Single‐Crystalline Perovskite Microlasers for High‐Contrast and Sub‐Diffraction Imaging

Bottom‐up synthesized single‐crystalline micro‐ and nanolasers have been intensively studied in past decades. While the potential of single‐crystalline lasers in integrated photonics has been seriously considered for years, their device performances are restricted by the scattering loss. Here, in contrast to the utilization of Q‐factor or laser linewidth, the ultrasmooth surfaces of lead halide perovskite microplate lasers are exploited and their potential in subdiffraction limit imaging is explored for the first time. The nanostructures on the surface of the microplate can effectively scatter the evanescent waves and make the corresponding subwavelength spatial information detectable at far field. With the assistance of perovskite microlasers, a 41 nm nanogap and complex nanostructures are resolved with a conventional microscope. Meanwhile, more than 1000 determinants within the lasing are imaged simultaneously and the image contrast is further improved by the amplification of perovskite microlasers. This work shall revolutionize the applications of single‐crystalline microlasers and subdiffraction limit imaging techniques.     

Improved Stability and Photodetector Performance of CsPbI3 Perovskite Quantum Dots by Ligand Exchange with Aminoethanethiol

A surface engineering strategy aimed at improving the stability of CsPbI₃ perovskite quantum dots (QDs) both in solution and as films is demonstrated, by performing partial ligand exchange with a short chain ligand, 2‐aminoethanethiol (AET), in place of the original long chain ligands, oleic acid (OA) and oleylamine (OAm), used in synthesis. This results in the formation of a compact ligand barrier around the particles, which prevents penetration of water molecules and thus degradation of the films and, in addition, at the same time improves carrier mobility. Moreover, the AET ligand can passivate surface traps of the QDs, leading to an enhanced photoluminescence (PL) efficiency. As a result, AET‐CsPbI₃ QDs maintain their optical performance both in solution and as films, retaining more than 95% of the initial PL intensity in water after 1 h, and under ultraviolet irradiation for 2 h. Photodetectors based on the AET‐CsPbI₃ QD films exhibit remarkable performance, such as high photoresponsivity (105 mA W^?1) and detectivity (5 × 10¹³ Jones at 450 nm and 3 × 10¹³ Jones at 700 nm) without an external bias. The photodetectors also show excellent stability, retaining more than 95% of the initial responsivity in ambient air for 40 h without any encapsulation.     

Interfacial‐Tunneling‐Effect‐Enhanced CsPbBr3 Photodetectors Featuring High Detectivity and Stability

Inorganic halide perovskite (HP)‐based photodetectors (PDs) have exhibited fast response speed and high responsivity, but with low detectivity due to the high dark current of devices. Additionally, the intrinsic instability of HPs and interface deterioration originating from ion migration inhibit their practical applications severely. A tunneling organic layer is introduced to solve both these problems. Light‐induced charge carriers can flow across the interfacial (poly(methyl methacrylate), PMMA) layer with appropriate thickness via the Fowler–Nordheim tunneling effect. Due to the effective control of dark current, the photo‐/dark‐current ratio reaches a giant value of 2.13 × 10⁸, and the peak detectivity is as high as 1.24 × 10¹³ Jones. With such superiority, light signal as weak as 244 pW is accurately imaged by a PD array. Additionally, the hydrophobic organic layer inhibits the destruction of HPs caused by moisture and ion migration induced interface reaction, and negligible response attenuation is observed during continuous work in a humid environment for 48 h. This heterojunction structure design provides a new strategy to enhance the performance and stability of perovskite‐based photoelectric and photovoltaic devices.     

Self-Organized Co3O4-SrCO3 Percolative Composites Enabling Nanosized Hole Transport Pathways for Perovskite Solar Cells

Perovskite solar cells (PSCs) are expected to profoundly impact the photovoltaic society on account of its high-efficiency and cost-saving manufacture. As a key component in efficient PSCs, the hole transport layer (HTL) can selectively collect photogenerated carriers from perovskite absorbers and prevent the charge recombination at interfaces. However, the mainstream organic HTLs generally require multi-step synthesis and hygroscopic dopants that significantly limit the practical application of PSCs. Here, a self-organized percolative architecture composed of narrow bandgap oxides (e.g., Co₃O₄, NiO, CuO, Fe₂O₃, and MnO₂) and wide bandgap SrCO₃ oxysalt as efficient HTLs for PSCs is presented. The percolation of dual phases offers nanosized hole transport pathways and optimized interfacial band alignments, enabling significantly improved charge collection compared with the single phase HTLs. As a consequence, the power conversion efficiency boosted from 8.08% of SrCO₃ based device and 15.47% of Co₃O₄ based device to 21.84% of Co₃O₄-SrCO₃ based one without notable hysteresis. The work offers a new direction by employing percolative materials for efficient charge transport and collection in PSCs, and would be applicable to a wide range of opto-electronic thin film devices.     

Solution-Processed Selective Area Homoepitaxial Growth of Suspended MAPbX3 (X = Cl,Br) Perovskite Micro-Arrays

Suspended nano/microstructures on semiconductor surfaces that can manage light are attractive for various on-chip and efficiency-enhanced optoelectronics. Hybrid halide perovskites have shown considerable potential for optoelectronic and photonic applications. However, the ionic and soft lattices of perovskites are sensitive to polar solvents, photons, and heat, limiting the post-processing of suspended microstructures. Herein, a solution-processed selective area homoepitaxial growth (SAEG) method is introduced to create well-ordered, suspended microstructure arrays on the surface of MAPbX₃ (X = Br, Cl) single-crystalline thin films. The suspended micro-arrays exhibit single crystalline structures and 11.2 fold photoluminescence enhancement compared to the thin-film substrates. The success of SAEG lies in the making use of perovskite supersaturated HX aqueous solutions that not only repair surface defects induced by lithography but also satisfy homoepitaxial growth kinetics. This study paves a pathway for the fabrication of cost-effective perovskite surface-suspended microstructures for efficiency-enhanced and on-chip optoelectronic devices.     

Sustainable and Self‐Enhanced Electrochemiluminescent Ternary Suprastructures Derived from CsPbBr3 Perovskite Quantum Dots

Lead halide perovskite quantum dots (QDs) are promising electrochemiluminescence (ECL) nanoemitters due to their fascinating photophysical properties. However, due to their poor structural stability against the external environment, the trade‐off between their colloidal stability and carrier injection/transport efficiency is a major challenge in the advancement of perovskite‐based ECL technology. In this work, intense and stable ECL from CsPbBr₃ (CPB) QDs is achieved by simultaneously encapsulating CPB QDs and coreactant (CoR) into in situ generated SiO₂ matrix via hydrolysis of tetramethyl orthosilicate. The well‐designed architecture of the as‐obtained CPB‐CoR@SiO₂ nanocomposites (NCs) guarantees not only greatly improved stability thanks to the peripheral SiO₂ protecting matrix, but also efficient self‐enhanced ECL between CPB and the intra‐coreactants. Consequently, by elaborately selecting the CoR molecules with different tertiary/secondary amines and functional groups, multifold higher (up to 10.2 times) ECL efficiencies are obtained for the CPB‐CoR@SiO₂ NCs alone in reference to the standard Ru(bpy)₃²⁺/tri‐n‐propylamine system. This work provides an efficient design strategy for obtaining stable and highly efficient ECL from perovskite QDs, and offers a new perspective for the development and application of perovskite‐based ECL system.     

Experimental Strategy and Mechanistic View to Boost the Photocatalytic Activity of Cs3Bi2Br9 Lead-Free Perovskite Derivative by g-C3N4 Composite Engineering

The rational design of heterojunctions based on metal halide perovskites (MHPs) is an effective route to create novel photocatalysts to run relevant solar-driven reactions. In this work, an experimental and computational study on the synergic coupling between a lead-free Cs₃Bi₂Br₉ perovskite derivative and g-C₃N₄ is presented. A relevant boost of the hydrogen photogeneration by more than one order of magnitude is recorded when going from pure g-C₃N₄ to the Cs₃Bi₂Br₉/g-C₃N₄ system. Effective catalytic activity is also achieved in the degradation of the organic pollutant with methylene blue as a model molecule. Based upon complementary experimental outputs and advanced computational modeling, a rationale is provided to understand the heterojunction functionality as well as the trend of hydrogen production as a function of perovskite loading. This work adds further solid evidence for the possible application of MHPs in photocatalysis, which is emerging as an extremely appealing and promising field of application of these superior semiconductors.     

Single Crystal Perovskite Solar Cells: Development and Perspectives

The efficiency of perovskite solar cells has increased to a certified value of 25.2% in the past 10 years, benefiting from the superior properties of metal halide perovskite materials. Compared with the widely investigated polycrystalline thin films, single crystal perovskites without grain boundaries have better optoelectronic properties, showing great potential for photovoltaics with higher efficiency and stability. Additionally, single crystal perovskite solar cells are a fantastic model system for further investigating the working principles related to the surface and grain boundaries of perovskite materials. Unfortunately, only a handful of groups have participated in the development of single crystal perovskite solar cells; thus, the development of this area lags far behind that of its polycrystalline counterpart. Therefore, a review paper that discusses the recent developments and challenges of single crystal perovskite solar cells is urgently required to provide guidelines for this emerging field. In this progress report, the optical and electrical properties of single crystal and polycrystalline perovskite thin films are compared, followed by the recent developments in the growth of single crystal perovskite thin films and the photovoltaic applications of this material. Finally, the challenges and perspectives of single crystal perovskite solar cells are discussed in detail.     

Engineering the Exciton Dissociation in Quantum‐Confined 2D CsPbBr3 Nanosheet Films

Recent years have witnessed a rapid development of all‐inorganic halide perovskite in optoelectronic devices. Ultrathin 2D CsPbBr₃ nanosheets (NSs) with large lateral dimensions have demonstrated exceptional photophysical properties because of their analogous exciton electronic structure to quantum wells. Despite the incredible progress on device performance, the photophysics and carrier transportation parameters of quantum‐confined CsPbBr₃ NSs are lacking, and the fundamental understanding of the exciton dissociation mechanism is far less developed. Here, a ligands rearrangement mechanism is proposed to explain why annealed NS films have an increased charge transfer rate and a decreased exciton binding energy and lifetime, prompting tunneling as a dominant way of exciton dissociation to separate photogenerated excitons between neighboring NSs. This facile but efficient method provides a new insight to manipulate perovskite nanocrystals coupling. Moreover, ultrathin 2D CsPbBr₃ NS film is demonstrated to have a enhanced absorption cross section and high carrier mobility of 77.9 cm² V^?1 s^?1, contributing to its high responsivity of 0.53 A W^?1. The photodetector has a long‐term stability up to three months, which are responsible for reliable perovskite‐based device performance.     

Mixed Halide Formation in Lead-Free Antimony-Based Halide Perovskite for Boosted CO2 Photoreduction: Beyond Band Gap Tuning

Photocatalytic conversion of carbon dioxide (CO₂) into value-added fuels is a vastly promising anthropogenic chemical carbon cycle to combat the greenhouse effect while meeting the ever-increasing energy demand. Recently, lead-based halide perovskites have demonstrated great potential in various applications including photochemical reduction of CO₂. However, in view of lead toxicity, the exploration of a lead-free alternative is crucial for long term application. Herein, a series of lead-free mixed halide perovskites Cs₃Sb₂Cl_xBr_9−x (0 ≤ x ≤ 9) is prepared via a facile antisolvent recrystallization technique, where the incorporation of a secondary halide enhances the charge transfer and separation while allowing precise tuning of bandgap between 2.59 and 2.90 eV. Theoretical calculations further reveal that the formation of mixed Cl/Br halides engenders favorable charge redistribution due to lower octahedral distortion, which in turn strengthens CO₂ adsorption and activation. Under visible light illumination, the optimal dual halide perovskite, Cs₃Sb₂Cl₄Br₅ manifests substantial twofold and fourfold enhancements of CH₄ yield over the single halide perovskite, Cs₃Sb₂Br₉ and Cs₃Sb₂Cl₉, respectively. In brief, this study provides a compelling demonstration of lead-free mixed halide perovskites for photocatalytic CO₂ reduction, and it is anticipated to drive further application of perovskite-based photocatalysts toward a diverse range of artificial photoredox reactions.     

Piezoelectric Nanogenerator Based on In Situ Growth All-Inorganic CsPbBr3 Perovskite Nanocrystals in PVDF Fibers with Long-Term Stability

Inorganic lead halide perovskite has become an emerging material for modern photoelectric and electronic nanodevices due to its excellent optical and electronic properties. In view of its huge dielectric and electrical properties, inorganic CsPbBr₃ perovskite is introduced into the piezoelectric nanogenerator (PENG). Based on one-step electrospinning of solutions containing CsPbBr₃ precursors and polyvinylidene difluoride (PVDF), in situ growth of CsPbBr₃ nanocrystals in PVDF fibers (CsPbBr₃@PVDF composite fibers) with highly uniform size and spatial distribution are synthesized. The CsPbBr₃@PVDF composite fibers based PENG reveals an open-circuit voltage (V_oc) of 103 V and a density of short-circuit current (I_sc) of 170  µ A cm⁻², where the V_oc is comparable to the state-of-the-art hybrid composite piezoelectric nanogenerators (PENGs) and the density of I_sc is 4.86 times higher than that of lead halide perovskites counterpart ever reported. Moreover, CsPbBr₃@PVDF composite fibers based PENG exhibits fundamentally improved thermal/water/acid–base stabilities. This study suggests that the CsPbBr₃@PVDF composite fiber is a good candidate for fabricating high-performance PENGs, promising application potentials in mechanical energy harvesting and motion sensing technologies.     

Flexible and Self‐Powered Lateral Photodetector Based on Inorganic Perovskite CsPbI3–CsPbBr3 Heterojunction Nanowire Array

Self‐powered perovskite photodetectors mainly adopt the vertical heterojunction structure composed of active layer, electron–hole transfer layers, and electrodes, which results in the loss of incident light and interfacial accumulation of defects. To address these issues, a self‐powered lateral photodetector based on CsPbI₃–CsPbBr₃ heterojunction nanowire arrays is designed on both a rigid glass and a flexible polyethylene naphthalate substrate using an in situ conversion and mask‐assisted electrode fabrication method. Through adding the polyvinyl pyrrolidone and optimizing the concentration of precursors under the pressure‐assisted moulding process, both the crystallinity and stability of perovskite nanowire array are improved. The nanowire array–based lateral device shows a high responsivity of 125 mA W^?1 and a fast rise and decay time of 0.7 and 0.8 ms under a self‐powered operation condition. This work provides a new strategy to fabricate perovskite heterojunction nanoarrays towards self‐powered photodetection.     

The Role of Chlorine in the Formation Process of “CH3NH3PbI3‐xClx” Perovskite

CH₃NH₃PbI_3‐xCl_x is a commonly used chemical formula to represent the methylammonium lead halide perovskite fabricated from mixed chlorine‐ and iodine‐containing salt precursors. Despite the rapid progress in improving its photovoltaic efficiency, fundamental questions remain regarding the atomic ratio of Cl in the perovskite as well as the reaction mechanism that leads to its formation and crystallization. In this work we investigated these questions through a combination of chemical, morphological, structural and thermal characterizations. The elemental analyses reveal unambiguously the negligible amount of Cl atoms in the CH₃NH₃PbI_3‐xCl_x perovskite. By studying the thermal characteristics of methylammonium halides as well as the annealing process in a polymer/perovskite/FTO glass structure, we show that the formation of the CH₃NH₃PbI_3‐xCl_x perovskite is likely driven by release of gaseous CH₃NH₃Cl (or other organic chlorides) through an intermediate organometal mixed halide phase. Furthermore, the comparative study on CH₃NH₃I/PbCl₂ and CH₃NH₃I/PbI₂ precursor combinations with different molar ratios suggest that the initial introduction of a CH₃NH₃⁺ rich environment is critical to slow down the perovskite formation process and thus improve the growth of the crystal domains during annealing; accordingly, the function of Cl^? is to facilitate the release of excess CH₃NH₃⁺ at a relatively low annealing temperatures.     

CsPbBr3 Nanocrystal Films: Deviations from Bulk Vibrational and Optoelectronic Properties

Metal‐halide perovskites (MHP) are highly promising semiconductors for light‐emitting and photovoltaic applications. The colloidal synthesis of nanocrystals (NCs) is an effective approach for obtaining nearly defect‐free MHP that can be processed into inks for low‐cost, high‐performance device fabrication. However, disentangling the effects of surface ligands, morphology, and boundaries on charge‐carrier transport in thin films fabricated with these high‐quality NCs is inherently difficult. To overcome this fundamental challenge, terahertz (THz) spectroscopy is employed to optically probe the photoconductivity of CsPbBr₃ NC films. The vibrational and optoelectronic properties of the NCs are compared with those of the corresponding bulk polycrystalline perovskite and significant deviations are found. Charge‐carrier mobilities and recombination rates are demonstrated to vary significantly with the NC size. Such dependences derive from the localized nature of charge carriers within NCs, with local mobilities dominating over interparticle transport. It is further shown that the colloidally synthesized NCs have distinct vibrational properties with respect to the bulk perovskite, exhibiting blue‐shifted optical phonon modes with enhanced THz absorption strength that also manifest as strong modulations in the THz photoconductivity spectra. Such fundamental insights into NC versus bulk properties will guide the optimization of nanocrystalline perovskite thin films for optoelectronic applications.     

Exciton Dynamics and Optically Pumped Lasing in 1-Naphthylmethylamine-Based Quasi-2D Perovskite Films

Films of the quasi-2D perovskite based on 1-naphthylmethylamine (NMA) are promising as the gain medium for optically pumped lasing and future electrically pumped lasing because of its low lasing threshold and small electroluminescence efficiency rolloff. However, reasons for the low threshold and small efficiency rolloff are still unclear. Therefore, exciton dynamics are investigated in NMA-based quasi-2D perovskite films. It is found that quenching of bright excitons by other excitons or charge carriers is unlikely in NMA-based quasi-2D perovskite films, which is one reason for the low lasing threshold and small efficiency rolloff. Moreover, thermally stimulated current measurements reveal that the defect levels inside the band gap of the NMA-based quasi-2D perovskite are shallow, with a depth of ≈0.3 eV, causing a decrease in nonradiative exciton recombination through the defects. Therefore, population inversion can be easily achieved, leading to the low lasing threshold as well. For fabrication of NMA-based quasi-2D perovskite laser devices with even lower lasing thresholds, a circular-shaped optical resonator, and small-molecule-based defect passivation are used. Optically pumped lasing can be obtained from these devices, with a threshold of ≈1 µJ cm⁻², which is one of the lowest values ever reported in any perovskite lasers.     

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed-Halide Perovskite Films

Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic-force, optical, and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide-rich clusters as visualized by nano-X-ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light-induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity.     

Optoelectronic Synapses and Photodetectors Based on Organic Semiconductor/Halide Perovskite Heterojunctions: Materials,Devices, and Applications

Both photodetectors (PDs) and optoelectronic synaptic devices (OSDs) are optoelectronic devices converting light signals into electrical responses. Optoelectronic devices based on organic semiconductors and halide perovskites have aroused tremendous research interest owing to their exceptional optical/electrical characteristics and low-cost processability. The heterojunction formed between organic semiconductors and halide perovskites can modify the exciton dissociation/recombination efficiency and modulate the charge-trapping effect. Consequently, organic semiconductor/halide perovskite heterojunctions can endow PDs and OSDs with high photo responsivity and the ability to simulate synaptic functions respectively, making them appropriate for the development of energy-efficient artificial visual systems with sensory and recognition functions. This article summarizes the recent advances in this research field. The physical/chemical properties and preparation methods of organic semiconductor/halide perovskite heterojunctions are briefly introduced. Then the development of PDs and OSDs based on organic semiconductor/halide perovskite heterojunctions, as well as their innovative applications, are systematically presented. Finally, some prospective challenges and probable strategies for the future development of optoelectronic devices based on organic semiconductor/halide perovskite heterojunctions are discussed.