Enhanced On–Off Ratio Photodetectors Based on Lead‐Free Cs3Bi2I9 Single Crystal Thin Films

Hybrid organic–inorganic lead halide perovskite single crystal thin film (SCTF) recently has attracted enormous interest in the field of optoelectronic devices, since it efficiently resolves the trade‐off between thickness and carrier diffusion length. However, the toxicity of lead element and the instability induced by organic component still hinder its future developments. In this work, lead‐free all‐inorganic Cs₃Bi₂I₉ SCTF with a high orientation along (00h) has been in situ grown on indium tin oxide (ITO) glass via a space‐limited solvent evaporation crystallization method. The trap density of Cs₃Bi₂I₉ SCTF (5.7 × 10¹² cm^?3) is 263 folds lower than that of the polycrystalline thin film (PCTF) counterpart, together with a 5‐order‐of‐magnitude higher carrier mobility. These superior charge transfer properties enable a photoresponse on–off ratio as high as 11 000, which far surpasses that of the PCTF device by 460 folds, comparable to the lead halide perovskite. Furthermore, the Cs₃Bi₂I₉ SCTF photodetector exhibits outstanding stability even without any encapsulation, whose initial performance is well maintained after aging 1000 h in humid air of 50% RH or continuous on–off light illumination for 20 h. This work will pave the way to produce new families of high‐performance, stable, and nontoxic perovskite SCTF for future optoelectronic applications.     

Tuning Memristivity by Varying the Oxygen Content in a Mixed Ionic–Electronic Conductor

The rising interest shown for adaptable electronics and brain‐inspired neuromorphic hardware increases the need for new device architectures and functional materials to build such devices. The rational design of these memory components also benefits the comprehension and thus the control over the microscopic mechanisms at the origin of memristivity. In oxide‐based valence‐change memories, the control of the oxygen drift and diffusion kinetics is a key aspect in obtaining the gradual analog‐type change in resistance required for artificial synapse applications. However, only a few devices are designed with this in mind, as they are commonly built around ionic insulating active materials. This shortcoming is addressed by using a mixed ionic–electronic conductor as functional memristive material. This work demonstrates how the oxygen content in La₂NiO_4+δ (L2NO4), tuned through post‐annealing treatments, has a critical influence on the memory characteristics of L2NO4‐based memristive devices. The presence of interstitial oxygen point defects in L2NO4 affects both its structure and electrical properties. High oxygen stoichiometry in the pristine state leads to an increased electrical conductivity, ultimately resulting in an improved memory window with highly multilevel, analog‐type memory programing capabilities, desirable for analog computing and synaptic applications in particular.     

Pure CuBi2O4 Photoelectrodes with Increased Stability by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition

A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.     

Ultrathin Polydopamine Films with Phospholipid Nanodiscs Containing a Glycophorin A Domain

Cellular membranes have long served as an inspiration for nanomaterial research. The preparation of ultrathin polydopamine (PDA) films with integrated protein pores containing phospholipids and an embedded domain of a membrane protein glycophorin A as simplified cell membrane mimics is reported. Large area, ultrathin PDA films are obtained by electropolymerization on gold surfaces with 10–18 nm thickness and dimensions of up to 2.5 cm². The films are transferred from gold to various other substrates such as nylon mesh, silicon, or substrates containing holes in the micrometer range, and they remain intact even after transfer. The novel transfer technique gives access to freestanding PDA films that remain stable even at the air interfaces with elastic moduli of ≈6–12 GPa, which are higher than any other PDA films reported before. As the PDA film thickness is within the range of cellular membranes, monodisperse protein nanopores, so‐called “nanodiscs,” are integrated as functional entities. These nanodisc‐containing PDA films can serve as semi‐permeable films, in which the embedded pores control material transport. In the future, these simplified cell membrane mimics may offer structural investigations of the embedded membrane proteins to receive an improved understanding of protein‐mediated transport processes in cellular membranes.     

Unprecedented Improvement of Single Li‐Ion Conductive Solid Polymer Electrolyte Through Salt Additive

Solid‐state lithium metal (Li°) batteries (SSLMBs) are believed to be the most promising technologies to tackle the safety concerns and the insufficient energy density encountered in conventional Li‐ion batteries. Solid polymer electrolytes (SPEs) inherently own good processability and flexibility, enabling large‐scale preparation of SSLMBs. To minimize the growth of Li° dendrites and cell polarization in SPE‐based SSLMBs, an additive‐containing single Li‐ion conductive SPE is reported. The characterization results show that a small dose of electrolyte additive (2 wt%) substantially increases the ionic conductivity of single Li‐ion conductive SPEs as well as the interfacial compatibility between electrode and SPE, allowing the cycling of SPE‐based cells with good electrochemical performance. This work may provide a paradigm shift on the design of highly cationic conductive electrolytes, which are essential for developing safe and high‐performance rechargeable batteries.     

Facet Control for Trap‐State Suppression in Colloidal Quantum Dot Solids

Trap states in colloidal quantum dot (QD) solids significantly affect the performance of QD solar cells, because they limit the open‐circuit voltage and short circuit current. The {100} facets of PbS QDs are important origins of trap states due to their weak or missing passivation. However, previous investigations focused on synthesis, ligand exchange, or passivation approaches and ignored the control of {100} facets for a given dot size. Herein, trap states are suppressed from the source via facet control of PbS QDs. The {100} facets of ≈3 nm PbS QDs are minimized by tuning the balance between the growth kinetics and thermodynamics in the synthesis. The PbS QDs synthesized at a relatively low temperature with a high oversaturation follow a kinetics‐dominated growth, producing nearly octahedral nanoparticles terminated mostly by {111} facets. In contrast, the PbS QDs synthesized at a relatively high temperature follow a thermodynamics‐dominated growth. Thus, a spherical shape is preferred, producing truncated octahedral nanoparticles with more {100} facets. Compared to PbS QDs from thermodynamics‐dominated growth, the PbS QDs with less {100} facets show fewer trap states in the QD solids, leading to a better photovoltaic device performance with a power conversion efficiency of 11.5%.     

Halide Double‐Perovskite Light‐Emitting Centers Embedded in Lattice‐Matched and Coherent Crystalline Matrix

Through first‐principles calculations, it is found that two lattice‐matched halide double‐perovskites, Cs₂NaBiBr₆ and Cs₂AgBiBr₆, have a type‐I band alignment and can form highly miscible alloys in which the disordering makes the bandgaps become direct and activates the direct transition from the valence to conduction band edge, leading to a strong optical absorption and high radiative recombination rate. The bandgaps of the alloys are tunable in a wide range of 1.93–3.24 eV, while the lattice constants remain unchanged. This advantage inspires the design of a coherent crystalline matrix based on Cs₂(Na,Ag)BiBr₆ alloys, in which the Ag‐rich and narrower‐bandgap regions are embedded in the Na‐rich and wide‐bandgap region with lattice‐matched and coherent interfaces. The type‐I band alignment drives the photogenerated excitons into the narrower‐bandgap Ag‐rich regions, so the regions become light‐emitting centers with a high photoluminescence quantum yield (PLQY). The bandgaps of the Ag‐rich regions are tunable, so the color of emitted light can be adjusted, making a broadband emission possible. Such kind of coherent crystalline matrix with high‐PLQY and broadband emission can also be fabricated based on the alloys of other lattice‐matched halide double‐perovskites, demonstrating the flexibility of band structure engineering in the coherent heterostructures of various halide double‐perovskites.     

Biodegradable Polyanhydrides as Encapsulation Layers for Transient Electronics

Bioresorbable electronic systems represent an emerging class of technology of interest due to their ability to dissolve, chemically degrade, disintegrate, and/or otherwise physically disappear harmlessly in biological environments, as the basis for temporary implants that avoid the need for secondary surgical extraction procedures. Polyanhydride‐based polymers can serve as hydrophobic encapsulation layers for such systems, as a subset of the broader field of transient electronics, where biodegradation eventually occurs by chain scission. Systematic experimental studies that involve immersion in phosphate‐buffered saline solution at various pH values and/or temperatures demonstrate that dissolution occurs through a surface erosion mechanism, with little swelling. The mechanical properties of this polymer are well suited for use in soft, flexible devices, where integration can occur through a mold‐based photopolymerization technique. Studies of the dependence of the polymer properties on monomer compositions and the rates of permeation on coating thicknesses reveal some of the underlying effects. Simple demonstrations illustrate the ability to sustain operation of underlying biodegradable electronic systems for durations between a few hours to a week during complete immersion in aqueous solutions that approximate physiological conditions. Systematic chemical, physical, and in vivo biological studies in animal models reveal no signs of toxicity or other adverse biological responses.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation

Understanding crystallization processes and their pathways in metal‐halide perovskites is of crucial importance as this strongly affects the film microstructure, its stability, and device performance. While many approaches are developed to control perovskite formation, the mechanisms of film formation are still poorly known. Using time‐resolved in situ grazing incidence wide‐angle X‐ray scattering, the film formation of perovskites is investigated with average stoichiometry Cs_0.15FA_0.85PbI₃, where FA is formamidinium, using the popular antisolvent dropping and gas jet treatments and this is contrasted with untreated films. i) The crystallization pathways during spin coating, ii) the subsequent postdeposition thermal annealing, and iii) crystallization during blade coating are studied. The findings reveal that the formation of a nonperovskite FAPbI₃ phase during spin coating is initially dominant regardless of the processing and that the processing treatment (e.g., antisolvent dropping, gas jet) has a significant impact on the as‐cast film structure and affects the phase evolution during subsequent thermal treatment. It is shown that blade coating can be used to overcome the nonperovskite phase formation via solvothermal direct crystallization of perovskite phase. This work shows how real‐time investigation of perovskite formation can help to establish processing–microstructure–functionality relationships.