Artificial Synapse Based on a δ-FAPbI3/Atomic-Layer-Deposited SnO2 Bilayer Memristor.

Halide perovskite-based resistive switching memory (memristor) has potential in an artificial synapse. However, an abrupt switch behavior observed for a formamidinium lead triiodide (FAPbI3)-based memristor is undesirable for an artificial synapse. Here, we report on the δ-FAPbI3/atomic-layer-deposited (ALD)-SnO2 bilayer memristor for gradual analogue resistive switching. In comparison to a single-layer δ-FAPbI3 memristor, the heterojunction δ-FAPbI3/ALD-SnO2 bilayer effectively reduces the current level in the high-resistance state. The analog resistive switching characteristics of δ-FAPbI3/ALD-SnO2 demonstrate exceptional linearity and potentiation/depression performance, resembling an artificial synapse for neuromorphic computing. The nonlinearity of long-term potentiation and long-term depression is notably decreased from 12.26 to 0.60 and from -8.79 to -3.47, respectively. Moreover, the δ-FAPbI3/ALD-SnO2 bilayer achieves a recognition rate of ≤94.04% based on the modified National Institute of Standards and Technology database (MNIST), establishing its potential in an efficient artificial synapse.

Aqueous synthesis of perovskite precursors for highly efficient perovskite solar cells.

High-purity precursor materials are vital for high-efficiency perovskite solar cells (PSCs) to reduce defect density caused by impurities in perovskite. In this study, we present aqueous synthesized perovskite microcrystals as precursor materials for PSCs. Our approach enables kilogram-scale mass production and synthesizes formamidinium lead iodide (FAPbI3) microcrystals with up to 99.996% purity, with an average value of 99.994 ± 0.0015%, from inexpensive, low-purity raw materials. The reduction in calcium ions, which made up the largest impurity in the aqueous solution, led to the greatest reduction in carrier trap states, and its deliberate introduction was shown to decrease device performance. With these purified precursors, we achieved a power conversion efficiency (PCE) of 25.6% (25.3% certified) in inverted PSCs and retained 94% of the initial PCE after 1000 hours of continuous simulated solar illumination at 50°C.

Atmospheric Humidity Underlies Irreproducibility of Formamidinium Lead Iodide Perovskites.

Metal halide perovskite solar cells (PSCs) are infamous for their batch-to-batch and lab-to-lab irreproducibility in terms of stability and performance. Reproducible fabrication of PSCs is a critical requirement for market viability and practical commercialization. PSC irreproducibility plagues all levels of the community; from institutional research laboratories, start-up companies, to large established corporations. In this work, the critical function of atmospheric humidity to regulate the crystallization and stabilization of formamidinium lead triiodide (FAPbI3) perovskites is unraveled. It is demonstrated that the humidity content during processing induces profound variations in perovskite stoichiometry, thermodynamic stability, and optoelectronic quality. Almost counterintuitively, it is shown that the presence of humidity is perhaps indispensable to reproduce phase-stable and efficient FAPbI3-based PSCs.

Homogenizing out-of-plane cation composition in perovskite solar cells.

Perovskite solar cells with the formula FA1-xCsxPbI3, where FA is formamidinium, provide an attractive option for integrating high efficiency, durable stability and compatibility with scaled-up fabrication. Despite the incorporation of Cs cations, which could potentially enable a perfect perovskite lattice1,2, the compositional inhomogeneity caused by A-site cation segregation is likely to be detrimental to the photovoltaic performance of the solar cells3,4. Here we visualized the out-of-plane compositional inhomogeneity along the vertical direction across perovskite films and identified the underlying reasons for the inhomogeneity and its potential impact for devices. We devised a strategy using 1-(phenylsulfonyl)pyrrole to homogenize the distribution of cation composition in perovskite films. The resultant p-i-n devices yielded a certified steady-state photon-to-electron conversion efficiency of 25.2% and durable stability.

Facet-Dependent Passivation for Efficient Perovskite Solar Cells.

Understanding the interplay between the surface structure and the passivation materials and their effects associated with surface structure modification is of fundamental importance; however, it remains an unsolved problem in the perovskite passivation field. Here, we report a surface passivation principle for efficient perovskite solar cells via a facet-dependent passivation phenomenon. The passivation process selectively occurs on facets, which is observed with various post-treatment materials with different functionality, and the atomic arrangements of the facets determine the alignments of the passivation layers. The profound understanding of facet-dependent passivation leads to the finding of 2-amidinopyridine hydroiodide as the material for a uniform and effective passivation on both (100) and (111) facets. Consequently, we achieved perovskite solar cells with an efficiency of 25.10% and enhanced stability. The concept of facet-dependent passivation can provide an important clue on unidentified passivation principles for perovskite materials and a novel means to enhance the performance and stability of perovskite-based devices.

Lattice engineering for stabilized black FAPbI3 perovskite single crystals for high-resolution x-ray imaging at the lowest dose.

Preliminary theoretical analyses indicate that lattice relaxation may be used to release lattice strain in the FAPbI3 perovskite to warrant both high x-ray detection performance and improved stability. Herein, we demonstrate stable black α-phase FAPbI3 single crystals (SCs) realized by lattice engineering via annealing in the ambient atmosphere. The engineered α-FAPbI3 SC detector shows almost all the best figures of merit including a high sensitivity of 4.15 × 105 µC Gyair-1 cm-2, a low detection limit of 1.1 nGyair s-1, a high resolution of 15.9 lp mm-1, and a short response time of 214 µs. We further demonstrate high-definition x-ray imaging at a dose rate below 10 nGyair s-1 on the FAPbI3 SC, indicating a minimal dose-area product of 0.048 mGyair cm2 to the patient for one-time posteroanterior chest diagnosis, which is more than 3000 times lower than the international reference level of 150 mGyair cm2. In addition, the robust long-term stability enables the FAPbI3 SC x-ray detector to work steadily for more than 40 years.

Lead immobilization for environmentally sustainable perovskite solar cells.

Lead halide perovskites are promising semiconducting materials for solar energy harvesting. However, the presence of heavy-metal lead ions is problematic when considering potential harmful leakage into the environment from broken cells and also from a public acceptance point of view. Moreover, strict legislation on the use of lead around the world has driven innovation in the development of strategies for recycling end-of-life products by means of environmentally friendly and cost-effective routes. Lead immobilization is a strategy to transform water-soluble lead ions into insoluble, nonbioavailable and nontransportable forms over large pH and temperature ranges and to suppress lead leakage if the devices are damaged. An ideal methodology should ensure sufficient lead-chelating capability without substantially influencing the device performance, production cost and recycling. Here we analyse chemical approaches to immobilize Pb2+ from perovskite solar cells, such as grain isolation, lead complexation, structure integration and adsorption of leaked lead, based on their feasibility to suppress lead leakage to a minimal level. We highlight the need for a standard lead-leakage test and related mathematical model to be established for the reliable evaluation of the potential environmental risk of perovskite optoelectronics.

Unraveling Optical and Electrical Gains of Perovskite Solar Cells with an Antireflective and Energetic Cascade Electron Transport Layer.

Electron transport layers (ETLs) are imperative in n-i-p structured perovskite solar cells (PSCs) because of their capability to affect light propagation, electron extraction, and perovskite crystallization, and any mismatch of optical constants, band position, and surface potential between the ETLs and the perovskites can cause unintentional optical and electrical losses. Herein, an antireflective and energetic cascade bilayer ETL with ubiquitously used SnO2 and TiO2 was constructed at 150 °C for PSCs, and the in-depth mechanism for performance improvement was systematically unraveled. It was revealed that the construction of an ETL with gradually increasing refractive indices can circumvent light reflection loss, resulting in enhanced photocurrent. The combined ETL forms an energetic cascade to promote electronic conductivity and facilitate electron extraction with reduced energy loss. Moreover, topologic perovskite growth with improved crystallinity and vertical orientation was preferred owing to the relative dewetting behavior, leading to reduced defect states and enhanced carrier mobility in the perovskite layer.

Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance.

Crystallization kinetic controls the crystallographic orientation, inducing anisotropic properties of the materials. As a result, preferential orientation with advanced optoelectronic properties can enhance the photovoltaic devices' performance. Although incorporation of additives is one of the most studied methods to stabilize the photoactive α-phase of formamidinium lead tri-iodide (α-FAPbI3 ), no studies focus on how the additives affect the crystallization kinetics. Along with the role of methylammonium chloride (MACl) as a "stabilizer" in the formation of α-FAPbI3 , herein, the additional role as a "controller" in the crystallization kinetics is pointed out. With microscopic observations, for example, electron backscatter diffraction and selected area electron diffraction, it is examined that higher concentration of MACl induces slower crystallization kinetics, resulting in larger grain size and [100] preferred orientation. Optoelectronic properties of [100] preferentially oriented grains with less non-radiative recombination, a longer lifetime of charge carriers, and lower photocurrent deviations in between each grain induce higher short-circuit current density (Jsc ) and fill factor. Resulting MACl40 mol% attains the highest power conversion efficiency (PCE) of 24.1%. The results provide observations of a direct correlation between the crystallographic orientation and device performance as it highlights the importance of crystallization kinetics resulting in desirable microstructures for device engineering.

Atomic layer deposition of SnO2 using hydrogen peroxide improves the efficiency and stability of perovskite solar cells.

Low-temperature processed SnO2 is a promising electron transporting layer in perovskite solar cells (PSCs) due to its optoelectronic advantage. Atomic layer deposition (ALD) is suitable for forming a conformal SnO2 layer on a high-haze substrate. However, oxygen vacancy formed by the conventional ALD process using H2O might have a detrimental effect on the efficiency and stability of PSCs. Here, we report on the photovoltaic performance and stability of PSCs based on the ALD-SnO2 layer with low oxygen vacancies fabricated via H2O2. Compared to the ALD-SnO2 layer formed using H2O vapors, the ALD-SnO2 layer prepared via H2O2 shows better electron extraction due to a reduced oxygen vacancy associated with the highly oxidizing nature of H2O2. As a result, the power conversion efficiency (PCE) is enhanced from 21.42% for H2O to 22.34% for H2O2 mainly due to an enhanced open-circuit voltage. Operational stability is simultaneously improved, where 89.3% of the initial PCE is maintained after 1000 h under an ambient condition for the H2O2-derived ALD SnO2 as compared to the control device maintaining 72.5% of the initial PCE.

Unveiling facet-dependent degradation and facet engineering for stable perovskite solar cells.

A myriad of studies and strategies have already been devoted to improving the stability of perovskite films; however, the role of the different perovskite crystal facets in stability is still unknown. Here, we reveal the underlying mechanisms of facet-dependent degradation of formamidinium lead iodide (FAPbI3) films. We show that the (100) facet is substantially more vulnerable to moisture-induced degradation than the (111) facet. With combined experimental and theoretical studies, the degradation mechanisms are revealed; a strong water adhesion following an elongated lead-iodine (Pb-I) bond distance is observed, which leads to a δ-phase transition on the (100) facet. Through engineering, a higher surface fraction of the (111) facet can be achieved, and the (111)-dominated crystalline FAPbI3 films show exceptional stability against moisture. Our findings elucidate unknown facet-dependent degradation mechanisms and kinetics.

Future Research Directions in Perovskite Solar Cells: Exquisite Photon Management and Thermodynamic Phase Stability.

As power conversion efficiency (PCE) of perovskite solar cells (PSCs) has rapidly increased up to 25.7% in 2022, a curiosity about the achievable limit of the PCE has prevailed and demands understanding about the underlying fundamentals to step forward. Meanwhile, outstanding long-term stability of PSCs over 1000 h has been reported at operating conditions or under damp heat test with 85 °C/85% relative humidity. Herein comes the question as to whether the phase stability issue of perovskite crystal is completely resolved in the most recent state-of-the-art perovskite film or if it deceives everyone into believing so by significantly slowing the kinetics. On the one hand, the fundamental origins of a discrepancy between reported values and the theoretical limit are thoroughly examined, where the importance of light management is greatly emphasized with the introduction of external luminescence as a key parameter to narrow the gap. On the other hand, the phase stability of a perovskite film is understood from thermodynamic point of view to address viable approaches to lower the Gibbs free energy, distinguishing the kinetically trapped condition from the thermodynamically stable phase.

Suppressing ion migration in metal halide perovskite via interstitial doping with a trace amount of multivalent cations.

Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote the performance and stability of perovskite optoelectronics. However, such interstitial doping inevitably leads to lattice microstrain that impairs the long-range ordering and stability of the crystals, causing a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with a reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). The photovoltaic performances and operational stability of the prototypical perovskite solar cells are enhanced with a trace amount of Nd3+ doping while minimizing the sacrificial trade-off.

Strain Control to Stabilize Perovskite Solar Cells.

Perovskite solar cells (PSCs) are rivaling most commercial photovoltaics in the aspect of efficiency and cost, while their intrinsic instability remains a major concern for their practical deployment. The presence of undesirable strain in PSCs during device fabrication and operation refers to the extension/narrowing of chemical bonds and expansion/shrinkage of lattice volume, which largely affects device stability due to promoted phase transition, chemical decomposition, and mechanical fragility. Pioneering investigations and remarkable achievements have revealed that strain control is indispensable in the design of stable PSCs. Herein, the evolution of strain in perovskite thin films and its effect on device performance is elucidated, and state-of-the-art strategies of strain modulation are systematically reviewed. A thorough understanding and cautious control of the strain-related phenomenon pave the pathway to derive perovskite materials with desired properties.

Mixed-Dimensional Formamidinium Bismuth Iodides Featuring In-Situ Formed Type-I Band Structure for Convolution Neural Networks.

For valence change memory (VCM)-type synapses, a large number of vacancies help to achieve very linearly changed dynamic range, and also, the low activation energy of vacancies enables low-voltage operation. However, a large number of vacancies increases the current of artificial synapses by acting like dopants, which aggravates low-energy operation and device scalability. Here, mixed-dimensional formamidinium bismuth iodides featuring in-situ formed type-I band structure are reported for the VCM-type synapse. As compared to the pure 2D and 0D phases, the mixed phase increases defect density, which induces a better dynamic range and higher linearity. In addition, the mixed phase decreases conductivity for non-paths despite a large number of defects providing lots of conducting paths. Thus, the mixed phase-based memristor devices exhibit excellent potentiation/depression characteristics with asymmetricity of 3.15, 500 conductance states, a dynamic range of 15, pico ampere-scale current level, and energy consumption per spike of 61.08 aJ. A convolutional neural network (CNN) simulation with the Canadian Institute for Advanced Research-10 (CIFAR-10) dataset is also performed, confirming a maximum recognition rate of approximately 87%. This study is expected to lay the groundwork for future research on organic bismuth halide-based memristor synapses usable for a neuromorphic computing system.

Stability-limiting heterointerfaces of perovskite photovoltaics.

Optoelectronic devices consist of heterointerfaces formed between dissimilar semiconducting materials. The relative energy-level alignment between contacting semiconductors determinately affects the heterointerface charge injection and extraction dynamics. For perovskite solar cells (PSCs), the heterointerface between the top perovskite surface and a charge-transporting material is often treated for defect passivation1-4 to improve the PSC stability and performance. However, such surface treatments can also affect the heterointerface energetics1. Here we show that surface treatments may induce a negative work function shift (that is, more n-type), which activates halide migration to aggravate PSC instability. Therefore, despite the beneficial effects of surface passivation, this detrimental side effect limits the maximum stability improvement attainable for PSCs treated in this way. This trade-off between the beneficial and detrimental effects should guide further work on improving PSC stability via surface treatments.

Rethinking the A cation in halide perovskites.

The A cation in ABX3 organic-inorganic lead halide perovskites (OLHPs) was conventionally believed to hardly affect their optoelectronic properties. However, more recent developments have unraveled the critical role of the A cation in the regulation of the physicochemical and optoelectronic properties of OLHPs. We review the important breakthroughs enabled by the versatility of the A cation and highlight potential opportunities and unanswered questions related to the A cation in OLHPs.

Antiseptic Povidone-Iodine Heals the Grain Boundary of Perovskite Solar Cells.

Povidone, also know as polyvinylpyrrolidone (PVP), is used as a reservoir for iodine, and the povidone-iodine (PVP-I) complex has antiseptic properties for wound healing by releasing iodine. In this report, we utilized this unique characteristic of PVP-I to heal the photovoltaic parameters of perovskite solar cells (PSCs). PVP-I was added in the perovskite precursor solution, where the effect of the PVP-I concentration on the photovoltaic performance was investigated. The power conversion efficiency (PCE) of PSC was enhanced from 20.73% to 22.59% by addition of 0.1 mg/mL PVP-I, mainly due to an improved fill factor from 0.76 to 0.80 together with a slight increase in current density. Scanning electron microscopy revealed that the grain boundaries were passivated by PVP-I. Conductive atomic force microscopy combined with time-resolved photoluminesence and space charge-limited current studies showed that the addition of PVP-I decreased the defect density of the perovskite film together and enhanced the film conductivity. Furthermore, better stability was observed from the PVP-I-treated PSCs than the control device without the additive, which is probably owing to the grain boundary healing effect.

Characterization of a C-Type Lectin Domain-Containing Protein with Antibacterial Activity from Pacific Abalone (Haliotis discus hannai).

Genes that influence the growth of Pacific abalone (Haliotis discus hannai) may improve the productivity of the aquaculture industry. Previous research demonstrated that the differential expression of a gene encoding a C-type lectin domain-containing protein (CTLD) was associated with a faster growth in Pacific abalone. We analyzed this gene and identified an open reading frame that consisted of 145 amino acids. The sequence showed a significant homology to other genes that encode CTLDs in the genus Haliotis. Expression profiling analysis at different developmental stages and from various tissues showed that the gene was first expressed at approximately 50 days after fertilization (shell length of 2.47 ± 0.13 mm). In adult Pacific abalone, the gene was strongly expressed in the epipodium, gill, and mantle. Recombinant Pacific abalone CTLD purified from Escherichia coli exhibited antimicrobial activity against several Gram-positive bacteria (Bacillus subtilis, Streptococcus iniae, and Lactococcus garvieae) and Gram-negative bacteria (Vibrio alginolyticus and Vibrio harveyi). We also performed bacterial agglutination assays in the presence of Ca2+, as well as bacterial binding assays in the presence of the detergent dodecyl maltoside. Incubation with E. coli and B. subtilis cells suggested that the CTLD stimulated Ca2+-dependent bacterial agglutination. Our results suggest that this novel Pacific abalone CTLD is important for the pathogen recognition in the gastropod host defense mechanism.

Challenges for Thermally Stable Spiro-MeOTAD toward the Market Entry of Highly Efficient Perovskite Solar Cells.

Perovskite solar cells (PSCs) have drawn great attention because they have seen a dramatic increase in power conversion efficiency (PCE) over only a decade and reached 25.5% of certified PCE in 2021. The efficiency competitiveness with a low production cost puts up PSCs as a candidate for next-generation photovoltaics, encouraging the stability assessment. Research on PSCs, however, still struggles with the stability issue, particularly at elevated temperature, which is mainly ascribed to the use of spiro-MeOTAD as a hole transport material (HTM). Though many attempts have been made to explore a new HTM to replace spiro-MeOTAD, the improved stability is mostly obtained at the expense of losing efficiency. Likewise, the question of the effectiveness of alternatives for spiro-MeOTAD consistently remains. In this perspective, the morphological stability of spiro-MeOTAD at elevated temperatures is discussed to determine the underlying origins of the thermal stability issue and find feasible strategies to resolve it.