-healing (SH) of (opto)electronic material damage can have a huge impact on resource sustainability. The rising interest in halide perovskite (HaP) compounds over the past decade is due to their excellent semiconducting properties for crystals and films, even if made by low-temperature solution-based processing. Direct proof of self-healing in Pb-based HaPs is demonstrated through photoluminescence recovery from photodamage, fracture healing and their use as high-energy radiation and particle detectors. Here, the question of how to find additional semiconducting materials exhibiting SH, in particular lead-free ones is addressed. Applying a data-mining approach to identify semiconductors with favorable mechanical and thermal properties, for which Pb HaPs are clear outliers, it is found that the Cs₂Au^IAu^IIIX₆, (X = I, Br, Cl) family, which is synthesized and tested for SH. This is the first demonstration of self-healing of Pb-free inorganic HaP thin films, by photoluminescence recovery.

The class of materials termed halide perovskites has experienced a meteoric rise in popularity due to their potential for photovoltaic and related applications, rivaling the well-established silicon devices within a few short years of development. These materials are characterized by several intriguing properties, among them their mechanical behavior. The study of their response to stress is essential for proper device development, while being of fundamental scientific interest in its own right. In this perspective, we highlight the key concerns surrounding this topic, critically analyzing the measurement techniques and considering the challenges in the current level of understanding.

Two-dimensional (2D) halide perovskites, HaPs, can provide chemical stability to three-dimensional (3D) HaP surfaces, protecting them from exposure to ambient species and from reacting with contacting layers. Both actions occur with 2D HaPs, with the general stoichiometry R2PbI4 (R: long or bulky organic amine) covering the 3D ones. Adding such covering films can also boost power conversion efficiencies of photovoltaic cells by passivating surface/interface trap states. For maximum benefit, we need conformal ultrathin and phase-pure (n = 1) 2D layers to enable efficient tunneling of photogenerated charge carriers through the 2D film barrier. Conformal coverage of ultrathin (

DOI: 10.1002/adfm.202204283 The following funding information is added to the Acknowledgments: This project received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 893194. These errors do not affect the conclusions of the report. The authors apologize for any inconvenience caused.

We demonstrate that the direction of current rectification via one of natures most efficient light-harvesting systems, the photosystem 1 complex (PS1), can be controlled by its orientation on Au substrates. Molecular self-assembly of the PS1 complex using four different linkers with distinct functional head groups that interact by electrostatic and hydrogen bonds with different surface parts of the entire protein PS1 complex was used to tailor the PS1 orientation. We observe an orientation-dependent rectification in the currentvoltage characteristics for linker/PS1 molecule junctions. Results of an earlier study using a surface two-site PS1 mutant complex having its orientation set by covalent binding to the Au substrate supports our conclusion. Currentvoltagetemperature measurements on the linker/PS1 complex indicate off-resonant tunneling as the main electron transport mechanism. Our ultraviolet photoemission spectroscopy results highlight the importance of the protein orientation for the energy level alignment and provide insight into the charge transport mechanism via the PS1 transport chain.

The development of vacuum-deposited perovskite materials and devices is partially slowed down by the minor research effort in this direction, due to the high cost of the required research tools. But there is also another factor, thermal co-deposition in high vacuum involves the simultaneous sublimation of several precursors with an overall deposition rate in the range of few Å s⁻¹. This leads to a deposition time of hours with only a single set of process parameters per batch, hence to a long timeframe to optimize even a single perovskite composition. Here we report the combinatorial vacuum deposition of wide bandgap perovskites using 4 sources and a non-rotating sample holder. By using small pixel substrates, more than 100 solar cells can be produced with different perovskite absorbers in a single deposition run. The materials are characterized by spatially resolved methods, including optical, morphological, and structural techniques. By fine-tuning of the deposition rates, the gradient can be altered and the best-performing formulations in standard depositions with rotation can be reproduced. This is viewed as an approach that can serve as a basis to prototype other compositions, overcoming the current limitations of vacuum deposition as a research tool for perovskite films.

Halide perovskites (HaPs) are functional semiconductors that can be prepared in a simple, near-room-temperature process. With thin polycrystalline HaP films, excellent solar cells, light-emitting diodes (LEDs), and (also as single crystals) highenergy radiation detectors have been demonstrated. The very low single-crystal defect densities make HaP thin single crystals (TSCs), instead of polycrystalline HaP films an attractive option, to boost device performances and for fundamental research. However, growing TSCs is challenging primarily because of random multiple nucleations, which, in the often-used space-confined geometry, is favored at the substrate boundaries, where loss of organo-amines and solvents occurs. We show that fewer and better quality thin crystals nucleate and grow reproducibly away from the substrate edges in the substrate center, if we localize the heating (needed for inverse-temperature crystallization, the preferred crystal growth method) there. Using a further finding of ours that lowers the crystallization temperature, TSCs of methylammonium lead bromide (MAPbBr3), the HaP we focus on here, grow also directly on flexible substrates. 1H NMR measurements show how the observed lower crystallization temperature results from slow humidity-mediated chemical changes in the HaP precursor solution during its storage.

An electrocatalyst composed of RuO₂ surrounded by interfacial carbon, is synthesized through controllable oxidization-calcination. This electrocatalyst provides efficient charge transfer, numerous active sites, and promising activity for pH-universal electrocatalytic overall seawater splitting. An electrolyzer with this catalyst gives current densities of 10 mA cm⁻² at a record low cell voltage of 1.52 V, and shows excellent durability at current densities of 10 mA cm⁻² for up to 100 h. Based on the results, a mechanism for the catalytic activity of the composite is proposed. Finally, a solar-driven system is assembled and used for overall seawater splitting, showing 95% Faraday efficiency.

The environment humidity effects on performance of halide perovskites (HaPs), especially MAPbI3, are known. Nevertheless, it is hard to find direct experimental evidence of H2O in the bulk materials at the levels lower than that of Monohydrate (MAPbI3.H2O). Here, for the first time, direct experimental evidence of water being released from bulk (µms deep) of MAPbI3 single crystal is reported. The thermogravimetric analysis coupled with mass spectrometry (TGAMS) of evolved gases is used to detect the MS signal of H2O from the penetrable depth and correlate it with the TGA mass loss due to H2O leaving the material. These measurements yield an estimate of the average H2O content of 1 H2O molecule per three MAPbI3 formula units (MAPbI3.0.33H2O). Under the relatively low temperature conditions no other evolved gases that can correspond to MAPbI3 decomposition products, are observed in the MS. In addition to being direct evidence that there is H2O inside MAPbI3, the data show that H2O diffuses into it. With this article, a solid basis is proved for further studies on the mechanisms through which water modifies the properties of MAPbI3 and all the other halide perovskites.
Direct evidence of release of H2O from bulk MAPbI3, under the conditions where the MAPbI3 crystal structure is intact and with an indication of a H2O gradient of MAPbI3.xH2O with x=1 at the surface to x=0 in the bulk.

The future of halide perovskites (HaPs) is beclouded by limited understanding of their long-term stability. While HaPs can be altered by radiation that induces multiple processes, they can also return to their original state by \u201cself-healing.\u201d Here two-photon (2P) absorption is used to effect light-induced modifications within MAPbI₃ single crystals. Then the changes in the photodamaged region are followed by measuring the photoluminescence, from 2P absorption with 2.5 orders of magnitude lower intensity than that used for photodamaging the MAPbI₃. After photodamage, two brightening and one darkening process are found, all of which recover but on different timescales. The first two are attributed to trap-filling (the fastest) and to proton-amine-related chemistry (the slowest), while photodamage is attributed to the lead-iodide sublattice. Surprisingly, while after 2P-irradiation of crystals that are stored in dry, inert ambient, photobrightening (or \u201clight-soaking\u201d) occurs, mostly photodarkening is seen after photodamage in humid ambient, showing an important connection between the self-healing of a HaP and the presence of H₂O, for long-term steady-state illumination, practically no difference remains between samples kept in dry or humid environments. This result suggests that photobrightening requires a chemical-reservoir that is sensitive to the presence of H₂O, or possibly other proton-related, particularly amine, chemistry.

Attempts to dope halide perovskites (HaPs) extrinsically have been mostly unsuccessful. Still, oxygen (O2) is an efficient pdopant for polycrystalline HaP films. To an extent, this doping is reversible, i.e., the films can be dedoped by decreasing the O2 partial pressure. Here results are reported, aimed at understanding the mechanism of such reversible doping, as it has been argued that doping involves interaction of oxygen with defects inside bulk HaP. These experimental results clearly point out that O2surface interactions suffice to dope the bulk of the films. Such behavior fits what is known for other polycrystalline semiconductors, where surface charge transferadducts can form and be removed. Thus, controlling the O2 partial pressure to which the HaP film is exposed, can, after proper encapsulation, achieve the desired bulk doping of the film.

Adding a 2D character to halide perovskite (HaP) active layers in ambient-protected cells can improve their stability drastically, which is not obvious from the hydrophobicity of the large cations that force the HaP into a 2D structure. Results of two-photon confocal microscopy are reported to study inherent photo-stability of 2D Pb iodide HaPs in the interior of single crystals. Compared to 3D HaP crystals, 2D ones have higher photo-stability and, under a few sun-equivalent conditions, self-heal efficiently after photo-damage. Using both photoluminescence (PL) intensities (as function of time after photo-damage) and spectra, self-healing dynamics of 2D HaP (C4H9NH3)(2)PbI4, 2D/3D (C4H9NH3)(2)(CH3NH3)(2)Pb3I10 and 3D MAPbI(3) are compared. Differences in response to photo-damage and self-healing ability from different degrees of photo-damage are found between these HaPs. Based on the findings, a possible chemical mechanism for photo-damage and self-healing of the 2D HaPs is suggested: the layered lattice arrangement limits out-diffusion of degradation products, facilitating damage reversal, leading to better 2D HaP photo-stability and self-healing uniformity than for 2D/3D HaPs. One implication of the layered structures' resilience to photo-damage is transfer of their increased stability to devices made with them, such as photovoltaic solar cells and light-emitting diodes.

Considering the toxicity of lead ions, substituting Pb with nontoxic elements in halide perovskites, HaPs, has become one of the most significant challenges associated with these materials. Here, we report on replacing Pb with Sn and Ge, focusing on an all-inorganic HaP, CsSn x Ge1x Br3, and using a multihead spray deposition setup for thin-film formation to overcome the low solubility of the precursors and improve film coverage. We find that, in this way, we can form CsSn x Ge1x Br3 films up to high x values as homogeneous solid solutions; i.e., we obtain a range of compositions with one crystal structure (rather than clusters of two phases). The cubic structure of pure CsSnBr3 is maintained up to 77 atom % Ge, with the lattice spacing decreasing with increasing Ge concentration. The optical band gap is tunable between 1.8 and 2.5 eV, from pure Sn to pure Ge HaP. Most importantly, the perovskite structural stability increases with increasing concentration of Ge, with less oxidation of both Ge and Sn to the +4 state, which can be ascribed to less octahedral tilting and stronger bonding. Electrical and electronic transport measurements show the potential of these materials as Pb-free absorbers for solar cells, particularly, given their band gap range as the top cell of a tandem photovoltaic device.

Among many riddles posed by halide perovskites, the surprising apparent near-absence of harmful defects stands out. This is commonly explained by invoking defect tolerance (DT), but the term is used loosely, sometimes interchangeably with self-healing (SH). Also, the relation between underlying physical and chemical mechanisms and device behavior is often murky. Here, we offer our views as to what DT and SH constitute, the evidence for and against them, and what research challenges remain.

We find significant differences between degradation and healing at the surface or in the bulk for each of the different APbBr3 single crystals (A = CH3NH3+, methylammonium (MA); HC(NH2)2+, formamidinium (FA); and cesium, Cs+). Using 1- and 2-photon microscopy and photobleaching we conclude that kinetics dominate the surface and thermodynamics the bulk stability. Fluorescence-lifetime imaging microscopy, as well as results from several other methods, relate the (damaged) state of the halide perovskite (HaP) after photobleaching to its modified optical and electronic properties. The A cation type strongly influences both the kinetics and the thermodynamics of recovery and degradation: FA heals best the bulk material with faster self-healing; Cs+ protects the surface best, being the least volatile of the A cations and possibly through O-passivation; MA passivates defects via methylamine from photo-dissociation, which binds to Pb2+. DFT simulations provide insight into the passivating role of MA, and also indicate the importance of the Br3- defect as well as predicts its stability. The occurrence and rate of self-healing are suggested to explain the low effective defect density in the HaPs and through this, their excellent performance. These results rationalize the use of mixed A-cation materials for optimizing both solar cell stability and overall performance of HaP-based devices, and provide a basis for designing new HaP variants.

Direct detection of intrinsic defects in halide perovskites (HaPs) by standard methods utilizing optical excitation is quite challenging, due to the low density of defects in most samples of this family of materials (≤1015 cm-3 in polycrystalline thin films and ≤1011 cm-3 in single crystals, except melt-grown ones). While several electrical methods can detect defect densities 2 eV) HaPs. By measuring HaP layers on both hole- and electron-contact layers, as well as single crystals without contacts, we conclude that the observed deep defects are intrinsic to the Br-based HaP, and we propose a passivation route via the incorporation of a 2Dforming ligand into the precursor solution.

We observe reversible, bias-induced switching of conductance via a blue copper protein azurin mutant, N42C Az, with a nearly 10-fold increase at |V| > 0.8 V than at lower bias. No such switching is found for wild-type azurin, WT Az, up to |1.2 V|, beyond which irreversible changes occur. The N42C Az mutant will, when positioned between electrodes in a solid-state AuproteinAu junction, have an orientation opposite that of WT Az with respect to the electrodes. Current(s) via both proteins are temperature-independent, consistent with quantum mechanical tunneling as dominant transport mechanism. No noticeable difference is resolved between the two proteins in conductance and inelastic electron tunneling spectra at

We describe the growth of single crystals of the halide perovskites APbBr3, with varying ratios of Cs to methylammonium (MA) on the A site, by antisolvent vapor-assisted crystallization (AVC) and characterize the structural and compositional homogeneity of the grown crystals. We find improved thermostability for the Cs-rich mixed crystals and suggest that this is caused by a combination of locking-in of the relatively large MA in the smaller lattice of the Cs-rich material as well as by stronger hydrogen bonding between the nitrogen of MA and Br due to reduced lattice size and/or octahedral tilting with increased Cs. We also show that it is possible to grow either compositionally homogeneous crystals or core-shell, compositionally graded crystals by changing the ratio of antisolvent to solvent in the AVC method.

Although halide perovskites (HaPs) are synthesized in ways that appear antithetical to those required for yielding high-quality semiconductors, the properties of the resulting materials imply, particularly for single crystals, ultralow densities of optoelectronically active defects. This article provides different views of this unusual behavior. We pose the question: Can present models of point defects in solids be used to interpret the experimental data and provide predictive power? The question arises because the measured ultralow densities refer to static defects using our present methods and models, while dynamic defect densities are ultrahigh, a result of the material being relatively soft, with a shallow electrostatic energy landscape, and with anharmonic lattice dynamics. All of these factors make the effects of dynamic defects on the materials' optoelectronic properties minimal. We hope this article will stimulate discussions on the nontrivial question: Are HaPs, and especially the defects within them, business as usual?

Successful integration of proteins in solid-state electronics requires contacting them in a non-invasive fashion, with a solid conducting surface for immobilization as one such contact. The contacts can affect and even dominate the measured electronic transport. Often substrates, substrate treatments, protein immobilization, and device geometries differ between laboratories. Thus the question arises how far results from different laboratories and platforms are comparable and how to distinguish genuine protein electronic transport properties from platform-induced ones. We report a systematic comparison of electronic transport measurements between different laboratories, using all commonly used large-area schemes to contact a set of three proteins of largely different types. Altogether we study eight different combinations of molecular junction configurations, designed so that A(geo) of junctions varies from 10(5) to 10(-3) mu m(2). Although for the same protein, measured with similar device geometry, results compare reasonably well, there are significant differences in current densities (an intensive variable) between different device geometries. Likely, these originate in the critical contact-protein coupling (similar to contact resistance), in addition to the actual number of proteins involved, because the effective junction contact area depends on the nanometric roughness of the electrodes and at times, even the proteins may increase this roughness. On the positive side, our results show that understanding what controls the coupling can make the coupling a design knob. In terms of extensive variables, such as temperature, our comparison unanimously shows the transport to be independent of temperature for all studied configurations and proteins. Our study places coupling and lack of temperature activation as key aspects to be considered in both modeling and practice of protein electronic transport experiments.

Perovskite photovoltaics has witnessed an unprecedented increase in power conversion efficiency over the last decade. The choice of transport layers, through which photo-generated electrons and holes are transported to electrodes, is a crucial factor for further improving both the device performance and stability. In this perspective, we critically examine the application of optical spectroscopy to characterize the quality of the transport layer-perovskite interface. We highlight the power of complementary studies that use both continuous wave and time-resolved photoluminescence to understand non-radiative losses and additional transient spectroscopies for characterizing the potential for loss-less carrier extraction at the solar cell interfaces. Based on this discussion, we make recommendations on how to extrapolate results from optical measurements to assess the quality of a transport layer and its impact on solar cell efficiency.

Extended x-ray absorption fine structure spectroscopy of the light-harvesting formamidinium lead bromide (FAPbBr(3)) perovskite, a system with attractive optoelectronic performance, shows anomalously large variance in Pb-Br bond length, some 50% larger than in its inorganic CsPbBr3 counterpart. Using first-principles molecular dynamics simulations, we find a significant contribution to this variance coming from the FA cation, and show that the FA does not just tumble in its cuboctahedral Br-12 cage, but instead stochastically sticks to, and detaches from one of the 12 nearest Br atoms after another, leading to the large variance in Pb-Br bond length. Our results demonstrate dynamic coupling between the FA-Br moiety and perovskite cage vibrations, and that tunability in dynamics can be achieved by changing the cation type and perovskite lattice parameter. Thus, our results provide information that needs to be considered in any of the intensely debated models of electron-phonon coupling in lead halide perovskites.

Solid-state electronic transport (ETp) via the electron-transfer copper protein azurin (Az) was measured in Au/Az/Au junction configurations down to 4 K, the lowest temperature for solid-state protein-based junctions. Not only does lowering the temperature help when observing fine features of electronic transport, but it also limits possible electron transport mechanisms. Practically, wire-bonded devices-on-chip, carrying Az-based microscopic junctions, were measured in liquid He, minimizing temperature gradients across the samples. Much smaller junctions, in conducting-probe atomic force microscopy measurements, served, between room temperature and the protein's denaturation temperature (similar to 323 K), to check that conductance behavior is independent of device configuration or contact nature and thus is a property of the protein itself. Temperature-independent currents were observed from similar to 320 to 4 K. The experimental results were fitted to a single-level Landauer model to extract effective energy barrier and electrode-molecule coupling strength values and to compare data sets. Our results strongly support that quantum tunneling, rather than hopping, dominates ETp via Az.

The primary sequence and secondary structure of a peptide are crucial to charge migration, not only in solution (electron transfer, ET), but also in the solid-state (electron transport, ETp). Hence, understanding the charge migration mechanisms is fundamental to the development of biomolecular devices and sensors. We report studies on four Aib-containing helical peptide analogues: two acyclic linear peptides with one and two electron-rich alkene-based side chains, respectively, and two peptides that are further rigidified into a macrocycle by a side bridge constraint, containing one or no alkene. ETp was investigated across Au/peptide/Au junctions, between 80 and 340 K in combination with the molecular dynamic (MD) simulations. The results reveal that the helical structure of the peptide and electron-rich side chain both facilitate the ETp. As temperature increases, the loss of helical structure, change of monolayer tilt angle, and increase of thermally activated fluctuations affect the conductance of peptides. Specifically, room temperature conductance across the peptide monolayers correlates well with previously observed ET rate constants, where an interplay between backbone rigidity and electron-rich side chains was revealed. Our findings provide new means to manipulate electronic transport across solid-state peptide junctions.

Halide perovskites are promising optoelectronic materials. Despite impressive device performance, especially in photovoltaics, the femtosecond dynamics of elementary optical excitations and their interactions are still debated. Here we combine ultrafast two-dimensional electronic spectroscopy (2DES) and semiconductor Bloch equations (SBEs) to probe the room-temperature dynamics of nonequilibrium excitations in CsPbBr3 crystals. Experimentally, we distinguish between excitonic and free-carrier transitions, extracting a similar to 30 meV exciton binding energy, in agreement with our SBE calculations and with recent experimental studies. The 2DES dynamics indicate remarkably short,

The Shockley-Queisser model is a landmark in photovoltaic device analysis by defining an ideal situation as reference for actual solar cells. However, the model and its implications are easily misunderstood. Thus, we present a guide to help understand and to avoid misinterpreting it.

Halide perovskites (HaPs) have rapidly grown as highly promising photovoltaic materials. Despite the impressive device efficiencies, however, the fundamental mechanisms governing their unusual optoelectronic properties are still unclear [1]. In particular, the nature of their elementary optical excitations, their dynamics and interactions on ultrafast timescales are currently debated. Due to the comparatively low exciton binding energy, typically

Lead bromide-based halide perovskites are of interest for wide-band-gap (>1.75 eV) absorbers for low-cost solar spectrum splitting to boost solar-to-electrical energy conversion efficiency/area by adding them to c-Si or Cu(In,Ga)Se-2 PV cells and for photoelectrochemical solar fuel synthesis. Deep in-gap electronic states in PV absorbers serve as recombination centers and are detrimental for the cell's photovoltaic performance, especially for the open-circuit voltage (V-oc). We find four different deep defect states in polycrystalline layers of mixed-cation lead tribromide from high-sensitivity modulated surface photovoltage (SPV) spectroscopy. Measurements were performed with different contact configurations, on complete solar cells and on samples before and after aging or stressing at 85 degrees C under illumination. Three of the four states, with energies of similar to 0.63, 0.73, and 1.35 eV below the conduction band edge, are assigned to intrinsic defects, whereas defect states in the middle of the band gap could be associated with (uncontrolled) impurities.

Design and modification of interfaces, always a critical issue for semiconductor devices, has become a primary tool to harness the full potential of halide perovskite (HaP)-based optoelectronics, including photovoltaics and light-emitting diodes. In particular, the outstanding improvements in HaP solar cell performance and stability can be primarily ascribed to a careful choice of the interfacial layout in the layer stack. In this review, we describe the unique challenges and opportunities of these approaches (section 1). For this purpose, we first elucidate the basic physical and chemical properties of the exposed HaP thin film and crystal surfaces, including topics such as surface termination, surface reactivity, and electronic structure (section 2). This is followed by discussing experimental results on the energetic alignment processes at the interfaces between the HaP and transport and buffer layers. This section includes understandings reached as well as commonly proposed and applied models, especially the often-questionable validity of vacuum level alignment, the importance of interface dipoles, and band bending as the result of interface formation (section 3). We follow this by elaborating on the impact of the interface formation on device performance, considering effects such as chemical reactions and surface passivation on interface energetics and stability. On the basis of these concepts, we propose a roadmap for the next steps in interfacial design for HaP semiconductors (section 4), emphasizing the importance of achieving control over the interface energetics and chemistry (i.e., reactivity) to allow predictive power for tailored interface optimization.

Different batches of Si wafers with nominally the same specifications were found to respond differently to identical chemical surface treatments aimed at regrowing Si oxide on them. We found that the oxides produced on different batches of wafer differ electrically, thereby affecting solid-state electron transport (ETp) via protein films assembled on them. These results led to the another set of experiments, where we studied this phenomenon using two distinct chemical methods to regrow oxides on the same batch of Si wafers. We have characterized the surfaces of the regrown oxides and of monolayers of linker molecules that connect proteins with the oxides and examined ETp via ultrathin layers of the protein bacteriorhodopsin, assembled on them. Our results illustrate the crucial role of (near) surface charges on the substrate in defining the ETp characteristics across the proteins. This is expressed most strikingly in the observed current's temperature dependences, and we propose that these are governed by the electrostatic landscape at the electrode-protein interface rather than by intrinsic protein properties. This study's major finding, relevant to protein bioelectronics, is that protein-electrode coupling in junctions is a decisive factor in ETp across them. Hence,surface electrostatics can create a barrier that dominates charge transport and controls the transport mode across the junction. Our findings' wider importance lies in their relevance to hybrid junctions of Si with (polyelectrolyte) biomolecules, a likely direction for future bioelectronics. A remarkable corollary of presented results is that once an electron is injected into the protein, transport within the proteins is so efficient that it does not encounter a measurable barrier down to 160 K.

Junctions built from metallic nanoparticles (NPs) can circumvent the diffraction limit and combine molecular/nanoelectronics with plasmonics. However, experimental advances in plasmon-assisted electron transport at the nanoscale have been limited. We construct junctions of a robust, molecule-free, suspended film, built solely from AuNPs, capped by SiO2 shells (Au@SiO2), which give insulating tunneling gaps up to 3.6 nm between the NPs. Current measured across monolayers of such AuNPs shows ultra-long-range, plasmon-enabled electron transport (P-transport), beyond the range of normal electron tunneling across insulators. This finding challenges the present understanding of electron transport in such systems and opens possibilities for future combinations of plasmonics and nanoelectronics.

Multi-heme cytochrome c (Cytc) proteins are key for transferring electrons out of cells, to enable intracellular oxidation to proceed in the absence of O-2. In these proteins most of the hemes are arranged in a linear array suggesting a facile path for electronic conduction. To test this, we studied solvent-free electron transport across two multi-heme Cytc-type proteins: MtrF (deca-heme Cytc) and STC (tetra-heme Cytc). Transport is measured across monolayers of these proteins in a solid state configuration between Au electrodes. Both proteins showed 1000x higher conductance than single heme, or heme-free proteins, but similar conductance to monolayers of conjugated organics. Conductance is found to be temperature-independent (320-80 K), suggesting tunneling as the transport mechanism. This mechanism is consistent with I-V curves modelling, results of which could be interpreted by having protein-electrode coupling as rate limiting, rather than transport within the proteins.

Time-resolved, pulsed excitation methods are widely used to deduce optoelectronic properties of semiconductors, including now also Halide Perovskites (HaPs), especially transport properties. However, as yet, no evaluation of their amenability and justification for the use of the results for the above-noted purposes has been reported. To check if we can learn from pulsed measurement results about steady-state phototransport properties, we show here that, although pulsed measurements can be useful to extract information on the recombination kinetics of HaPs, great care should be taken. One issue is that no changes in the material are induced during or as a result of the excitation, and another one concerns in how far pulsed excitation-derived data can be used to find relevant steady-state parameters. To answer the latter question, we revisited pulsed excitation and propose a novel way to compare between pulsed and steady state measurements at different excitation intensities. We performed steady-state photoconductivity and ambipolar diffusion length measurements, as well as pulsed time-resolved microwave conductivity and time-resolved photoluminescence measurements as a function of excitation intensity on the same samples of different MAPbI(3) thin films, and found good quasi-quantitative agreement between the results, explaining them with a generalized single level recombination model that describes the basic physics of phototransport of HaP absorbers. Moreover, we find the first experimental manifestation of the boundaries between several effective recombination regimes that exist in HaPs, by analyzing their phototransport behavior as a function of excitation intensity. Published by AlP Publishing.

Electrochemical CO2 reduction on Cu electrode has attracted the attention of many researchers in the last decades, because of its potential to generate significant amounts of hydrocarbons at high reaction rates over sustained periods of time. As a result, substantial effort has been devoted to determining the unique catalytic performance of Cu and to elucidate the mechanism through which hydrocarbons are formed. Here we report new insights into CO2 reduction on Cu by electrochemical impedance spectroscopy (EIS) in terms of adsorption/desorption of the reduction intermediates. The potential dependence of charge transfer kinetics is discussed on the basis of EIS results. We revisit the mechanism of the formation of hydrocarbons, taking into account the pH adjacent to the electrode surface, adsorption of HCO3- and CO32-, and the role of active hydrogen. In addition to the enol-like intermediate, proposed previously, we proposed that *COOH center dot radicals, originating from the active involvement of HCO3- and/or CO32- upon reduction are key intermediates for the formation of a variety of C2 and C3 products. Thus, our results provide an additional crucial guideline for the design of future catalysts that can efficiently and selectively reduce CO2 into value-added chemicals.

Lead-based halide perovskites (APbX(3)) are fascinating optoelectronic materials. Because of toxicity issues of Pb, Sn-based halide perovskites are studied, although less so, as an alternative. Adding SnF2 often improves the properties of Sn halide perovskite-based devices. This effect is usually ascribed to suppression of Sn2+ -> Sn4+ oxidation and/or decreased Sn vacancy concentration. These effects will change the doping, sometimes in opposite directions. Here we review the effect of addition of SnF2 during the formation of ASnX(3) layers as observed by different groups, both to the properties of the layers themselves and to photovoltaic cells made from these layers. SnF2 can affect many different properties of the ASnX(3) perovskites, including film morphology, doping, control over formation of unwanted crystal phases, material stability to various factors, and energy level positions. It also improves (in general) the performance of photovoltaic cells made with these layers. Besides focusing on all these issues, we also describe possible doping scenarios for the perovskites, including some that do not appear to have been considered before and conclude that the doping mechanism depends strongly on whether the oxidation of Sn2+ to Sn2+ occurs during the materials preparation or after the film is formed, and if oxygen is involved.

Metalloproteins, proteins containing a transition metal ion cofactor, are electron transfer agents that perform key functions in cells. Inspired by this fact, electron transport across these proteins has been widely studied in solid-state settings, triggering the interest in examining potential use of proteins as building blocks in bioelectronic devices. Here, we report results of low-temperature (10 K) electron transport measurements via monolayer junctions based on the blue copper protein azurin (Az), which strongly suggest quantum tunneling of electrons as the dominant charge transport mechanism. Specifically, we show that, weakening the protein-electrode coupling by introducing a spacer, one can switch the electron transport from off-resonant to resonant tunneling. This is a consequence of reducing the electrode's perturbation of the Cu(II)localized electronic state, a pattern that has not been observed before in protein-based junctions. Moreover, we identify vibronic features of the Cu(II) coordination sphere in transport characteristics that show directly the active role of the metal ion in resonance tunneling. Our results illustrate how quantum mechanical effects may dominate electron transport via protein-based junctions.

Peptide-based molecular electronic devices are promising due to the large diversity and unique electronic properties of biomolecules. These electronic properties can change considerably with peptide structure, allowing diverse design possibilities. In this work, we explore the effect of the side-chain of the peptide on its electronic properties, by using both experimental and computational tools to detect the electronic energy levels of two model peptides. The peptides include 2Ala and 2Trp as well as their 3-mercaptopropionic acid linker which is used to form monolayers on an Au surface. Specifically, we compare experimental ultraviolet photoemission spectroscopy measurements with density functional theory based computational results. By analyzing differences in frontier energy levels and molecular orbitals between peptides in gas-phase and in a monolayer on gold, we find that the electronic properties of the peptide side-chain are maintained during binding of the peptide to the gold substrate. This indicates that the energy barrier for the peptide electron transport can be tuned by the amino acid compositions, which suggests a route for structural design of peptide-based electronic devices.

Molecular monolayers at metal/semiconductor heterointerfaces affect electronic energy level alignment at the interface by modifying the interface's electrical dipole. On a free surface, the molecular dipole is usually manipulated by means of substitution at its external end. However, at an interface such outer substituents are in close proximity to the top contact, making the distinction between molecular and interfacial effects difficult. To examine how the interface dipole would be influenced by a single atom, internal to the molecule, we used a series of three molecules of identical binding and tail groups, differing only in the inner atom: aryl vinyl ether (PhO), aryl vinyl sulfide (PhS), and the corresponding molecule with a CH2 group allyl benzene (PhC). Molecular monolayers based on all three molecules have been adsorbed on a flat, oxide-free Si surface. Extensive surface characterization, supported by density functional theory calculations, revealed high-quality, well-aligned monolayers exhibiting excellent chemical and electrical passivation of the silicon substrate, in all three cases. Current voltage and capacitance voltage analysis of Hg/PhX (X = C, 0, S)/Si interfaces established that the type of internal atom has a significant effect on the Schottky barrier height at the interface, i.e., on the energy level alignment. Surprisingly, despite the formal chemical separation of the internal atom and the metallic electrode, Schottky barrier heights were not correlated to changes in the semiconductor's effective work function, deduced from Kelvin probe and ultraviolet photoemission spectroscopy on the monolayer-adsorbed Si surface. Rather, these changes correlated well with the ionization potential of the surface-adsorbed molecules. This is interpreted in terms of additional polarization at the molecule/metal interface, driven by potential equilibration considerations even in the absence of a formal chemical bond to the top Hg contact.

We present a measurement of the energies and capture cross-sections of defect states in methylammonium lead bromide (MAPbBr₃) 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.

Negative capacitance in photovoltaic devices has been observed and reported in several cases, but its origin, at low or intermediate frequencies, is under debate. Here we unambiguously demonstrate a direct correlation between the observation of this capacitance and a corresponding decrease in performance of a halide perovskite (HaP; CsPbBr3)-based device, expressed as reduction of open-circuit voltage and fill factor. We have prepared highly stable CsPbBr3 HaPs that do not exhibit any degradation over the duration of the impedance spectroscopy measurements, ruling out degradation as the origin of the observed phenomena. Reconstruction of current voltage curves from the impedance spectroscopy provided further evidence of the deleterious role of negative capacitance on photoconversion performance.

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 (1mJ) 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.

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.

Using several metals with different work functions as solar cell back contact we identify majority carrier type inversion in methylammonium lead bromide (MAPbBr3, without intentional doping) as the basis for the formation of a p-n junction. MAPbBr₃ films deposited on TiO₂ are slightly n-type, whereas in a full device they are strongly p-type. The charge transfer between the metal electrode and the halide perovskite (HaP) film is shown to determine the dominant charge carrier type of the HaP and, thus, also of the final cells. Usage of Pt, Au and Pb as metal electrodes shows the effects of metal work function on minority carrier diffusion length and majority carrier concentration in the HaP, as well as on built-in voltage, band bending, and open circuit voltage (V_OC) within a solar cell. V_OC > 1.5 V is demonstrated. The higher the metal WF, the higher the carrier concentration induced in the HaP, as indicated by a narrower space charge region and a smaller minority carrier diffusion length. From the analysis of bias-dependent electron beam-induced currents, the HaP carrier concentrations are estimated to be ∼ 1 × 10¹⁷ cm^-3 with Au and 2-3 × 10¹⁸ cm^-3 with Pt. A model in which type-inversion stretches across the entire film width implies formation of the p-n junction away from the interface, near the back-contact metal electrode. This work highlights the importance of the contact metal on device performance in that contact engineering can also serve to control the carrier concentration in HaP.

Simple organic salts are used as a cheap alternative for hole-conducting materials in methylammonium lead bromide perovskite solar cells and obtaining power conversion efficiency of 4.4%. The findings suggest that the polar organic salts interact with the perovskite surface, leading to formation of a surface dipole or change of an existing one on the perovskites that changes its effective work function.

We investigate the effect of high work function contacts in halide perovskite absorber-based photovoltaic devices. Photoemission spectroscopy measurements reveal that band bending is induced in the absorber by the deposition of the high work function molybdenum trioxide (MoO₃). We find that direct contact between MoO₃ and the perovskite leads to a chemical reaction, which diminishes device functionality. Introducing an ultrathin spiro-MeOTAD buffer layer prevents the reaction, yet the altered evolution of the energy levels in the methylammonium lead iodide (MAPbI₃) layer at the interface still negatively impacts device performance.

Charge migration for electron transfer via the polypeptide matrix of proteins is a key process in biological energy conversion and signaling systems. It is sensitive to the sequence of amino acids composing the protein and, therefore, offers a tool for chemical control of charge transport across biomaterial-based devices. We designed a series of linear oligoalanine peptides with a single tryptophan substitution that acts as a "dopant," introducing an energy level closer to the electrodes' Fermi level than that of the alanine homopeptide. We investigated the solid-state electron transport (ETp) across a selfassembled monolayer of these peptides between gold contacts. The single tryptophan "doping" markedly increased the conductance of the peptide chain, especially when its location in the sequence is close to the electrodes. Combining inelastic tunneling spectroscopy, UV photoelectron spectroscopy, electronic structure calculations by advanced density-functional theory, and dc current-voltage analysis, the role of tryptophan in ETp is rationalized by charge tunneling across a heterogeneous energy barrier, via electronic states of alanine and tryptophan, and by relatively efficient direct coupling of tryptophan to a Au electrode. These results reveal a controlled way of modulating the electrical properties of molecular junctions by tailormade "building block" peptides.

Hysteresis in the current-voltage characteristics of hybrid organic-inorganic perovskite-based solar cells is one of the fundamental aspects of these cells that we do not understand well. One possible cause, suggested for the hysteresis, is polarization of the perovskite layer under applied voltage and illumination bias, due to ion migration within the perovskite. To study this problem systemically, current-voltage characteristics of both regular (light incident through the electron conducting contact) and so-called inverted (light incident through the hole conducting contact) perovskite cells were studied at different temperatures and scan rates. We explain our results by assuming that the effects of scan rate and temperature on hysteresis are strongly correlated to ion migration within the device, with the rate-determining step being ion migration at/across the interfaces of the perovskite layer with the contact materials. By correlating between the scan rate with the measurement temperature, we show that the inverted and regular cells operate in different hysteresis regimes, with different activation energies of 0.28 ± 0.04 eV and 0.59 ± 0.09 eV, respectively. We suggest that the differences observed between the two architectures are due to different rates of ion migration close to the interfaces, and conclude that the diffusion coefficient of migrating ions in the inverted cells is 3 orders of magnitude higher than in the regular cells, leading to different accumulation rates of ions near the interfaces. Analysis of V_OC as a function of temperature shows that the main recombination mechanism is trap-assisted (Shockley-Read Hall, SRH) in the space charge region, similar to what is the case for other thin film inorganic solar cells.

We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI₃, MAPbBr₃, CsPbBr₃), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI₃ VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites.

ConspectusHybrid alkylammonium lead halide perovskite solar cells have, in a very few years of research, exceeded a light-to-electricity conversion efficiency of 20%, not far behind crystalline silicon cells. These perovskites do not contain any rare element, the amount of toxic lead used is very small, and the cells can be made with a low energy input. They therefore already conform to two of the three requirements for viable, commercial solar cells-efficient and cheap. The potential deal-breaker is their long-term stability. While reasonable short-term (hours) and even medium term (months) stability has been demonstrated, there is concern whether they will be stable for the two decades or more expected from commercial cells in view of the intrinsically unstable nature of these materials. In particular, they have a tendency to be sensitive to various types of irradiation, including sunlight, under certain conditions.This Account focuses on the effect of irradiation on the hybrid (and to a small degree, all-inorganic) lead halide perovskites and their solar cells. It is split up into two main sections. First, we look at the effect of electron beams on the materials. This is important, since such beams are used for characterization of both the perovskites themselves and cells made from them (electron microscopy for morphological and compositional characterization; electron beam-induced current to study cell operation mechanism; cathodoluminescence for charge carrier recombination studies). Since the perovskites are sensitive to electron beam irradiation, it is important to minimize beam damage to draw valid conclusions from such measurements. The second section treats the effect of visible and solar UV irradiation on the perovskites and their cells. As we show, there are many such effects. However, those affecting the perovskite directly need not necessarily always be detrimental to the cells, while those affecting the solar cells, which are composed of several other phases as well as the perovskite light absorber, are not always due to the perovskite itself. While we cannot yet say whether perovskite solar cells will or will not be stable over the long-term, the information in this Account should be a useful source to help achieve this goal.

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.

Electron transport properties via a photochromic biological photoreceptor have been studied in junctions of monolayer assemblies in solid-state configurations. The photoreceptor studied was a member of the LOV domain protein family with a bound flavin chromophore, and its photochemically inactive mutant due to change of a crucial cysteine residue by a serine. The photochemical properties of the protein were maintained in dry, solid state conditions, indicating that the proteins in the junctions were assembled in native state-like conditions. Significant current magnitudes (>20 μA at 1.0 V applied bias) were observed with a mechanically deposited gold pad (area ∼0.002 cm²) as top electrode. The current magnitudes are ascribed to electrode-cofactor coupling originating from the apparent perpendicular orientation of the protein's cofactor embedded between the electrodes, and its proximity to the electrodes. Temperature independent electron transport across the protein monolayers demonstrated that solid-state electron transport is dominated by tunneling. Modulation of the observed current by illumination of the wildtype protein suggested conformation-dependent electron conduction efficiency across the solid-state protein junctions.

We report a combined ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) study of the electronic structure of aromatic self-assembled monolayers covalently bound to Si, using several different aromatic groups (phenyl, biphenyl, and fluorene) and binding groups (O, NH, and CH₂). We obtain excellent agreement between theory and experiment, which allows for a detailed interpretation of the experimental results. Our analysis reveals a significant effect of the binding group on state hybridization at the organic/inorganic interface. Specifically, it highlights that lone-pair electrons in the binding atom facilitate hybridization between the aromatic system and the Si substrate, resulting in a significant induced density of interface states (IDIS). These interface states are manifested as a broadened HOMO peak in the experimental UPS data and are clearly observed in a theoretical spatially-resolved density of states map. This provides means to control the degree of coupling between substrate and molecule, which may prove useful in the design of transport across organic/inorganic interfaces.

We observe temperature-independent electron transport, characteristic of tunneling across a ∼6 nm thick Halorhodopsin (phR) monolayer. phR contains both retinal and a carotenoid, bacterioruberin, as cofactors, in a trimeric protein-chromophore complex. This finding is unusual because for conjugated oligo-imine molecular wires a transition from temperature-independent to -dependent electron transport, ETp, was reported at ∼4 nm wire length. In the ∼6 nm long phR, the ∼4 nm 50-carbon conjugated bacterioruberin is bound parallel to the α-helices of the peptide backbone. This places bacterioruberins ends proximal to the two electrodes that contact the protein; thus, coupling to these electrodes may facilitate the activation-less current across the contacts. Oxidation of bacterioruberin eliminates its conjugation, causing the ETp to become temperature dependent (>180 K). Remarkably, even elimination of the retinal-protein covalent bond, with the fully conjugated bacterioruberin still present, leads to temperature-dependent ETp (>180 K). These results suggest that ETp via phR is cooperatively affected by both retinal and bacterioruberin cofactors.

Many novel applications in bioelectronics rely on the interaction between biomolecules and electronically conducting substrates. However, crucial knowledge about the relation between electronic transport via peptides and their amino-acid composition is still absent. Here, we report results of electronic transport measurements via several homopeptides as a function of their structural properties and temperature. We demonstrate that the conduction through the peptide depends on its length and secondary structure as well as on the nature of the constituent amino acid and charge of its residue. We support our experimental observations with high-level electronic structure calculations and suggest off-resonance tunneling as the dominant conduction mechanism via extended peptides. Our findings indicate that both peptide composition and structure can affect the efficiency of electronic transport across peptides.

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 perovskite 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 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.

A central vision in molecular electronics is the creation of devices with functional molecular components that may provide unique properties. Proteins are attractive candidates for this purpose, as they have specific physical (optical, electrical) and chemical (selective binding, self-assembly) functions and offer a myriad of possibilities for (bio-)chemical modification. This Progress Report focuses on proteins as potential building components for future bioelectronic devices as they are quite efficient electronic conductors, compared with saturated organic molecules. The report addresses several questions: how general is this behavior; how does protein conduction compare with that of saturated and conjugated molecules; and what mechanisms enable efficient conduction across these large molecules? To answer these questions results of nanometer-scale and macroscopic electronic transport measurements across a range of organic molecules and proteins are compiled and analyzed, from single/few molecules to large molecular ensembles, and the influence of measurement methods on the results is considered. Generalizing, it is found that proteins conduct better than saturated molecules, and somewhat poorer than conjugated molecules. Significantly, the presence of cofactors (redox-active or conjugated) in the protein enhances their conduction, but without an obvious advantage for natural electron transfer proteins. Most likely, the conduction mechanisms are hopping (at higher temperatures) and tunneling (below ca. 150-200 K).

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 CH₃NH₃PbI_3-x Cl_x 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 diff usion length. In this work we investigate the crystallization parameters relevant to fabrication of perovskite materials based on CH₃NH₃PbI₃ and CH₃NH₃PbBr₃. We find that the addition of PbCl₂ to the solutions used in the perovskite synthesis has a remarkable eff ect 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 perovskite, 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.

Organometallic lead-halide perovskite-based solar cells now approach 18% efficiency. Introducing a mixture of bromide and iodide in the halide composition allows tuning of the optical bandgap. We prepare mixed bromide-iodide lead perovskite films CH₃NH₃Pb(I _1-xBr_x)₃ (0 ≤ x ≤ 1) by spin-coating from solution and obtain films with monotonically varying bandgaps across the full composition range. Photothermal deflection spectroscopy, photoluminescence, and X-ray diffraction show that following suitable fabrication protocols these mixed lead-halide perovskite films form a single phase. The optical absorption edge of the pure triiodide and tribromide perovskites is sharp with Urbach energies of 15 and 23 meV, respectively, and reaches a maximum of 90 meV for CH ₃NH₃PbI_1.2Br_1.8. We demonstrate a bromide-iodide lead perovskite film (CH₃NH₃PbI _1.2Br_1.8) with an optical bandgap of 1.94 eV, which is optimal for tandem cells of these materials with crystalline silicon devices.

The built-in voltage of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)-nSi hybrid solar cells is demonstrated to indicate strong inversion over most substrate donor concentrations. This implies a p-n homojunction, induced in the Si surface by the high work function of the top contact. This induced homojunction is then used to form the source and drain electrodes in a field-effect transistor.

Electronic coupling to electrodes, G, as well as that across the examined molecules, H, is critical for solid-state electron transport (ETp) across proteins. Assessing the importance of each of these couplings helps to understand the mechanism of electron flow across molecules. We provide here experimental evidence for the importance of both couplings for solid-state ETp across the electron- mediating protein cytochrome c (CytC), measured in a monolayer configuration. Currents via CytC are temperature-independent between 30 and -130 K, consistent with tunneling by superexchange, and thermally activated at higher temperatures, ascribed to steady-state hopping. Covalent protein-electrode binding significantly increases G, as currents across CytC mutants, bound covalently to the electrode via a cysteine thiolate, are higher than those through electrostatically adsorbed CytC. Covalent binding also reduces the thermal activation energy, Ea, of the ETp by more than a factor of two. The importance of H was examined by using a series of seven CytC mutants with cysteine residues at different surface positions, yielding distinct electrode-protein(-heme) orientations and separation distances. We find that, in general, mutants with electrode-proximal heme have lower Ea values (from high-temperature data) and higher conductance at low temperatures (in the temperatureindependent regime) than those with a distal heme. We conclude that ETp across these mutants depends on the distance between the heme group and the top or bottom electrode, rather than on the total separation distance between electrodes (protein width).

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.

CH₃NH₃PbI₃-based solar cells were characterized with electron beam-induced current (EBIC) and compared to CH ₃NH₃PbI_3-xCl_x 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 CH ₃NH₃PbI₃-based cells require mesoporous electron conductors, while CH₃NH₃PbI_3-xCl _x 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 CH₃NH₃PbBr_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 ∼1 to ∼4 mA/cm².

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 S_N reaction, whereas with UV irradiation RCR dominates, with S_N as a secondary path. We show that the site-sensitive S_N 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 S_N 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.

Integrating proteins in molecular electronic devices requires control over their solid-state electronic transport behavior. Unlike "traditional" electron transfer (ET) measurements of proteins that involve liquid environments and a redox cycle, no redox cofactor is needed for solid-state electron transport (ETp) across the protein. Here we show the fundamental difference between these two approaches by macroscopic area measurements, which allow measuring ETp temperature dependence down to cryogenic temperatures, via cytochrome C (Cyt C), an ET protein with a heme (Fe-porphyrin) prosthetic group as a redox centre. We compare the ETp to electrochemical ET measurements, and do so also for the protein without the Fe (with metal-free porphyrin) and without porphyrin. As removing the porphyrin irreversibly alters the protein's conformation, we repeat these measurements with human serum albumin (HSA), 'doped' (by non-covalent binding) with a single hemin equivalent, i.e., these natural and artificial proteins share a common prosthetic group. ETp via Cyt C and HSA-hemin are very similar in terms of current magnitude and temperature dependence, which suggests similar ETp mechanisms via these two systems, thermally activated hopping (with ∼0.1 eV activation energy) >190 K and tunneling by superexchange

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.

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 ∼ 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.

The quinhydrone/methanol treatment has been reported to yield outstanding passivation of the H-terminated Si(100) surface. Here, we report on the mechanism of this process by comparing the resulting surface to that of freshly etched H-terminated Si, of Si with chemically grown oxide, and of Si treated with hydroquinone/methanol solution of the same concentration. We find that the benzoquinone moieties of the quinhydrone react with the surface to yield a Si-hydroquinone surface termination, while the methanol molecules bind as well to form methoxy-terminated Si. The slightly negative-charged benzene ring of the hydroquinone acts to repel majority carrier electrons from the surface and inhabits the surface recombination. The higher the ratio of surface-bound hydroquinone to surface-bound methoxy species, the larger the minority carrier life-time measured by microwave photoconductivity. Thus, our results lead us to conclude that this treatment results in field effect passivation; remarkably, this effect is caused by a molecular monolayer alone.

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, V₀, 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 V₀ (TVS) provides genuine indication on fundamental tunneling features. Furthermore, we show that the prevailing concept that V₀ is proportional to the barrier height holds only in the case of resonant tunneling, while for off-resonant or deep tunneling, V₀ 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.

Organic monolayers derived from ω-fluoro-1-alkynes of varying carbon chain lengths (C₁₀-C₁₈) were prepared on Si(111) surfaces, resulting in changes of the physical and electronic properties of the surface. Analysis of the monolayers using XPS, Infrared Reflection Absorption Spectroscopy, ellipsometry and static water contact angle measurements provided information regarding the monolayer thickness, the tilt angle, and the surface coverage. Additionally, PCFF molecular mechanics studies were used to obtain information on the optimal packing density and the layer thickness, which were compared to the experimentally found data. From the results, it can be concluded that the monolayers derived from longer chain lengths are more ordered, possess a lower tilt angle, and have a higher surface coverage than monolayers derived from shorter chains. We also demonstrate that by substitution of an H by F atom in the terminal group, it is possible to controllably modify the surface potential and energy barrier for charge transport in a full metal/monolayer- semiconductor (MOMS) junction.

Keywords: Physics, Applied; Physics, Condensed Matter

We demonstrate a solar cell that uses fixed negative charges formed at the interface of n-Si with Al₂O₃ to generate strong inversion at the surface of n-Si by electrostatic repulsion. Built-in voltages of up to 755 mV are found at this interface. In order to harness this large built-in voltage, we present a photovoltaic device where the photocurrent generated in this inversion layer is extracted via an inversion layer induced by a high work function transparent organic top contact, deposited on top of a passivating and dipole-inducing molecular monolayer. Results of the effect of the molecular monolayer on device performance yield open-circuit voltages of up to 550 mV for moderately doped Si, demonstrating the effectiveness of this contact structure in removing the Fermi level pinning that has hindered past efforts in developing this type of solar cell with n-type Si.

Good passivation of Si, both electrically and chemically, is achieved by monolayers of 1,9-decadiene, directly bound to an oxide-free Si surface. The terminal C - C bond of the decadiene serves for further in situ reaction, without harming the surface passivation, to -OH- or -Br-terminated monolayers that have different dipole moments. Such a two-step procedure meets the conflicting requirements of binding mutually repelling dipolar groups to a surface, while chemically blocking all surface reactive sites. We demonstrate a change of 0.15 eV in the Si surface potential, which translates into a 0.4 eV variation in the Schottky barrier height of a Hg junction to those molecularly modified n-Si surfaces. Charge transport across such junctions is controlled both by tunneling across the molecular monolayer and by the Si space charge. For reliable insight into transport details, we resorted to detailed numerical simulations, which reveal that the Si space charge and the molecular tunneling barriers are coupled. As a result, attenuation due to the molecular tunneling is much weaker than in metal/molecule/metal molecular junctions. Simulation shows also that some interface states are present but that they have a negligible effect on Fermi level pinning. These states are efficiently decoupled from the metal (Hg) and interact mostly with the Si.

Despite the rapid increase in solar cell manufacturing capacity (∼50 GW _p in 2011), maintaining this continued expansion will require resolving some major fabrication issues. Crystalline Si, the most common type of cell, requires a large energy input in the manufacturing process, which results in an energy payback time of years. CdTe/CdS thin film cells, which have captured around 10% of the global market, may not be sustainable for very large-scale use because of limited Te availability. Thus, research in this field is emphasizing cells that are energy efficient and inexpensive and use readily available materials. The extremely thin absorber (ETA) cell, the subject of this Account, is one of these new generation cells. Since the active light absorber in an ETA cell is no more than tens of nanometers thick, the direct recombination of photogenerated electrons and holes in the absorber should not compete as much with charge removal in the form of photocurrent as in thicker absorber materials. As a result, researchers expect that poorer quality semiconductors can be used in an ETA cell, which would expand the choice of semiconductors over those currently in use.We first describe the ETA cell, comparing and contrasting it to the dye-sensitized cell (DSC) from which it developed and describing its potential advantages and disadvantages. We then explain the mechanism(s) of operation of the ETA cell, which remain controversial: different ETA cells most likely operate by different mechanisms, particularly in their photovoltage generation. We then present a general description of how we prepare ETA cells in our laboratory, emphasizing solution methods to form the various layers and solution treatments of these layers to minimize manufacturing costs. This is followed by a more specific discussion of the various layers and treatments used to make and complete a cell with emphasis on solution treatments that are important in optimizing cell performance and explaining the possible modes of action of each of these treatments. Finally, we show how ETA cells have improved over the years, their present efficiencies, our expectations for the future, and the challenges that we foresee to fulfill these expectations.

Solar cells based on crystalline semiconductors such as Si and GaAs provide nowadays the highest performance, but photovoltaic (PV) cells based on less pure materials, such as poly- or nano-crystalline or amorphous inorganic or organic materials, or a combination of these, should relax production requirements and lower the cost towards reliable, sustainable and economic electrical power from sunlight. So as to be able to compare the operation of different classes of solar cells we first summarize general photovoltaic principles and then consider implications of using less than ideal materials. In general, lower material purity means more disorder, which introduces a broad distribution of energy states of the electronic carriers that affects all the aspects of PV performance, from light absorption to the generation of voltage and current. Specifically, disorder penalizes energy output by enhanced recombination, with respect to the radiative limit, and also imposes a lowering of quasi-Fermi levels into the gap, which decreases their separation, i.e., reduces the photovoltage. In solar cells based on organic absorbers, such as dye-sensitized or bulk heterojunction solar cells, vibronic effects cause relaxation of carriers in the absorber, which implies an energy price in terms of obtainable output.

Freezing out of molecular motion and increased molecular tilt enhance the efficiency of electron transport through alkyl chain monolayers that are directly chemically bound to oxide-free Si. As a result, the current across such monolayers increases as the temperature decreases from room temperature to ∼80 K, i.e., opposite to thermally activated transport such as hopping or semiconductor transport. The 30-fold change for transport through an 18-carbon long alkyl monolayer is several times the resistance change for actual metals over this range. FTIR vibrational spectroscopic measurements indicate that cooling increases the packing density and reduces the motional freedom of the alkyl chains by first stretching the chains and then gradually tilting the adsorbed molecules away from the surface normal. Ultraviolet photoelectron spectroscopy shows drastic sharpening of the valence band structure as the temperature decreases, which we ascribe to decreased electron-phonon coupling. Although conformational changes are typical in soft molecular systems, in molecular electronics they are rarely observed experimentally or considered theoretically. Our findings, though, indicate that the molecular conformational changes are a prominent feature, which imply behavior that differs qualitatively from that described by models of electronic transport through inorganic mesoscopic solids.

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.

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.

Despite many recent research efforts, the influence of grain boundaries (GBs) on device properties of CuIn_1-xGa_xSe₂ solar cells is still not fully understood Here, we present a microscopic approach to characterizing GBs in polycrystalline CuIn_1-xGa _xSe₂ films with x = 0.33. On samples from the same deposition process we applied methods giving complementary information, i.e., electron backscatter diffraction (EBSD), electron-beam induced current measurements (EBIC), conductive atomic force microscopy (c-AFM), variable-temperature Kelvin probe force microscopy (KPFM), and scanning capacitance microscopy (SCM). By combining EBIC with EBSD, we find a decrease in charge-carrier collection for non-σ3 GBs, while σ 3 GBs exhibit no variation with respect to grain interiors. In contrast, a higher conductance of GBs compared to grain interiors was found by c-AFM at low bias and under illumination. By KPFM, we directly measured the band bending at GBs, finding a variation from - 80 up to + 115 mV. Depletion and even inversion at GBs was confirmed by SCM. We comparatively discuss the apparent differences between the results obtained by various microscopic techniques.

Understanding how quantum dot (QD)-sensitized solar cells operate requires accurate determination of the offset between the lowest-unoccupied molecular orbital (LUMO) of the sensitizer quantum dot and the conduction band of the metal oxide electrode. We present detailed optical spectroscopy, low-energy photoelectron spectroscopy, and two-photon photoemission studies of the energetics of size-selected CdSe colloidal QDs deposited on TiO₂ electrodes. Our experimental findings show that in contrast to the prediction of simplified models based on bulk band offsets and effective mass considerations, band alignment in this system is strongly modified by the interaction between the QDs and the electrode. In particular, we find relatively small conduction band- LUMO offsets, and near "pinning" of the QD LUMO relative to the conduction band of the TiO₂ electrode, which is explained by the strongQD-electrode interaction. That interaction is the origin for the highly efficientQDto electrode charge transfer, and it also bears on the possibility of hot carrier injection in these types of cells.

Focus During the last decade the direct conversion of solar energy to electricity by photovoltaic cells has emerged from a pilot technology to one that produced 11 GW_p of electricity generating capacity in 2009. With production growing at 50%70% a year (at least until 2009) photovoltaics (PV) is becoming an important contributor to the next generation of renewable green power production. The question is that of how we can move to the terawatt (TW) scale [1]. Synopsis The rapid evolution of PV as an alternative means of energy generation is bringing it closer to the point where it can make a significant contribution to challenges posed by the rapid growth of worldwide energy demand and the associated environmental issues. Together with the main existing technology, which is based on silicon (Si), the growth of the field is intertwined with the development of new materials and fabrication approaches. The PV industry, which was, until recently, based primarily on crystalline, polycrystalline, and amorphous Si, grew at an average annual rate of 50% during 20002010. This rate was increasing, at least until the 2008 economic crisis, with production of ~11 gigawatts (GW_p) per year in 2009 [2]. While this may seem a very large number, PV installations in total are still supplying only

Protein structures can facilitate long-range electron transfer in solution. But a fundamental question remains: can these structures also serve as solid-state electronic conductors? Answering this question requires methods for studying conductivity of the "dry" protein (which only contains tightly bound structured water molecules) sandwiched between two electronic conductors in a solid-state type configuration. If successful, such systems could serve as the basis for future, bioinspired electronic device technology. In this Account, we survey, analyze, and compare macroscopic and nanoscopic (scanning probe) solid-state conductivities of proteins, noting the inherent constraints of each of these, and provide the first status report on this research area. This analysis shows convincing evidence that "dry" proteins pass orders of magnitude higher currents than saturated molecules with comparable thickness and that proteins with known electrical activity show electronic conductivity, nearly comparable to that of conjugated molecules ("wires"). These findings suggest that the structural features of proteins must have elements that facilitate electronic conductivity, even if they do not have a known electron transfer function. As a result, proteins could serve not only as sensing, polar,or photoactive elements in devices (such as field-effect transistor configurations) but also as electronic conductors. Current knowledge of peptide synthesis and protein modification paves the way toward a greater understanding of how changes in a protein's structure affect its conductivity. Such an approach could minimize the need for biochemical cascades in systems such as enzyme-based circuits, which transduce the protein's response to electronic current. In addition, as precision and sensitivity of solid-state measurements increase, and as knowledge of the structure and function of "dry" proteins grows, electronic conductivity may become an additional approach to study electron transfer in proteins and solvent effects without the introduction of donor or acceptor moieties. We are particularly interested in whether evolution might have prompted the electronic carrier transport capabilities of proteins for which no electrically active function is known in their native biological environment and anticipate that further research may help address this fascinating question.

One of the major problems in molecular electronics is how to make electronically conducting contact to the "soft" organic and biomolecules without altering the molecules. As a result, only a small number of metals can be applied, mostly by special deposition methods with severe limitations. Transferring a predefined thin metal leaf onto a molecular layer provides a nondestructive, noninvasive contacting method that is, in principle, applicable to many types of metal and a variety of metal/molecules combinations. Here we report a modification of our earlier lift-off, float-on (LOFO) method, using as a basis its offspring, the polymer-assisted lift-off (PALO) method, where a backing polymer enables simultaneous deposition of multiple contacts as well as reduces wrinkles in the thin metal leaf. The modified PALO (MoPALO) method, reported here, adds lithography steps to obviate the need to punch through the polymer, as is done to complete PALO contacts. Morphological characterization of the electrodes indicates highly uniform, wrinkle-free contacts of negligible roughness. The good electrical performance of the MoPALO contacts was proven with metal/organic-monolayer/semiconductor (MOMS) junctions, which are known to be very sensitive to molecular degradation and metal penetration. We also show how MoPALO contacts enabled us to compare the effect of varying the metal work function and contact area on the current-voltage characteristics of MOMS devices.

Electron transfer (ET) through proteins, a fundamental element of many biochemical reactions, is studied Intensively in aqueous solutions. Over the past decade, attempts were made to Integrate proteins into solid-state Junctions in order to study their electronic conductance properties. Most such studies to date were conducted with one or very few molecules In the Junction, using scanning probe techniques. Here we present the high-yield, reproducible preparation of large-area monolayer Junctions, assembled on a Si platform, of proteins of three different families: azurln (Az), a blue-copper ET protein, bacterlorhodopsln (bR), a membrane proteln-chromophore complex with a proton pumping function, and bovine serum albumin (BSA). We achieve highly reproducible electrical current measurements with these three types of monolayers using appropriate top electrodes. Notably, the current-voltage (i-V) measurements on such Junctions show relatively minor differences between Az and bR, even though the latter lacks any known ET function. Electron Transport (ETp) across both Az and bR is much more efficient than across BSA, but even for the latter the measured currents are higher than those through a monolayer of organic, C18 alkyl chains that is about half as wide, therefore suggesting transport mechanlsm(s) different from the often considered coherent mechanism. Our results show that the employed proteins maintain their conformation under these conditions. The relatively efficient ETp through these proteins opens up possibilities for using such blomolecules as current-carrying elements in solid-state electronic devices.

Some simple criteria can serve to estimate to what extent further developments are possible for the various types of photovoltaic cells and to which degree basic limitations may affect such developments. To do so, we use several yardsticks, namely 1. The fraction that the efficiency of the best commercially available module represents of the most efficient, reported laboratory cell; 2. The fractions of the maximal possible current for this cell that are represented by the short circuit current and the current at maximum power of this best laboratory cell; and 3. The fractions of the optical bandgap or the energy of the effective optical absorption edge of the cell, that are represented by the open circuit voltage and the voltage at maximum power of this best laboratory cell. An additional yardstick is the fraction of the efficiency of the best laboratory cell of the Shockley-Queisser (SQ) efficiency. This last yardstick reflects mostly academic ability rather than industrial promise. To some extent the first yardstick expresses the manufacturing maturity of the cell type, shown by the higher value for CdTe than for CIGS, or for the single-, compared to the multi-junction a-Si modules, with the ratios for the dye and organic systems much lower still. The ratio for the highly developed Si cells does show what can be expected. While the second and the third yardsticks express a limit, related to the SQ one, the rather low molecular cell values appear to indicate basic limitations for such cells, which we note. The significant differences between a-Si on the one hand and CdTe and CIGS cells on the other hand genuinely reflect the different physics of these polycrystalline systems. The need to identify and define limitations and distinguish then from immaturity is becoming critical for future thin film cell development and this type of analysis can, therefore help us making our choices for the future.

The electronic band structure of different alkyl/Si(111) self-assembled monolayers (SAMs) was investigated using photoelectron spectroscopy (PES) with variable photon energy. We observe a significant dispersion in the valence-band spectra and a large density-of-states (DOS) effect. The dispersion can be described by quantum well states, which depend only on the local properties of the alkanes with a dispersion relation similar to polyethylene and without any significant influence of the Si/molecule interface. Furthermore, the DOS effect is due to averaging over molecules with different tilt angles and thus can be considered as indicator for the degree of orientational order within the SAM. Finally we present a structural model for a description of the PES data, which takes both aspects into account.

We report on electronic transport measurements through dense monolayers of CH ₃(CH ₂) _nPO ₃H ₂ molecules of varying chain lengths, with a strong and stable bond through the phosphonic acid end group to a 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.

Alkyl chain molecules on n-Si were used to test the concept of hybrid metal-organic insulator-semiconductor (MOIS) solar cells. Test structures were made by binding alkyl chain molecules via Si-O-C bonds to oxide-free n-Si surfaces, using self-assembly. With thiol groups at the terminals away from the Si, binding of Au nanoparticles, followed by electroless Au plating yields semitransparent top contacts. First cells give, under 25 mW/ cm² white light illumination, open-circuit voltage V_oc =0.48 V and fill factor FF=0.58. Because with sulfur termination the molecules have a dipole that limits inversion of the Si, we also used methyl-terminated monolayers. Even though then we can work, at this point, only with a Hg top contact, without chemical bond to the molecules, we get, using only radiation (∼AM 1.5) collected around the contact, the expected higher V_oc =0.54 V, and respectable 0.8 FF, justifying further MOIS cell development.

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 on sustainable energy (and materials) resources.

Interfacing functional proteins with solid supports for device applications is a promising route to possible applications in bio-electronics, -sensors, and -optics. Various possible applications of bacteriorhodopsin (bR) have been explored and reviewed since the discovery of bR. This tutorial review discusses bR as a medium for biomolecular optoelectronics, emphasizing ways in which it can be interfaced, especially as a thin film, solid-state current-carrying electronic element.

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.

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.

Forget about 'the' solution. Instead, we need to work toward a strong, sustainable mosaic of many solutions.

(Figure Presented) Can we put organic molecules to use as electronic components? The answer to this question is to no small degree limited by the ability to contact them electrically without damaging the molecules. In this Account, we present some of the methods for contacting molecules that do not or minimally damage them and that allow formation of electronic junctions that can become compatible with electronics from the submicrometer to the macroscale. In "Linnaean" fashion, we have grouped contacting methods according to the following main criteria: (a) is a chemical bond is required between contact and molecule, and (b) is the contact "ready-made", that is, preformed, or prepared in situ? Contacting methods that, so far, seem to require a chemical bond include spin-coating a conductive polymer and transfer printing. In the latter, a metallic pattern on an elastomeric polymer is mechanically transferred to molecules with an exposed terminal group that can react chemically with the metal. These methods allow one to define structures from several tens of nanometers size upwards and to fabricate devices on flexible substrates, which is very difficult by conventional techniques. However, the requirement for bifunctionality severely restricts the type of molecules that can be used and can complicate their self-assembly into monolayers. Methods that rely on prior formation of the contact pad are represented by two approaches: (a) use of a liquid metal as electrode (e.g., Hg, Ga, various alloys), where molecules can be adsorbed on the liquid metal and the molecularly modified drop is brought into contact with the second electrode, the molecules can be adsorbed on the second electrode and then the liquid metal brought into contact with them, or bilayers are used, with a layer on both the metal and the second electrode and (b) use of preformed metal pads from a solid substrate and subsequent pad deposition on the molecules with the help of a liquid. These methods allow formation of contacts easily and rapidly and allow many types of monolayers and metals to be analyzed. However, in their present forms such approaches are not technologically practical. Direct in situ vacuum evaporation of metals has been used successfully only with bifunctional molecules because it is too invasive and damaging, in general. A more general approach is indirect vacuum evaporation, where the metal atoms and clusters, emitted from the source, reach the sample surface in an indirect line of sight, while cooled by multiple collisions with an inert gas. This method has clear technological possibilities, but more research is needed to increase deposition efficiency and find ways to characterize the molecules at the interface and to prevent metal penetration between molecules or through pinholes, also if molecules lack reactive termination groups. This Account stresses the advantages, weak points, and possible routes for the development of contacting methods. This way it shows that there is at present no one ideal soft contacting method, whether it is because of limitations and problems inherent in each of the methods or because of insufficient understanding of the interfacial chemistry and physics. Hopefully, this Account will present the latter issue as a research challenge to its readers.

We explore two main ways to use molecules in molecular electronics, electrostatically, as dipolar films and electrodynamically, where current passes through them. For the former we find that incomplete partial dipolar molecular films can control diode behaviour and that this effect extends to poly- and nano-crystalline solar cells. For the latter complete monolayers are needed, as ideal as possible to assure current transport through the molecules. Such systems with alkyl chain monolayers behave like ideal MIS diodes with significant photovoltaic activity, due to the remarkable insulating behavior of the monolayer. Recently we started to combine the two effects by adding dipolar character to the completely covering alkyl monolayers, enabling modulating the electronic quality of the monolayers. Chemically the interesting aspect is that the introduction of strong leaving groups on the monolayers allows nucleophilic substitutions, to allow further reactions. This, thus, creates a platform for further molecular device modification.

A reliable and reproducible method for preparing bacteriorhodopsin (bR)-containing metal-biomolecule-monolayer-metal planar junctions via vesicle fusion tactics and soft deposition of Au top electrodes is reported. Optimum monolayer and junction preparations, including contact effects, are discussed. The electron-transport characteristics of bR-containing membranes are studied systematically by incorporating native bR or artificial bR pigments derived from synthetic retinal analogues, into single solid-supported lipid bilayers. Current-voltage (I-V) measurements at ambient conditions show that a single layer of such bR-containing artificial lipid bilayers pass current in solid electrode/bilayer/solid electrode structures. The current is passed only if retinal or its analogue is present in the protein. Furthermore, the preparations show photoconductivity as long as the retinal can isomerize following light absorption. Optical characterization suggests that the junction photocurrents might be associated with a photochemically induced M-like intermediate of bR. I-V measurements along with theoretical estimates reveal that electron transfer through the protein is over four orders of magnitude more efficient than what would be estimated for direct tunneling through 5 nm of water-free peptides. Our results furthermore suggest that the light-driven proton-pumping activity of the sandwiched solid-state bR monolayer contributes negligibly to the steady-state light currents that are observed, and that the orientation of bR does not significantly affect the observed I-V characteristics.

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 Au 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.

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.

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 SiO₂, 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) π* 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.

Coupling of noble-metal nanoparticles (NPs) into electronics might lead to interesting new avenues in nanoelectronics. It was found that currents through metal//organic (or inorganic) insulator/Au NP monolayer//metal planar junctions (2) are orders of magnitude higher than what is obtained without the NP monolayer (1). (Graph Presented).

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 CdS 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.

Studying electron transport (ET) through proteins is hampered by achieving reproducible experimental configurations, particularly electronic contacts to the proteins. The transmembrane protein bacteriorhodopsin (bR), a natural light-activated proton pump in purple membranes of Halobacterium salinarum, is well studied for biomolecular electronics because of its sturdiness over a wide range of conditions. To date, related studies of dry bR systems focused on photovoltage generation and photoconduction with multilayers, rather than on the ET ability of bR, which is understandable because ET across 5-nm-thick, apparently insulating membranes is not obvious. Here we show that electronic current passes through bR-containing artificial lipid bilayers in solid "electrode-bilayer-electrode" structures and that the current through the protein is more than four orders of magnitude higher than would be estimated for direct tunneling through 5-nm, water-free peptides. We find that ET occurs only if retinal or a close analogue is present in the protein. As long as the retinal can isomerize after light absorption, there is a photo-ET effect. The contribution of light-driven proton pumping to the steady-state photocurrents is negligible. Possible implications in view of the suggested early evolutionary origin of halobacteria are noted.

The superior performance of certain polycrystalline (PX) solar cells compared to that of corresponding single-crystal ones has been an enigma until recently. Conventional knowledge predicted that grain boundaries serve as traps and recombination centers for the photogenerated carriers, which should decrease cell performance. To understand if cell performance is limited by grain bulk, grain surface, and/or grain boundaries (GBs), we performed high-resolution mapping of electronic properties of single GBs and grain surfaces in PX p-CdTe/n-CdS solar cells. Combining results from scanning electron and scanning probe microscopies, viz., capacitance, Kelvin probe, and conductive probe atomic force microscopies, and comparing images taken under varying conditions, allowed elimination of topography-related artifacts and verification of the measured properties. Our experimental results led to several interesting conclusions: 1) current is depleted near GBs, while photocurrents are enhanced along the GB cores; 2) GB cores are inverted, which explains GB core conduction. Conclusions (1) and (2) imply that the regions around the GBs function as an extension of the carrier-collection volume, i.e., they participate actively in the photovoltaic conversion process, while conclusion (2) implies minimal recombination at the GB cores; 3) the surface potential is diminished near the GBs; and 4) the photovoltaic and metallurgical junction in the n-CdS/p-CdTe devices coincide. These conclusions, taken together with gettering of defects and impurities from the bulk into the GBs, explain the good photovoltaic performance of these PX cells (at the expense of some voltage loss, as is indeed observed). We show that these CdTe GB features are induced by the CdCl ₂ heat treatment used to optimize these cells in the production process.

Two-dimensional arrangements of molecules can show remarkable cooperative electronic effects. Such effects can serve to achieve direct electronic sensing of chemical and physical processes via electrostatic effects, i.e., without transfer of charge or matter between the locus of sensing and that of detection.

Diodes made by (indirectly) evaporating Au on a monolayer of molecules that are adsorbed chemically onto GaAs, via either disulfide or dicarboxylate groups, show roughly linear but opposite dependence of their effective barrier height on the dipole moment of the molecules. We explain this by Au-molecule (electrical) interactions not only with the exposed end groups of the molecule but also with its binding groups. We arrive at this conclusion by characterizing the interface by in situ UPS-XPS, ex situ XPS, TOF-SIMS, and Kelvin probe measurements, by scanning microscopy of the surfaces, and by current-voltage measurements of the devices. While there is a very limited interaction of Au with the dicarboxylic binding groups, there is a much stronger interaction with the disulfide groups. We suggest that these very different interactions lead to different (growth) morphologies of the evaporated gold layer, resulting in opposite effects of the molecular dipole on the junction barrier height.

The effect of surface treatments on p-CdTe/n-CdS solar cell performance was examined. Adsorption of organic molecules with various magnitudes and directions of the dipole moment on p-CdTe resulted in controlled changes in electron affinity and surface band bending. Similar adsorption on CdTe in state-of-the-art p-CdTe/n-CdS solar cells changes the cell performance, and we explain this by a combination of increased series resistance and changes in light absorption and in cell photovoltage. While at this stage no improvement in performance has been found with these cell structures, which are the result of years of empirical optimization, the molecular effect on the photovoltage shows that it is possible in this way to control the photovoltaic effect at this junction. Separate optimization may well lead to improvement by inserting a dipole layer near the photovoltaic interface. Our results also show that this is even possible when dipole adsorption is performed on the complete polycrystalline thin-film cell.

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 _∝) 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.

We show reproducible, stable negative differential resistance (NDR) at room temperature in molecule-controlled, solvent-free devices, based on reversible changes in molecule-electrode interface properties. The active component is the cyclic disulfide end of a series of molecules adsorbed onto mercury. As this active component is reduced, the Hg-molecule contact is broken, and an insulating barrier at the molecule-electrode interface is formed. Therefore, the alignment of the molecular energy levels, relative to the Fermi levels of the electrodes, is changed. This effect results in a decrease in the current with voltage increase as the reduction process progresses, leading to the so-called NDR behavior. The effect is reproducible and repeatable over more than 50 scans without any reduction in the current. The stability of the system, which is in the "solid state" except for the Hg, is due to the molecular design where long alkyl chains keep the molecules aligned with respect to the Hg electrode, even when they are not bound to it any longer.

We review the status of the understanding of dye-sensitized solar cells (DSSC), emphasizing clear physical models with predictive power, and discuss them in terms of the chemical and electrical potential distributions in the device. Before doing so, we place the DSSC in the overall picture of photovoltaic energy converters, reiterating the fundamental common basis of all photovoltaic systems as well as their most important differences.

We 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 function 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.

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.

CdTe/CdS solar cells were subjected to heat stress at 200 °C in the dark under different environments (in N₂ and in air), and under illumination (in N₂). We postulate that two independent mechanisms can explain degradation phenomena in these cells: i) Excessive Cu doping of CdS: Accumulation of Cu in the CdS with stress, in the presence of Cl, will increase the photoconductivity of CdS. With limited amounts of Cu in CdS, this does NOT affect the photovoltaic behavior, but explains the crossover of light/dark current-voltage (J-V) curves. Overdoping of CdS with Cu can be detrimental to cell performance by creating deep acceptor states, acting as recombination centers, and compensating donor states. Under illumination, the barrier to Cu cations at the cell junction is reduced, and, therefore, Cu accumulation in the CdS is enhanced. Recovery of light-stress induced degradation in CdTe/CdS cells in the dark is explained by dissociation of the acceptor defects. ii) Back contact barrier: Oxidation of the CdTe back surface in O₂/H₂O-containing environment to form an insulating oxide results in a back-contact barrier. This barrier is expressed by a rollover in the J-V curve. Humidity is an important factor in air-induced degradation, as it accelerates the oxide formation. Heat treatment in the dark in inert atmosphere can stabilize the cells against certain causes of degradation, by completing the back contact anneal.

We present a concise, although admittedly non-exchaustive, but hopefully didactic review and discussion of some of the central and basic concepts related to the energetics of surfaces and interfaces of solids. This is of particular importance for surfaces and interfaces that involve organic molecules and molecular films. It attempts to pull together different views and terminologies used in the solid state, electrochemistry, and electronic device communities, regarding key concepts of local and absolute vacuum level, surface dipole, work function, electron affinity, and ionization energy. Finally, it describes how standard techniques like photoemission spectroscopy can be used to measure such quantities.

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/alkylthiols/p-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 current 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 (≤C₁₂), resulting in an additional route to charge transport by tunneling through space. In contrast, long chains (≥C₁₄) 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.

Using Hg/alkyl-chain-monolayer/p-Si devices we find that the type of contact between the chains and the electrodes (chemical bonding or not) is of critical importance for electronic transport across the junctions. As the semiconductor is p-type, the transport is that of holes. In agreement with theory we find that holes tunnel more efficiently through alkyl chains than do electrons.

The mechanism by which dicarboxylic acid molecules adsorb onto ambient-exposed GaAs (1 0 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.

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.

High efficiency CdTe/CdS thin-film solar cells require low resistance contacts to p-CdTe, which is frequently achieved by addition of Cu. Decreases in cell efficiency over time. however. have been associated with Cu from the contact. The question that is considered here is if Cu is really detrimental to cell performance? By performing a series of thermal stress tests the authors reach a far more optimistic conclusion than what has hitherto been assumed. The Figure shows the proposed model for action of Cu (and Cl) in the CdTe/CdS cell.

The onset wavelengths of the surface photovoltage (SPV) in dye-sensitized solar cells (DSSCs) with different mesoporous, wide-band gap electron conductor anode materials, viz., TiO₂ (anatase), Nb₂O₅ (amorphous and crystalline), and SrTiO₃, using the same Ru bis-bipyridyl dye for all experiments, are different. We find a clear dependence of these onset wavelengths on the conduction band edge energies (E_CB) of these oxides. This is manifested in a blue-shift for cells with Nb₂O₅ and SrTiO₃ compared to those with TiO₂. The E_CB levels of Nb₂O₅ and SrTiO₃ are known to be some 200-250 meV closer to the Vacuum level than that of our anatase films, while there is no significant difference between the optical absorption spectra of the dye on the various films. We, therefore, suggest that the blue shift is due to electron injection from excited-state dye levels above the LUMO into Nb₂O₅ and SrTiO₃. Such injection comes about because, in contrast to what is the case for anatase, the LUMO of the adsorbed dye in the solution is below the E_CB of these semiconductors, necessitating the involvement of higher vibrational and/or electronic levels of the dye, with the former being more likely than the latter. While for Nb₂O₅ hot electron injection has been proposed earlier, on the basis of flash photolysis experiments, this is the first evidence for such ballistic electron-transfer involving SrTiO₃, a material very similar to anatase but with a significantly smaller electron affinity. Additional features in the SPV spectra of SrTiO₃ and amorphous Nb₂O₅ (but not in those of crystalline Nb₂O₅) can be understood in terms of hole injection from the dye into the oxide via intraband gap surface states.

We suggest an alternative technique for electroluminescent device fabrication, based on our earlier findings of electric field (E-field)-induced bipolar transistor creation in Si, doped with Li. An external electric field served to induce μm sized electroluminescent device structures in Si, that had been doped prior to E-field application, with Li, and Er via thermal in-diffusion. Such devices exhibit low temperature, near infrared (IR) electroluminescence at ∼ 1.16 and 1.55 μm, corresponding to transitions associated with Li and Er levels, respectively, in the forbidden gap. While Li also creates radiative recombination centers in Si, the Er-based IR radiation is the most desirable one. At the same time Li-doping is what makes E-field-induced p-n junction fabrication possible.

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 cm²/s for a 3 year lifetime. Ways to overcome or mitigate this limitation are indicated.

The recent literature regarding the stability of CdTe/CdS photovoltaic cells (as 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.

The use of molecules to control electron transport is an interesting possibility, not least because of the anticipated role of molecules in future electronic devices(1). But physical implementations using discrete molecules are neither conceptually(2,3) simple nor technically straightforward (difficulties arise in connecting the molecules to the macroscopic environment). But the use of molecules in electronic devices is not limited to single molecules, molecular wires or bulk material. Here we demonstrate that molecules can control the electrical characteristics of conventional metal-semiconductor junctions, apparently without the need for electrons to be transferred onto and through the molecules. We modify diodes by adsorbing small molecules onto single crystals of n-type GaAs semiconductor. Gold contacts were deposited onto the modified surface, using a 'soft' method to avoid damaging the molecules(4). By using a series of multifunctional molecules whose dipole is varied systematically, we produce diodes with an effective barrier height that is tuned by the molecule's dipole moment. These barrier heights correlate well with the change in work function of the GaAs surface after molecular modification. This behaviour is consistent with that of unmodified metal-semiconductor diodes, in which the barrier height can depend on the metal's work function.

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 monolayer, a metalloporphyrin (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 Fen(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 ¹H 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 were 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 resulting from binding of O₂ to the monolayer.

The chemical effects of oxygenation of Cu(In,Ga)Se₂ (CIGS) interfaces are analyzed and are shown to involve passivation of Se deficiencies and Cu removal. The former effect is beneficial at grain boundaries, but detrimental at the CdS/CIGS interface. The latter effect is purely detrimental. Na and chemical bath deposition (CBD) treatments are shown to isolate the `good' oxygenation effect from the `bad' ones. Na is shown to promote oxygenation already before the deposition of the buffer and window layers, which allows a maximization of the benefits of Se deficiency passivation and a minimization of Cu removal. Next, the CBD of the CdS buffer layer restores the interface charge, due to creation of Cd_Cu interface donors and possibly a removal of O_Se interface acceptors. This highlights the crucial role that interface redox engineering plays in optimizing the performance of CIGS-based solar cells.

Geringe Konzentrationen von NO in physiologischen Pufferlösungen (1 ppm, ca. 3 μM) lassen sich mit dem gezeigten maßgeschneiderten molekularen Zweikomponentensystem ein pinzettenartig von einem organischen Liganden gehaltenes Eisen(III)porphyrin nachweisen, das mit einer Seite an einen Detektor auf GaAsBasis gekoppelt ist. Bindet NO an das Eisen(III)porphyrin, ändert sich die Stromstärke.

We present a simple, compact, and robust arrangement for surface photovoltage measurements of free semiconductor surfaces immersed in liquids. It is based on the classical Kelvin probe arrangement, where the semiconductor sample is put in a liquid-containing, electrically insulating vessel, with an optically transparent window, situated between the sample and the Kelvin probe. At the price of permitting relative, rather than absolute, contact potential difference values, this modification enables easy, routine surface photovoltage measurements of semiconductors in any kind of liquid ambient. The validity and efficiency of this approach are demonstrated by surface photovoltage spectra obtained from the p-InP(100) surface in various liquid etchants.

Communication: Is "self-healing" the source of the stability of Cu(In, Ga)Se-2-based solar modules? The proven remarkable stability and radiation hardness of Cu(In,Ga)Se-2 (CIGS) solar cells stand in apparent contradiction to the fact that CIGS shows both short-range (metastable defect centers) and long-range (significant Cu migration) instabilities. The authors suggest that these instabilities may in fact be a prerequisite for CIGS's stability as they allow a degree of flexibility or "smartness" in accommodating externally imposed changes. Two self-healing cycles are proposed, in which copper species play a particularly important role.

Photoelectron spectroscopy and admittance spectroscopy were used to analyze Cu(In,Ga)Se₂ (CIGS) based thin films and heterojunction solar cells based on chemical oxygenation and post-deposition air-annealing effects. The effect of CIGS surface chemistry on the electronic structure of the heterojunction solar cells and the influence on the CIGS layer of oxygenation-induced Cu redistribution were analyzed. Results showed that charge redistribution and compensation of the effective acceptor density can be achieved in the bulk of the absorber.

Dopant flux in a semiconductor junction due to chemical diffusion and drift (electromigration) was analyzed as a possible determining factor for device life expectancy at room temperature. Simple relations are derived and/or recalled to allow estimates of lifetimes. They are shown to be appropriate for III-V heterojunction bipolar transistors. We suggest that this chemical factor must be considered for compound semiconductor devices, as their dimensions shrink.

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

We have developed a new, efficient method to dope bulk single crystals of CdTe by In, via gas phase diffusion, using In₄Te₃ as the source. Doping was carried out on crystals of very high resistivity (>5 MΩ cm), following annealing in the temperature range of 350-1000°C. Resulting crystals showed n-type conductivity with a free carrier concentration in the range of 10¹⁵-10¹⁸ cm^-3 and carrier mobility of 100-750 cm²/(V s), depending on the annealing temperature and time, and on the cooling conditions. Incorporation of In was found to be a function of annealing time and temperature only. Up to 650°C, the In and the free electron concentrations are roughly the same.

We show that the chemisorption of dicarboxylic acids on GaAs (100) is described well by a two-site mechanism, in contrast to benzoic acid adsorption which fits to a one-site mechanism. We do so by using a novel electrical method for direct measurement of adsorption kinetics. In the method we measure the current through a GaAs/(Al, Ga)As-based device, where the bare surface between two contacts is used as the adsorption domain. The results, which are in agreement with FTIR absorption equilibrium data, are obtained in ambient notwithstanding the notorious instability of GaAs surfaces under such conditions. We conclude that these acids chemisorb on the GaAs surface and that binding is significantly stronger for the di-than for the monocarboxylic acids.

We show how sub-μm 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.

The structure of CuInSe2 was redetermined, using synchrotron X-radiation with 0.15 Angstrom wavelength, thus eliminating problems of uncertainties introduced by absorption corrections. This allowed us to look at the effect of subjecting crystals to strong electric fields, a process known to be able to type convert the material under relatively mild conditions. Proper refinement became possible after correcting for twinning. The main results are relatively high Cu temperature factors and significant electron density in octahedral interstitial sites. The main results of electric field application are a decrease in structure quality (increased R factor) and a slight increase in electron density on Cu sites. These preliminary results point to the need for further work with twin-free crystals.

The promising new generation of solar cells based on CIGS (Cu(I,Ga)Se-2) exhibits behavior differing from that of earlier cells because of changes in the method of preparation, leading, among other things, to a difference in sodium content. A simple defect chemical model is presented for the effects of sodium on the surface chemistry and electronic properties of CIGS thin films. The model, based on the well-known catalytic effect that alkali metals have on surface oxidation of semiconductors, is shown to be consistent with the experimental data available in the literature.

By growing CuInSe(2) with the traveling heater method, from an In melt (at a temperature below that of the sphalerite-chalcopyrite transition), twinning in the resulting single crystals was suppressed. The resulting crystals were n-type and could be converted to p-type by Se anneal. Both types were characterized structurally by X-ray diffraction, for composition by microprobe analyses, morphologically by AFM and SEM, and electrically. They were found to be mostly homogeneous, with mirror-like cleavage and without twins.

A doped semiconductor can be viewed as a mixed electronic-ionic conductor, with the dopants as mobile ions. Normally the temperature range where this becomes true is not even close to that where the (opto)electronic properties of the material are of interest. However notable exceptions exist and some examples of these are reviewed here. We limit ourselves to those cases where semiconductivity is preserved when the (mobile) dopant concentration changes and ambipolar behaviour can be obtained by dopant mobility. Dopant diffusion and drift are of interest not only in materials such as Si:Li, known from its use in radiation detectors, but also in ternary semiconductors, such as (HE,Cd)Te and CuInSe2. Understanding the phenomena is important not only for low-temperature doping, but also because of the implications that it has for device miniaturization, as dopant diffusion and drift impose chemical limits on device stability.