Experimental evidence for defect tolerance in Pb-halide perovskites.

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.

Near-Temperature-Independent Electron Transport Well beyond Expected Quantum Tunneling Range via Bacteriorhodopsin Multilayers.

A key conundrum of biomolecular electronics is efficient electron transport (ETp) through solid-state junctions up to 10 nm, often without temperature activation. Such behavior challenges known charge transport mechanisms, especially via nonconjugated molecules such as proteins. Single-step, coherent quantum-mechanical tunneling proposed for ETp across small protein, 2-3 nm wide junctions, but it is problematic for larger proteins. Here we exploit the ability of bacteriorhodopsin (bR), a well-studied, 4-5 nm long membrane protein, to assemble into well-defined single and multiple bilayers, from ∼9 to 60 nm thick, to investigate ETp limits as a function of junction width. To ensure sufficient signal/noise, we use large area (∼10-3 cm2) Au-protein-Si junctions. Photoemission spectra indicate a wide energy separation between electrode Fermi and the nearest protein-energy levels, as expected for a polymer of mostly saturated components. Junction currents decreased exponentially with increasing junction width, with uniquely low length-decay constants (0.05-0.5 nm-1). Remarkably, even for the widest junctions, currents are nearly temperature-independent, completely so below 160 K. While, among other things, the lack of temperature-dependence excludes, hopping as a plausible mechanism, coherent quantum-mechanical tunneling over 60 nm is physically implausible. The results may be understood if ETp is limited by injection into one of the contacts, followed by more efficient charge propagation across the protein. Still, the electrostatics of the protein films further limit the number of charge carriers injected into the protein film. How electron transport across dozens of nanometers of protein layers is more efficient than injection defines a riddle, requiring further study.

Topotactic, Vapor-Phase, In Situ Monitored Formation of Ultrathin, Phase-Pure 2D-on-3D Halide Perovskite Surfaces.

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 (<10 nm) R2PbI4 layers on 3D perovskites is challenging with spin coating; even more so is its upscaling for larger-area devices. We report on vapor-phase cation exchange of the 3D surface with the R2PbI4 molecules and real-time in situ growth monitoring by photoluminescence (PL) to determine limits for forming ultrathin 2D layers. We characterize the 2D growth stages, following the changing PL intensity-time profiles, by combining structural, optical, morphological, and compositional characterizations. Moreover, from quantitative X-ray photoelectron spectroscopy (XPS) analysis on 2D/3D bilayer films, we estimate the smallest width of a 2D cover that we can grow to be <5 nm, roughly the limit for efficient tunneling through a (semi)conjugated organic barrier. We also find that, besides protecting the 3D against ambient humidity-induced degradation, the ultrathin 2D-on-3D film also aids self-repair following photodamage.

A-Site Cation Dependence of Self-Healing in Polycrystalline APbI3 Perovskite Films.

In terms of sustainable use, halide perovskite (HaP) semiconductors have a strong advantage over most other classes of materials for (opto)electronics, as they can self-heal (SH) from photodamage. While there is considerable literature on SH in devices, where it may not be clear exactly where damage and SH occur, there is much less on the HaP material itself. Here we perform "fluorescence recovery after photobleaching" (FRAP) measurements to study SH on polycrystalline thin films for which encapsulation is critical to achieving complete and fast self-healing. We compare SH in three photoactive APbI3 perovskite films by varying the A-site cation ranging from (relatively) small inorganic Cs through medium-sized MA to large FA (the last two are organic cations). While the A cation is often considered electronically relatively inactive, it significantly affects both SH kinetics and the threshold for photodamage. The SH kinetics are markedly faster for γ-CsPbI3 and α-FAPbI3 than for MAPbI3. Furthermore, γ-CsPbI3 exhibits an intricate interplay between photoinduced darkening and brightening. We suggest possible explanations for the observed differences in SH behavior. This study's results are essential for identifying absorber materials that can regain intrinsic, insolation-induced photodamage-linked efficiency loss during its rest cycles, thus enabling applications such as autonomously sustainable electronics.

Protein Orientation Defines Rectification of Electronic Current via Solid-State Junction of Entire Photosystem-1 Complex.

We demonstrate that the direction of current rectification via one of nature's 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 current-voltage 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. Current-voltage-temperature 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.

Soil adsorption and transport of lead in the presence of perovskite solar cell-derived organic cations.

Perovskite photovoltaics offer a highly efficient and low-cost solar energy harvesting technology. However, the presence of lead (Pb) cations in photovoltaic halide perovskite (HaPs) materials is concerning, and quantifying the environmental hazard of accidental Pb2+ leaching into the soil is crucial for assessing the sustainability of this technology. Pb2+ from inorganic salts was previously found to remain in the upper soil layers due to adsorption. However, Pb-HaPs contain additional organic and inorganic cations, and competitive cation adsorption may affect Pb2+ retention in soils. Therefore, we measured, analyzed by simulations and report the depths to which Pb2+ from HaPs penetrates into 3 types of agricultural soil. Most of the HaP-leached Pb2+ is found to be retained already in the first cm of the soil columns, and subsequent rain events do not induce Pb2+ penetration below the first few cm of soil surface. Surprisingly, organic co-cations from the dissolved HaP are found to enhance the Pb2+ adsorption capacity in clay-rich soil, compared to non-HaP-based Pb2+ sources. Our results imply that installation over soil types with improved Pb2+ adsorption, and removal of only the contaminated topsoil, are sufficient means to prevent ground water contamination by HaP-leached Pb2+.

Phonon-driven intra-exciton Rabi oscillations in CsPbBr3 halide perovskites.

Coupling electromagnetic radiation with matter, e.g., by resonant light fields in external optical cavities, is highly promising for tailoring the optoelectronic properties of functional materials on the nanoscale. Here, we demonstrate that even internal fields induced by coherent lattice motions can be used to control the transient excitonic optical response in CsPbBr3 halide perovskite crystals. Upon resonant photoexcitation, two-dimensional electronic spectroscopy reveals an excitonic peak structure oscillating persistently with a 100-fs period for up to ~2 ps which does not match the frequency of any phonon modes of the crystals. Only at later times, beyond 2 ps, two low-frequency phonons of the lead-bromide lattice dominate the dynamics. We rationalize these findings by an unusual exciton-phonon coupling inducing off-resonant 100-fs Rabi oscillations between 1s and 2p excitons driven by the low-frequency phonons. As such, prevailing models for the electron-phonon coupling in halide perovskites are insufficient to explain these results. We propose the coupling of characteristic low-frequency phonon fields to intra-excitonic transitions in halide perovskites as the key to control the anharmonic response of these materials in order to establish new routes for enhancing their optoelectronic properties.

Experimental Data Confirm Carrier-Cascade Model for Solid-State Conductance across Proteins.

The finding that electronic conductance across ultrathin protein films between metallic electrodes remains nearly constant from room temperature to just a few degrees Kelvin has posed a challenge. We show that a model based on a generalized Landauer formula explains the nearly constant conductance and predicts an Arrhenius-like dependence for low temperatures. A critical aspect of the model is that the relevant activation energy for conductance is either the difference between the HOMO and HOMO-1 or the LUMO+1 and LUMO energies instead of the HOMO-LUMO gap of the proteins. Analysis of experimental data confirms the Arrhenius-like law and allows us to extract the activation energies. We then calculate the energy differences with advanced DFT methods for proteins used in the experiments. Our main result is that the experimental and theoretical activation energies for these three different proteins and three differently prepared solid-state junctions match nearly perfectly, implying the mechanism's validity.

A RuCoBO Nanocomposite for Highly Efficient and Stable Electrocatalytic Seawater Splitting.

Efficient and stable electrocatalysts are critically needed for the development of practical overall seawater splitting. The nanocomposite of RuCoBO has been rationally engineered to be an electrocatalyst that fits these criteria. The study has shown that a calcinated RuCoBO-based nanocomposite (Ru2Co1BO-350) exhibits an extremely high catalytic activity for H2 and O2 production in alkaline seawater (overpotentials of 14 mV for H2 evolution and 219 mV for O2 evolution) as well as a record low cell voltage (1.466 V@10 mA cm-2) and long-term stability (230 h @50 mA cm-2 and @100 mA cm-2) for seawater splitting. The results show that surface reconstruction of Ru2Co1BO-350 occurs during hydrogen evolution reaction and oxygen evolution reaction, which leads to the high activity and stability of the catalyst. The reconstructed surface is highly resistant to Cl- corrosion. The investigation suggests that a new strategy exists for the design of high-performance Ru-based electrocatalysts that resist anodic corrosion during seawater splitting.

Biotin Binding Hardly Affects Electron Transport Efficiency across Streptavidin Solid-State Junctions.

The electron transport (ETp) efficiency of solid-state protein-mediated junctions is highly influenced by the presence of electron-rich organic cofactors or transition metal ions. Hence, we chose to investigate an interesting cofactor-free non-redox protein, streptavidin (STV), which has unmatched strong binding affinity for an organic small-molecule ligand, biotin, which lacks any electron-rich features. We describe for the first time meso-scale ETp via electrical junctions of STV monolayers and focus on the question of whether the rate of ETp across both native and thiolated STV monolayers is influenced by ligand binding, a process that we show to cause some structural conformation changes in the STV monolayers. Au nanowire-electrode-protein monolayer-microelectrode junctions, fabricated by modifying an earlier procedure to improve the yields of usable junctions, were employed for ETp measurements. Our results on compactly integrated, dense, uniform, ∼3 nm thick STV monolayers indicate that, notwithstanding the slight structural changes in the STV monolayers upon biotin binding, there is no statistically significant conductance change between the free STV and that bound to biotin. The ETp temperature (T) dependence over the 80-300 K range is very small but with an unusual, slightly negative (metallic-like) dependence toward room temperature. Such dependence can be accounted for by the reversible structural shrinkage of the STV at temperatures below 160 K.

Electron transport via tyrosine-doped oligo-alanine peptide junctions: role of charges and hydrogen bonding.

A way of modulating the solid-state electron transport (ETp) properties of oligopeptide junctions is presented by charges and internal hydrogen bonding, which affect this process markedly. The ETp properties of a series of tyrosine (Tyr)-containing hexa-alanine peptides, self-assembled in monolayers and sandwiched between gold electrodes, are investigated in response to their protonation state. Inserting a Tyr residue into these peptides enhances the ETp carried via their junctions. Deprotonation of the Tyr-containing peptides causes a further increase of ETp efficiency that depends on this residue's position. Combined results of molecular dynamics simulations and spectroscopic experiments suggest that the increased conductance upon deprotonation is mainly a result of enhanced coupling between the charged C-terminus carboxylate group and the adjacent Au electrode. Moreover, intra-peptide hydrogen bonding of the Tyr hydroxyl to the C-terminus carboxylate reduces this coupling. Hence, the extent of such a conductance change depends on the Tyr-carboxylate distance in the peptide's sequence.

NiN-Passivated NiO Hole-Transport Layer Improves Halide Perovskite-Based Solar Cell.

The interfaces between inorganic selective contacts and halide perovskites (HaPs) are possibly the greatest challenge for making stable and reproducible solar cells with these materials. NiOx, an attractive hole-transport layer as it fits the electronic structure of HaPs, is highly stable and can be produced at a low cost. Furthermore, NiOx can be fabricated via scalable and controlled physical deposition methods such as RF sputtering to facilitate the quest for scalable, solvent-free, vacuum-deposited HaP-based solar cells (PSCs). However, the interface between NiOx and HaPs is still not well-controlled, which leads at times to a lack of stability and Voc losses. Here, we use RF sputtering to fabricate NiOx and then cover it with a NiyN layer without breaking vacuum. The NiyN layer protects NiOx doubly during PSC production. Firstly, the NiyN layer protects NiOx from Ni3+ species being reduced to Ni2+ by Ar plasma, thus maintaining NiOx conductivity. Secondly, it passivates the interface between NiOx and the HaPs, retaining PSC stability over time. This double effect improves PSC efficiency from an average of 16.5% with a 17.4% record cell to a 19% average with a 19.8% record cell and increases the device stability.

Interfacial Carbon Makes Nano-Particulate RuO2 an Efficient, Stable, pH-Universal Catalyst for Splitting of Seawater.

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.

Lead Sequestration from Halide Perovskite Solar Cells with a Low-Cost Thiol-Containing Encapsulant.

Perovskite solar cells (PSCs) are being studied and developed because of the outstanding properties of halide perovskites as photovoltaic materials and high conversion efficiencies achieved with the best PSCs. However, leaching out of lead (Pb) ions into the environment presents potential public health risks. We show that thiol-functionalized nanoparticles provide an economic way of minimizing Pb leaching in the case of PSC module damage and subsequent water exposure (at most, ∼2.5% of today's crystal silicon solar panel production cost per square meter). Using commercial materials and methods, we retain ∼90% of Pb without degrading the photovoltaic performance of the cells, compared with nonencapsulated devices, yielding a worst-case scenario of top-soil pollution below natural Pb levels and well below the U.S. Environmental Protection Agency limits.

Self-Healing and Light-Soaking in MAPbI3 : The Effect of H2 O.

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 "self-healing." 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 "light-soaking") 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 H2 O, 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 H2 O, or possibly other proton-related, particularly amine, chemistry.

Prospect of making XPS a high-throughput analytical method illustrated for a Cu x Ni1-x O y combinatorial material library.

Combinatorial material science crucially depends on robust, high-throughput characterization methods. While X-ray photoelectron spectroscopy (XPS) may provide detailed information about chemical and electronic properties, it is a time-consuming technique and, therefore, is not viewed as a high-throughput method. Here we present preliminary XPS data of 169 measurement spots on a combinatorial 72 × 72 cm2 Cu x Ni1-x O y compositional library to explore how characterization and evaluation routines can be optimized to improve throughput in XPS for combinatorial studies. In particular, two quantification approaches are compared. We find that a simple integration (of XPS peak regions) approach is suited for fast evaluation of, in the example system, the [Cu]/([Cu] + [Ni]) ratio. Complementary to that, the time-consuming (XPS peak-) fit approach provides additional insights into chemical speciation and oxidation state changes, without a large deviation of the [Cu]/([Cu] + [Ni]) ratio. This insight suggests exploiting the fast integration approach for 'real time' analysis during XPS data collection, paving the way for an 'on-the-fly' selection of points of interest (i.e., areas on the sample where sudden composition changes have been identified) for detailed XPS characterization. Together with the envisioned improvements when going from laboratory to synchrotron-based excitation sources, this will shorten the analysis time sufficiently for XPS to become a realistic characterization option for combinatorial material science.

Halide perovskite dynamics at work: Large cations at 2D-on-3D interfaces are mobile.

SignificanceSurface engineering of halide perovskites (HaPs), semiconductors with amazing optoelectronic properties, is critical to improve the performance and ambient stability of HaP-based solar cells and light emitting diodes (LEDs). Ultrathin layers of two-dimensional (2D) analogs of the three-dimensional (3D) HaPs are particularly attractive for this because of their chemical similarities but higher ambient stability. But do such 2D/3D interfaces actually last, given that ions in HaPs move readily-i.e., what happens at those interfaces on the atomic scale? A special electron microscopy, which as a bonus also reveals the true conditions for nondestructive analysis, shows that the large ions that are a necessary part of the 2D films can move into the 3D HaP, a fascinating illustration of panta rei in HaPs.

In Operando, Photovoltaic, and Microscopic Evaluation of Recombination Centers in Halide Perovskite-Based Solar Cells.

The origin of the low densities of electrically active defects in Pb halide perovskite (HaP), a crucial factor for their use in photovoltaics, light emission, and radiation detection, remains a matter of discussion, in part because of the difficulty in determining these densities. Here, we present a powerful approach to assess the defect densities, based on electric field mapping in working HaP-based solar cells. The minority carrier diffusion lengths were deduced from the electric field profile, measured by electron beam-induced current (EBIC). The EBIC method was used earlier to get the first direct evidence for the n-i-p junction structure, at the heart of efficient HaP-based PV cells, and later by us and others for further HaP studies. This manuscript includes EBIC results on illuminated cell cross sections (in operando) at several light intensities to compare optoelectronic characteristics of different cells made by different groups in several laboratories. We then apply a simple, effective single-level defect model that allows deriving the densities (Nr) of the defect acting as recombination center. We find Nr ≈ 1 × 1013 cm-3 for mixed A cation lead bromide-based HaP films and ∼1 × 1014 cm-3 for MAPbBr3(Cl). As EBIC photocurrents are similar at the grain bulk and boundaries, we suggest that the defects are at the interfaces with selective contacts rather than in the HaP film. These results are relevant for photovoltaic devices as the EBIC responses distinguish clearly between high- and low-efficiency devices. The most efficient devices have n-i-p structures with a close-to-intrinsic HaP film, and the selective contacts then dictate the electric field strength throughout the HaP absorber.

Response to Comment on "Eppur si Muove: Proton Diffusion in Halide Perovskite Single Crystals": Measure What is Measurable, and Make Measurable What is Not So: Discrepancies between Proton Diffusion in Halide Perovskite Single Crystals and Thin Films.

Buffeteau et al. note that the proton diffusion coefficient in MAPbI3 that is deduced (by the authors) from results, obtained by a suite of complementary techniques, on a large number of single crystals (Adv. Mater. 2020, 32, 2002467) is 5 orders of magnitude higher than what is estimated (by them) in J. Am. Chem. Soc. 2020, 142, 10431, from infrared spectroscopy on ultrathin MAPbI3 films; use of (deuterium/hydrogen) D/H isotope substitution is common to both studies. Buffeteau et al. speculated that proton diffusion in halide perovskite single crystals is dominated by 1D defects, which will somehow not be present in thin films, as those are made up of small-sized crystallites. It is shown here that the idea of a 1D defect is not supported by the body of experimental data gathered on these crystals, that the statistical analysis employed in to Buffeteau et al. to support the criticism is problematic, and it is concluded that the source of the difference must lie elsewhere. Constructive suggestions for this difference are provided and experiments to discern between possible reasons for it are proposed.