Making BaZrS3 Chalcogenide Perovskite Thin Films by Molecular Beam Epitaxy

The making of BaZrS₃ thin films by molecular beam epitaxy (MBE) is demonstrated. BaZrS₃ forms in the orthorhombic distorted-perovskite structure with corner-sharing ZrS₆ octahedra. The single-step MBE process results in films smooth on the atomic scale, with near-perfect BaZrS₃ stoichiometry and an atomically sharp interface with the LaAlO₃ substrate. The films grow epitaxially via two competing growth modes: buffered epitaxy, with a self-assembled interface layer that relieves the epitaxial strain, and direct epitaxy, with rotated-cube-on-cube growth that accommodates the large lattice constant mismatch between the oxide and the sulfide perovskites. This work sets the stage for developing chalcogenide perovskites as a family of semiconductor alloys with properties that can be tuned with strain and composition in high-quality epitaxial thin films, as has been long-established for other systems including Si-Ge, III-Vs, and II-VIs. The methods demonstrated here also represent a revival of gas-source chalcogenide MBE.     

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.     

Vapor Phase Growth of Centimeter-Sized Band Gap Engineered Cesium Lead Halide Perovskite Single-Crystal Thin Films with Color-tunable Stimulated Emission

Single crystal metal halide perovskites thin films are considered to be a promising optical, optoelectronic materials with extraordinary performance due to their low defect densities. However, it is still difficult to achieve large-scale perovskite single-crystal thin films (SCTFs) with tunable bandgap by vapor-phase deposition method. Herein, the synthesis of CsPbCl_3(1–x)Br_3x SCTFs with centimeter size (1 cm × 1 cm) via vapor-phase deposition is reported. The Br composition of CsPbCl_3(1–x)Br_3x SCTFs can be gradually tuned from x = 0 to x = 1, leading the corresponding bandgap to change from 2.29 to 2.91 eV. Additionally, an low-threshold (≈23.9 µJ cm⁻²) amplified spontaneous emission is achieved based on CsPbCl_3(1–x)Br_3x SCTFs at room temperature, and the wavelength is tuned from 432 to 547 nm by varying the Cl/Br ratio. Importantly, the high-quality CsPbCl_3(1–x)Br_3x SCTFs are ideal optical gain medium with high gain up to 1369.8 ± 101.2 cm⁻¹. This study not only provides a versatile method to fabricate high quality CsPbCl_3(1–x)Br_3x SCTFs with different Cl/Br ratio, but also paves the way for further research of color-tunable perovskite lasing.     

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.     

Millimeter-Size All-inorganic Perovskite Crystalline Thin Film Grown by Chemical Vapor Deposition

The chemical vapor deposition (CVD) method is a dry approach that can produce high quality crystals and thin films at large scale which can be easily adapted by industry. In this work, CVD technology is employed to grow high quality, large size all-inorganic cesium lead bromide perovskite crystalline film for the first time. The obtained films have millimeter size crystalline domains with high phase purity. The growth kinetics are examined in detail by optical microscopy and X-ray diffraction. The deposition rate and growth temperature are found to be the key parameters allowing to achieve large scale crystal growth. The large crystalline grains exhibit exceptional optical properties including negligible Stokes shift and uniform photoluminescence over a large scale. This suggests a high degree of crystallinity free from internal strain or defects. A lateral diode within one large crystalline grain is further fabricated and significant photo-generated voltage and short circuit current are observed, suggesting highly efficient carrier transport and collections without scattering within the grain. This demonstration suggests that the CVD grown all-inorganic perovskite thin films enable a promising fabrication route suitable for photovoltaic or photo-detector applications.     

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.     

Air‐Stable Highly Crystalline Formamidinium Perovskite 1D Structures for Ultrasensitive Photodetectors

State‐of‐the‐art optoelectronic devices based on metal‐halide perovskites demand solution‐processed structures with high crystallinity, controlled crystallographic orientation, and enhanced environmental stability. Formamidinium lead iodide (α‐FAPbI₃) possesses a suitable bandgap of 1.48 eV and enhanced thermal stability, whereas perovskite‐type polymorph (α‐phase) is thermodynamically instable at ambient temperatures. Stable α‐FAPbI₃ perovskite 1D structure arrays with high crystallinity and ordered crystallographic orientation are developed by controlled nucleation and growth in capillary bridges. By surface functionalization with phenylethylammonium ions (PEA⁺), FAPbI₃ wires sustain a stable α‐phase after 28 day storage in the ambient environment with a relative humidity of 50%. Enhanced photoluminescence (PL) intensity and elongated PL lifetime demonstrate suppressed trap density and high crystallinity in these 1D structures, which is also reflected by the enhanced diffraction density and pure (001) crystallographic orientation in the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) pattern. Based on these high‐quality 1D structures, sensitive photodetectors are achieved with average responsivities of 5282 A W^?1, average specific detectivities of more than 1.45 × 10¹⁴ Jones, and a fast response speed with a 3 dB bandwidth of 15 kHz.     

Epitaxial Growth of Large‐Scale Orthorhombic CsPbBr3 Perovskite Thin Films with Anisotropic Photoresponse Property

Inorganic cesium lead halide perovskite (CsPbX₃, X = Cl, Br, I) is a promising material for developing novel electronic and optoelectronic devices. Despite the substantial progress that has been made in the development of large perovskite single crystals, the fabrication of high‐quality 2D perovskite single‐crystal films, especially perovskite with a low symmetry, still remains a challenge. Herein, large‐scale orthorhombic CsPbBr₃ single‐crystal thin films on zinc‐blende ZnSe crystals are synthesized via vapor‐phase epitaxy. Structural characterizations reveal a “CsPbBr₃(110)//ZnSe(100), CsPbBr₃[?110]//ZnSe[001] and CsPbBr₃[001]//ZnSe[010]” heteroepitaxial relationship between the covering CsPbBr₃ layer and the ZnSe growth substrate. It is exciting that the epitaxial film presents an in‐plane anisotropic absorption property from 350 to 535 nm and polarization‐dependent photoluminescence. Photodetectors based on the epitaxial film exhibit a high photoresponsivity of 200 A W^?1, a large on/off current ratio exceeding 10⁴, a fast photoresponse time of about 20 ms, and good repeatability at room temperature. Importantly, a strong polarization‐dependent photoresponse is also found on the device fabricated using the epitaxial CsPbBr₃ film, making the orthorhombic perovskite promising building blocks for optoelectronic devices featured with anisotropy.     

High Responsivity and Response Speed Single‐Layer Mixed‐Cation Lead Mixed‐Halide Perovskite Photodetectors Based on Nanogap Electrodes Manufactured on Large‐Area Rigid and Flexible Substrates

Mixed‐cation lead mixed‐halide perovskites are employed as the photoactive material in single‐layer solution‐processed photodetectors fabricated with coplanar asymmetric nanogap Al–Au and indium tin oxide–Al electrodes. The nanogap electrodes, bearing an interelectrode distance of ≈10 nm, are patterned via adhesion lithography, a simple, low‐cost, and high‐throughput technique. Different electrode shapes and sizes are demonstrated on glass and flexible plastic substrates, effectively engineering the device architecture, and, along with perovskite film and material optimization, paving the way toward devices with tunable operational characteristics. The optimized coplanar nanogap junction perovskite photodetectors show responsivities up to 33 A W^?1, specific detectivity on the order of 10¹¹ Jones, and response times below 260 ns, while retaining a low dark current (0.3 nA) under ?2 V reverse bias. These values outperform the vast majority of perovskite photodetectors reported so far, while avoiding the complicated fabrication steps involved in conventional multilayer device structures. This work highlights the promising potential of the proposed asymmetric nanogap electrode architecture for application in the field of flexible optoelectronics.     

Highly Photoluminescent and Environmentally Stable Perovskite Nanocrystals Templated in Thin Self‐Assembled Block Copolymer Films

Ordered nanostructured crystals of thin organic–inorganic metal halide perovskites (OIHPs) are of great interest to researchers because of the dimensional‐dependence of their photoelectronic properties for developing OIHPs with novel properties. Top‐down routes such as nanoimprinting and electron beam lithography are extensively used for nanopatterning OIHPs, while bottom‐up approaches are seldom used. Herein, developed is a simple and robust route, involving the controlled crystallization of the OIHPs templated with a self‐assembled block copolymer (BCP), for fabricating nanopatterned OIHP films with various shapes and nanodomain sizes. When the precursor solution consisting of methylammonium lead halide (MAPbX₃, X = Br^?, I^?) perovskite and poly(styrene)‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) is spin‐coated on the substrate, a nanostructured BCP is developed by microphase separation. Spontaneous crystallization of the precursor ions preferentially coordinated with the P2VP domains yields ordered nanocrystals with various nanostructures (cylinders, lamellae, and cylindrical mesh) with controlled domain size (≈40–72 nm). The nanopatterned OIHPs show significantly enhanced photoluminescence (PL) with high resistance to both humidity and heat due to geometrically confining OIHPs in and passivation with the P2VP chains. The self‐assembled OIHP films with high PL performance provide a facile control of color coordinates by color conversion layers in blue‐emitting devices for cool‐white emission.     

GeTe薄膜的性质、应用及其红外探测研究进展

GeTe基半导体的非晶态,α-GeTe相和β-GeTe相可以相互转换,且在一定条件下稳定存在。利用高浓度空穴掺杂改善GeTe热电和铁电性能,以及非晶相和晶相间的巨大差异和快速切换,使其在热电、自旋器件、相变开关、相变存储等多个领域具有很大的应用前景。此外,GeTe具有窄光学带隙和高载流子迁移率,有望用于高性能红外光电探测,然而其在红外光电探测方面还处于初始阶段。本综述在详述其性质及在热电、相变等领域应用情况的基础上,根据GeTe的光电性质,展望了其在红外光电探测领域方面的应用。     

热蒸发紫外LaF3薄膜光学性能和结构表征

在不同的沉积温度下,用热蒸发方法在熔融石英(JGS1)上制备了LaF3单层薄膜。分别采用分光光度计测量了薄膜样品的透射率和反射率光谱,反演得出薄膜的折射率和消光系数;采用原子力显微镜(AFM)观察了样品的表面形貌,并通过表面粗糙度计算得出总积分散射损耗;采用X射线衍射仪(XRD)测试了薄膜的晶体结构,由衍射谱图拟合得到衍射峰的半峰全宽,进而计算出薄膜晶粒的平均尺寸。实验结果表明,随着沉积温度的升高,LaF3薄膜的结晶状况明显变好,晶粒尺寸逐渐变大,膜层变得更加致密,薄膜的光学常数和折射率不均匀性均呈线性变化。沉积温度的增加对薄膜表面粗糙度的影响不明显,散射损耗在光学损耗中所占比例较小,所以光学损耗的变化主要由吸收损耗引起。     

Liquid Phase Heteroepitaxial Growth of Moisture‐Tolerant MOF‐5 Isotype Thin Films and Assessment of the Sorption Properties by Quartz Crystal Microbalance

The moisture‐tolerant metal‐organic frameworks (MOFs) of formula [Zn₄O(L)₃]_n (L = di‐substituted carboxypyrazolate derivatives) are fabricated as thin films on self‐assembled monolayer (SAM) functionalized gold substrates by employing the step‐by‐step liquid phase epitaxial (LPE) deposition method in a continuous operation mode. The in situ monitoring of the deposition by quartz crystal microbalance (QCM) and grazing incidence X‐ray diffraction reveal different growth regimes and crystallinities of the obtained thin films in dependence of the chosen alkyl side chain functionality at the carboxypyrazolate linkers, L. To overcome the relatively poor crystallinity and low porosity of a particular homostructured metal‐organic framework type B film, the step‐by‐step heteroepitaxial growth of this MOF B on top of the crystallite surfaces of a well‐grown and lattice‐matched MOF type A is applied. This approach enables the fabrication of oriented, core‐shell‐like MOF B @ A surface mounted heterocrystals as an intergrown homogeneous coating for the selective adsorption of volatile organic compounds. The accessible pore volumes of the individual components and the heterostructured films are characterized by performing adsorption measurements of different organic probe molecules using an environmentally controlled QCM instrument. The results show good adsorption capacity, excellent size exclusion selectivity for alcohols, and a high degree of moisture‐tolerance of the heteroepitaxial MOF films.     

非致冷钛酸锶钡铁电薄膜红外探测器

采用半导体微机械(Micro-Electro-Mechanical System,MEMS)技术制备了具有热隔离微桥的8×8元非致冷Ba0.8Sr02TiO3薄膜红外探测器列阵原型器件.热释电性能优良的Ba0.8Sr0.2TiO3薄膜是使用浓度为0.05M的前躯体溶液、采用Sol-Gel制备的.在5～30℃的温度范围内,Ba0.8Sro2TiO3薄膜的热释电系数大于20nC/cm2K,在16.8℃处达到最大值41.3 nC/cm2K.在19℃的环境温度下,使用500 K黑体作为红外辐射源,测得10 Hz调制频率下,探测单元的探测率D*为5.9 × 107cmHz1/2W-1.对器件结构的进一步改进和测试条件的进一步改善可望获得更高的探测率.     

BaTiO3薄膜的水热合成与分析表征

采用水热合成法直接在高纯钛金属薄片上制备了BaTiO3薄膜;研究了水热反应温度对制备BaTiO3薄膜的影响;利用X-射线衍射(XRD)、扫描电子显微镜(SEM)和X-射线光电子能谱(XPS)对制备的薄膜进行分析表征。研究结果表明,当水热反应温度相对较低(低于200℃)时,得不到纯净的四方钙钛矿BaTiO3薄膜;在250℃下水热反应5 h,得到了纯净的四方钙钛矿BaTiO3薄膜,薄膜的晶粒呈球形,平均粒径为200~300 nm。     

High-Performance Ultraviolet Photodetectors Enabled by van der Waals Schottky Junction Based on TiO2 Nanorod Arrays/Au-Modulated Ti3C2Tx MXene

Two-dimensional transition metal carbides and nitrides (MXenes) show tremendous potential for optoelectronic devices due to their excellent electronic properties. Here, a high-performance ultraviolet photodetector based on TiO₂ nanorod arrays/Ti₃C₂T_x MXene van der Waals (vdW) Schottky junction by all-solution process technique is reported. The Ti₃C₂T_x MXene modulated by the Au electrode increases its work function from 4.41 to 5.14 eV to form a hole transport layer. Complemented by the dangling bond-free surface of Ti₃C₂T_x, the Fermi-level pinning effect is suppressed and the electric-field strength of the Schottky junction is enhanced, which promotes charge separation and transport. After applying a bias of −1.5 V, the photovoltaic effect is favorably reinforced, while the hole-trapping mechanism (between TiO₂ and oxygen) and reverse pyroelectric effect are largely eliminated. As a result, the responsivity and specific detectivity of the device with FTO/TiO₂ nanorod arrays/Ti₃C₂T_x/Au structure reach 1.95 × 10⁵ mA W⁻¹ and 4.3 × 10¹³ cm Hz^1/2 W⁻¹ (370 nm, 65 mW cm⁻²), respectively. This work provides an effective approach to enhance the performance of photodetectors by forming the vdW Schottky junction and choosing metal electrodes to modulate MXene as a suitable charge transport layer.     

热蒸镀法与溶胶-凝胶法制备的WO3薄膜

采用真空热蒸发沉积技术在衬底上沉积了WO3薄膜；以金属W粉为无机原料，溶胶—凝胶技术结合浸渍镀膜方法制备出WO3薄膜，借助SEM、可见光分光光度计、椭偏仪等仪器测量了薄膜的特性。实验表明：热处理使两种方法制得的薄膜致密，折射率增大，WO3颗粒增大；在热处理条件相同的情况下，溶胶—凝胶法制备的WO3薄膜折射率比热蒸镀法制备的WO3薄膜折射率小。     

温度对飞秒激光沉积ZnO/Si薄膜的结构和性能的影响

通过飞秒脉冲激光(50 fs,800 nm,1 kHz,2 mJ)沉积技术在n型Si(100)单晶基片上制备了ZnO薄膜.详细研究了基片温度变化以及退火处理对ZnO薄膜的结构、表面形貌及光学性质的影响.X射线衍射(XRD)结果表明,不同温度下(20~350℃)生长的ZnO薄膜具有纤锌矿结构,并且呈c轴择优取向;当基片温度为80℃时,薄膜沿(002)晶面高度择优生长;当基片温度为500℃时薄膜沿(103)晶面择优生长,场发射扫描电子显微镜(FEEM)结果表明薄膜呈纳米晶结构,并观察到了ZnO的六方结构.进一步通过透射光谱的测量讨论了基片温度及退火处理对ZnO薄膜光学透射率的影响,结果表明退火后薄膜的透射率增大.