Reaction-controlled shape evolution and insights into the growth mechanism of CsPbBr3 nanocrystals.

The correlation between structural transformation and optical characteristics of cesium lead bromide (CsPbBr3) nanocrystals (NCs) suggests insights into their growth mechanism and optical performance. Systematic control of reaction parameters led to the successful fabrication of on-demand shape-morphing CsPbBr3 NCs. Transmission electron microscopy observations showed that the shape transformation from nanocubes to microcrystals could be accelerated by increasing the precursor:ligand molar ratio and reaction time. Further evidence for orthorhombic CsPbBr3 NCs was obtained from their selected-area electron diffraction pattern, which exhibits a twin domain induced by the presence of large NCs. Likewise, we observed a substantial decrease in photoluminescence (PL) intensity of CsPbBr3 due to surface decomposition or surface ligand loss resulting from increased size. In addition, fusion of smaller particles having other dimensionality induced the increase in the PL full-width at half maximum. In particular, existence of larger bulk material caused a reduction in the peak intensity in the absorption spectra and a trend of decreasing tendency in intensity of the absorption bands related to bromoplumbate species provided direct evidence of fully converted Cs-oleate.

Mechanical and Ionic Characterization for Organic Semiconductor-Incorporated Perovskites for Stable 2D/3D Heterostructure Perovskite Solar Cells.

Hybrid metal halide perovskite (MHP) materials, while being promising for photovoltaic technology, also encounter challenges related to material stability. Combining 2D MHPs with 3D MHPs offers a viable solution, yet there is a gap in the understanding of the stability among various 2D materials. The mechanical, ionic, and environmental stability of various 2D MHP ligands are reported, and an improvement with the use of a quater-thiophene-based organic cation (4TmI) that forms an organic-semiconductor incorporated MHP structure is demonstrated. It is shown that the best balance of mechanical robustness, environmental stability, ion activation energy, and reduced mobile ion concentration under accelerated aging is achieved with the usage of 4TmI. It is believed that by addressing mechanical and ion-based degradation modes using this built-in barrier concept with a material system that also shows improvements in charge extraction and device performance, MHP solar devices can be designed for both reliability and efficiency.

Halide Perovskite Thin Film Lasing Mode Control.

Metal halide perovskite semiconductors have emerged as highly efficient amplifying materials; to ensure practical applicability, it is important to have precise control over the spectral and polarization characteristics of lasing emission. In this study, we present effective strategies for manipulating single- and multimode lasing from surface-emitting and optically pumped perovskite distributed feedback lasers. We show that cladding structures can be made to modify the optical properties of guided transverse electric and magnetic modes within the gain medium. This leads to spectral tuning of multipeak lasing emission and the generation of linear polarization modes. Our results are supported with a comprehensive multilayer slab waveguide model and confirmed with two different perovskite materials: methylammonium lead iodide and cesium lead bromide.

Reliable and Robust Two-Dimensional Perovskite Memristors for Flexible-Resistive Random-Access Memory Array.

Two-dimensional (2D) halide perovskites have become a promising class of memristive materials due to their low power consumption, compositional versatility, and microstructural anisotropy in electronics. However, implementing high-performance resistive random-access memory requires a higher reliability and moisture resistance. To address these issues, component studies and attempts to improve the phase stability have been reported but have not been able to achieve sufficient reliability. Here, highly textured thin films grown perpendicular to the substrate in Ruddlesden-Popper 2D perovskites exhibited highly stable and reliable binary memory performance. We further built a flexible crossbar array to verify data storage capability, achieving a high device yield, robust endurance, long retention, reliability to operate under bending conditions, and moisture stability over a year. These device performances are attributed to preformed vertically oriented nanocrystals that allow the conductive filaments to operate reliably. Our finding provides the material design strategy that can be extended to the development of semiconductor materials for next-generation memory devices.

High-Throughput Computational Study and Machine Learning Prediction of Electronic Properties in Transition Metal Dichalcogenide/Two-Dimensional Layered Halide Perovskite Heterostructures.

Heterostructures formed by transition metal dichalcogenides (TMDs) and two-dimensional layered halide perovskites (2D-LHPs) have attracted significant attention due to their unique optoelectronic properties. However, theoretical studies face challenges due to the large number of atoms and the need for lattice matching. With the discovery of more 2D-LHPs, there is an urgent need for methods to rapidly predict and screen TMDs/2D-LHPs heterostructures. This study employs first-principles calculations to perform high-throughput computations on 602 TMDs/2D-LHPs heterostructures. Results show that different combinations exhibit diverse band alignments, with MoS2 and WS2 more likely to form type-II heterostructures with 2D-LHPs. The highest photoelectric conversion efficiency of type-II structures reaches 23.26%, demonstrating potential applications in solar cells. Notably, some MoS2/2D-LHPs form type-S structures, showing promise in photocatalysis. Furthermore, we found that TMDs can significantly affect the conformation of organic molecules in 2D-LHPs, thus modulating the electronic properties of the heterostructures. To overcome computational cost limitations, we constructed a crystal graph convolutional neural network model based on the calculated data to predict the electronic properties of TMDs/2D-LHPs heterostructures. Using this model, we predicted the bandgaps and band alignment types of 9,360 TMDs/2D-LHPs heterostructures, providing a comprehensive theoretical reference for research in this field.

Engineering Spacer Conjugation for Efficient and Stable 2D/3D Perovskite Solar Cells and Modules.

Incorporating 2D perovskite in 3D perovskite absorber holds great potential to improve the stability and efficiency of perovskite solar cells (PSCs). However, the bulky-cation-based 2D structures often exhibit poor charge transport and are prone to formation of charge-extraction barrier that impedes efficient device operation. We address these issues by introducing aromatic spacers with enhanced molecular conjugation. Among our tested aromatic spacers, the pyrenylbutanamine (PyBA) spacer was shown to endow 2D perovskites with superior charge transport properties and efficient charge extraction from the bulk perovskite in 2D/3D PSCs, due to the highest degree of conjugation. As a result, we achieved a power conversion efficiency of up to 25.3% in a 0.16-cm2 single cell and 21.0% in a 24.8-cm2 module. Moreover, the incorporated PyBA substantially raised the resistance of 2D/3D PSCs against moisture and ion migration, resulting in enhanced environmental, thermal, and operational stability. Notably, the PyBA-based devices retained over 90% of their initial efficiency after 2000 hours at 25 ℃ and 80% relative humidity, or 1000 hours at 85 ℃ and 85% humidity, or 3000 hours of operation under continuous 1-Sun illumination at 40 ℃, showcasing their enhanced stability compared to previously reported 2D/3D PSCs.

First-principle calculations to investigate mechanical and acoustical properties of predicted stable halide Perovskite ABX3.

This work examines the predicted stable halide perovskites' elastic, acoustical, and thermal characteristics. The work uses the Full Potential-Linearized Augmented Plane Wave (FP-LAPW) technique through PBE-GGA to compute compounds in the WIEN2K algorithm. The ELATE program for the evaluation of elastic tensors to plot 2D and 3D graphs was also used. The bulk modulus, Young's modulus, shear modulus, anisotropy factors, Cauchy pressure, Pugh's ratio, Poisson's ratio, Kleinman's parameter, Lame's coefficient, Vicker's hardness, sound velocities, Gruneisen parameter and even melting and Debye temperature were computed. The mechanical and elastic properties are reported for the first time for most of the compounds, demonstrating that the investigated HPs-aside from TlBeF3, BaAgBr3, and CsTcl3-are mechanically stable and exhibit weaker resistance against shear distortion than they do to unidirectional compression. The results of Poisson's, Pugh's, and Frantsevich's ratios data prove that all materials are ductile except SrLiF3. The estimated Poisson's ratio data indicates the metallic bonding nature of HPs, whereas only SrLiF3 exhibits covalent behavior with ν = 0.23. Debye temperature for SrLiF3, ZnLiF3, ZnScF3, CsRhCl3, CsRuCl3, and CsBeCl3 is greater than 200 K which signifies their hardness, thermal conductivity, and high sound velocities. The large melting temperature values, make them suitable for high-temperature industrial applications. The anharmonicity effect is highest for CaCuBr3 (3.265) and lowest for SrLiF3 (1.402). The current approach calculates elastic and mechanical properties, providing a practical understanding of various physical processes and enabling technology developers to utilize compounds in diverse applications.

Anomalous Behavior in Dark-Bright Splitting Impacts the Biexciton Binding Energy in (BA)2(MA)n-1PbnBr3n+1 (n = 1-3).

Two-dimensional Ruddlesden-Popper series are an excellent system for tuning physical properties of the perovskite by controlling the layer number (n). For instance, bandgap and exciton binding energies of the series gradually increase upon reducing n via enhanced quantum and dielectric confinements. Here, we present findings that challenge the anticipated trend in electron-hole exchange interaction within (BA)2MAn-1PbnBr3n+1 (n = 1-3), which causes spin-dependent exciton level splitting into bright and dark states, where the latter is partially visible near the surface of the Br-based two-dimensional Ruddlesden-Popper series. Contrary to expectations, the smallest gap between bright and dark exciton levels is observed from n = 2 at 10 K. This anomaly results in the strongest biexciton binding between two dark excitons occurring at n = 2, rather than at n = 1 as initially hypothesized. The observed anomaly arises from a phase transition induced by octahedral tilting occurring only for n = 2 near 100 K as confirmed by temperature-dependent optical and X-ray diffraction measurements. Our results show that Coulomb interaction need not vary gradually with n, which can impact the optoelectronic properties of the Ruddlesden-Popper series.

Entropy-Driven Reversible Melting and Recrystallization of Layered Hybrid Perovskites.

Typical layered 2D A2PbX4 (A: organic ammonium cation, X: Br, I) perovskites undergo irreversible decomposition at high temperatures. Can they be designed to melt at lower temperatures without decomposition? Which thermodynamic parameter drive the melting of layered perovskites? These questions are addressed by considering the melt of A2PbX4 as a mixture of ions (like ionic liquids), and hypothesized that the increase in the structural entropy of fusion (ΔSfus) will be the driving force to decrease their melting temperature. Then to increase structural ΔSfus, A-site cations are designed that are rigid in the solid crystal, and become flexible in the molten state. Different tail groups in the A-site cations form hydrogen-, halogen- and even covalent bonding-interactions, making the cation-layer rigid in the solid form. Additionally, the rotation of ─NH3 + head group is suppressed by replacing ─H with ─CH3, further enhancing the rigidity. Six A2PbX4 crystals with high ΔSfus and low melting temperatures are prepared using this approach. For example, [I-(CH2)3-NH2(CH3)]2PbI4 reversibly melts at 388 K (decomposition temperature 500 K), and then recrystallizes back upon cooling. Consequently, melt-pressed films are grown demonstrating the solvent- and vacuum-free perovskite films for future optoelectronic devices.

Efficient and Stable Red Perovskite Light-Emitting Diodes via Thermodynamic Crystallization Control.

Efficient and stable red perovskite light-emitting diodes (PeLEDs) demonstrate promising potential in high-definition displays and biomedical applications. Although significant progress has been made in device performance, meeting commercial demands remains a challenge in the aspects of long-term stability and high external quantum efficiency (EQE). Here, an in situ crystallization regulation strategy is developed for optimizing red perovskite films through ingenious vapor design. Mixed vapor containing dimethyl sulfoxide and carbon disulfide (CS2) is incorporated to conventional annealing, which contributes to thermodynamics dominated perovskite crystallization for well-aligned cascade phase arrangement. Additionally, the perovskite surface defect density is minimized by the CS2 molecule adsorption. Consequently, the target perovskite films exhibit smooth exciton energy transfer, reduced defect density, and blocked ion migration pathways. Leveraging these advantages, spectrally stable red PeLEDs are obtained featuring emission at 668, 656, and 648 nm, which yield record peak EQEs of 30.08%, 32.14%, and 29.04%, along with prolonged half-lifetimes of 47.7, 60.0, and 43.7 h at the initial luminances of 140, 250, and 270 cd m-2, respectively. This work provides a universal strategy for optimizing perovskite crystallization and represents a significant stride toward the commercialization of red PeLEDs.

Ultralow Lattice Thermal Conductivity and Large Glass-Like Contribution in Cs3Bi2I6Cl3: Rattling Atoms and p-Band Electrons Driven Dynamic Rotation.

Understanding the origin of ultralow lattice thermal conductivity κL of halide perovskites is of great significance in the energy conversion field. The soft phonon modes and the large anharmonicity corresponding to the dynamic rotation of halogen atoms play an important role in limiting the thermal transport of halide perovskites. The dynamic rotation has long been thought to originate from the electrostatic repulsion of lone pairs around halogen atoms. Here, by studying the layered perovskite Cs3Bi2I6Cl3, it is found that the interaction between the lone pairs contributed by the s bands of halogen atoms is short-range, and the dynamic rotation is really driven by the occupied p-band electrons. It dominates Cs3Bi2I6Cl3 with ultralow κL, < 0.2 W mK-1 at 300 K. Moreover, soft optical phonons are presented ≈1 and 2.2 THz that constitute relatively flat and dense bands due to the rattling Cs and Cl atoms, contributing a large glass-like component to the κL. The results have important implications for understanding the origin of the ultralow κL in halide perovskites and for designing novel perovskites to serve the energy conversion field.

Palladium-Doped Cs2AgBiBr6 with 1300 nm Near-Infrared Photoresponse.

Lead-free halide double perovskite (HDP) Cs2AgBiBr6 has set a benchmark for research in HDP photoelectric applications due to its attractive optoelectronic properties. However, its narrow absorption range is a key limitation of this material. Herein, a novel dopant, palladium (Pd), is doped into Cs2AgBiBr6 and significantly extends the absorption to ≈1400 nm. Pd2+ ions are partially doped in the host lattice, most probably replacing Ag atoms and introducing a sub-bandgap state within the host bandgap, as indicated by the combination of spectroscopical measurements and theoretical calculations. Importantly, this sub-bandgap state extends the photoresponse of Cs2AgBiBr6 up to the NIR-II region of 1300 nm, setting a new record for HDPs. This work demonstrates a novel and efficient dopant for HDPs and highlights the effectiveness of employing a sub-bandgap to broaden the absorption of HDPs, shedding new light on tailoring large bandgap HDPs for NIR optoelectronic applications.

Chemical Synergic Stabilization of High Br-Content Mixed-Halide Wide-Bandgap Perovskites for Durable Multi-Terminal Tandem Solar Cells with Minimized Pb Leakage.

High Br-content mixed-halide perovskites with wide-bandgap (WBG) of 1.6-2.0 eV have showcased vast potential to be used in tandem solar cells. However, they often suffer from severe halide segregation, phase separation and ion migration issues, which would accelerate the decomposition of perovskites films, deteriorate the photovoltaic performance and even aggravate the lead leakage from damaged devices. Here, we report a novel chemical synergic interaction strategy to mitigate the abovementioned issues. A small amount of cationic ß-cyclodextrin, composed of multiple ammonium cations, chlorine ions and abundant hydroxyl functional groups, was introduced into WBG perovskites, which effectively stabilized the halide ions and homogenized the phase distribution, comprehensively passivated the defects,and efficiently immobilized the Pb2+ ions. Encouragingly, the cationic ß-cyclodextrin was universal and useful for different WBG perovskites, which favorably boosted the efficiencies by 10%-36% and extended the device operational stability to 2680 h. The integrated four-terminal or six-terminal all-perovskite tandem solar cells exhibited efficiencies up to 24.39% and 22.42%, respectively. We demonstrated the cationic ß-cyclodextrin-assisted internal chemical encapsulation effectively prevented the Pb leakage from severely damaged devices with only 5.63 ppb Pb leaching out. The target tandem solar cells with cationic ß-cyclodextrin modification also realized a Pb sequestration efficiency of 93.4%.

Metal Halide Perovskites for Photocatalysis: Performance and Mechanistic Studies.

Metal halide perovskites, both lead-based and lead-free variants, have emerged as highly versatile materials with widespread applications across various fields, including photovoltaics, optoelectronics, and photocatalysis. This review provides a succinct overview of the recent advancements in the utilization of lead and lead-free halide perovskites specifically in photocatalysis. We explore the diverse range of photocatalytic reactions enabled by metal halide perovskites, including organic transformations, carbon dioxide reduction, and pollutant degradation. We highlight key developments, mechanistic insights, and challenges in the field, offering our perspectives on the future research directions and potential applications. By summarizing recent findings from the literature, this review aims to provide a timely resource for researchers interested in harnessing the full potential of metal halide perovskites for sustainable and efficient photocatalytic processes.

Photolithography-Free, Solution-Processable Perovskite Electrodes for High-Performance Organic Transistors.

Solution-processable electrodes are promising for next-generation electronics due to their simplicity, cost-effectiveness, and potential for large-area fabrication. However, current solution-processable electrodes based on conductive polymers, carbon-based compounds, and metal nanowires face challenges related to stability, patterning, and production scalability. Here we introduce a novel approach using 3D tin halide perovskites (THPs) combined with a photolithography-free solution patterning technique to fabricate solution-processed electrodes. We demonstrate the preparation of highly conductive CsSnI3 films (234.9 S cm-1) and the fabrication of patterned 35 × 35 perovskite electrode arrays on a 4-in. silicon wafer. These electrodes, used as source/drain electrodes in organic transistors, resulted in devices showing high uniformity and stability. This electrode fabrication strategy is also applicable to other 3D THPs like FASnI3 and MASnI3, showcasing versatility for diverse applications. The results highlight the feasibility and advantages of using 3D THPs as solution-processable electrodes, providing a new material system for the advancement of solution-processed electronics.

Thin Film Stoichiometry and Defects Management for Low Threshold and Air Stable Near-Infrared Perovskite Laser.

While significant efforts have been devoted to optimize the thin-film stoichiometry and processing of perovskites for applications in photovoltaic and light-emitting diodes, there is a noticeable lack of emphasis on tailoring them for lasing applications. In this study, it is revealed that thin films engineered for efficient light-emitting diodes, with passivation of deep and shallow trap states and a tailored energetic landscape directing carriers toward low-energy emitting states, may not be optimal for light amplification systems. Instead, amplified spontaneous emission (ASE) is found to be sustained by shallow defects, driven by the positive correlation between the ASE threshold and the ratio of carrier injection rate in the emissive state to the recombination rate of excited carriers. This insight has informed the development of an optimized perovskite thin film and laser device exhibiting a low threshold (≈ 60 µJ cm-2) and stable ASE emission exceeding 21 hours in ambient conditions.

Single Crystal Sn-Based Halide Perovskites.

Sn-based halide perovskites are expected to be the best replacement for toxic lead-based counterparts, owing to their similar ionic radii and the optimal band gap for use in solar cells, as well as their versatile use in light-emitting diodes and photodetection applications. Concerns, however, exist about their stability under ambient conditions, an issue that is exacerbated in polycrystalline films because grain boundaries present large concentrations of defects and act as entrance points for oxygen and water, causing Sn oxidation. A current thriving research area in perovskite materials is the fabrication of perovskite single crystals, promising improved optoelectronic properties due to excellent uniformity, reduced defects, and the absence of grain boundaries. This review summarizes the most recent advances in the fabrication of single crystal Sn-based halide perovskites, with emphasis on synthesis methods, compositional engineering, and formation mechanisms, followed by a discussion of various challenges and appropriate strategies for improving their performance in optoelectronic applications.

Air-Processed Efficient Cesium-Based Two-Dimensional Perovskite Solar Cells Based on Asymmetric Chiral Ammonium Salts.

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, (R)-α-phenylethylamine acrylate (R-α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R-α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R-α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs (R-α-PEA2Cs4Pb5I16, n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions.

The fabrication of stable perovskite nanofilm patterns is important for the development of functional optical devices. However, current production approaches are limited by the requirement for strict inert gas protection and long processing times. Here, a confined flash printing synthesis method is presented to generate perovskite nanofilms under ambient conditions, combining precursor transfer, perovskite synthesis, crystallization, and polymer protection in a single step within milliseconds. A laser simultaneously prints and induces the flash synthesis, confined in a polymer nanofilm, under normal ambient conditions. Due to its simplicity and flexibility, the method enables the combination and screening of many different perovskite precursor materials on various substrates. Besides for the development of novel perovskite materials and devices, the nanofilms can be applied for biodetection. The unique H2O2-responsive property of the ultrathin perovskite quantum dot film is applied for biomolecule detection based on oxidase-catalyzed enzymatic reactions.

Lead-Free Perovskite With Efficient Tellurium Ion Activation for Multifunctional Applications.

Lead-free perovskite materials have received extensive attention due to their non-toxicity, super environmental stability and adjustable photoelectric properties. However, the inherent problems of low luminous efficiency and low photoluminescence quantum yields (PLQYs) limit its development in multifunctional applications. Here, Te4+ doped Cs2ZrCl6 with high luminous efficiency and stability for multifunctional applications are developed. Te4+ ions are used as emission centers to improve the optical properties of Cs2ZrCl6 to make efficient and stable single-component white light-emitting diodes (WLEDs), and can be used as scintillator materials to improve scintillation performance to achieve high-resolution and low-dose X-ray imaging detection. In addition, it is found for the first time that Te4+ ions can be introduced into the trap center, so that the Cs2ZrCl6:Te4+ perovskite material exhibits excellent persistent luminescence (PersL) and mechanoluminescence (ML) after X-ray radiation, which has potential applications in the fields of delayed imaging and stress sensing. This work provides a method for designing lead-free perovskites with high optical performance and scintillating properties, as well as developing multifunctional applications.