Iodine Vacancy Redistribution in Organic–Inorganic Halide Perovskite Films and Resistive Switching Effects

Organic–inorganic halide perovskite (OHP) materials, for example, CH₃NH₃PbI₃ (MAPbI₃), have attracted significant interest for applications such as solar cells, photodectors, light‐emitting diodes, and lasers. Previous studies have shown that charged defects can migrate in perovskites under an electric field and/or light illumination, potentially preventing these devices from practical applications. Understanding and control of the defect generation and movement will not only lead to more stable devices but also new device concepts. Here, it is shown that the formation/annihilation of iodine vacancies (V_I's) in MAPbI₃ films, driven by electric fields and light illumination, can induce pronounced resistive switching effects. Due to a low diffusion energy barrier (≈0.17 eV), the V_I's can readily drift under an electric field, and spontaneously diffuse with a concentration gradient. It is shown that the V_I diffusion process can be suppressed by controlling the affinity of the contact electrode material to I^? ions, or by light illumination. An electrical‐write and optical‐erase memory element is further demonstrated by coupling ion migration with electric fields and light illumination. These results provide guidance toward improved stability and performance of perovskite‐based optoelectronic systems, and can lead to the development of solid‐state devices that couple ionics, electronics, and optics.     

Hybrid Organic–Inorganic Perovskite Photodetectors

Hybrid organic–inorganic perovskite materials garner enormous attention for a wide range of optoelectronic devices. Due to their attractive optical and electrical properties including high optical absorption coefficient, high carrier mobility, and long carrier diffusion length, perovskites have opened up a great opportunity for high performance photodetectors. This review aims to give a comprehensive summary of the significant results on perovskite‐based photodetectors, focusing on the relationship among the perovskite structures, device configurations, and photodetecting performances. An introduction of recent progress in various perovskite structure‐based photodetectors is provided. The emphasis is placed on the correlation between the perovskite structure and the device performance. Next, recent developments of bandgap‐tunable perovskite and hybrid photodetectors built from perovskite heterostructures are highlighted. Then, effective approaches to enhance the stability of perovskite photodetector are presented, followed by the introduction of flexible and self‐powered perovskite photodetectors. Finally, a summary of the previous results is given, and the major challenges that need to be addressed in the future are outlined. A comprehensive summary of the research status on perovskite photodetectors is hoped to push forward the development of this field.     

Hybrid Perovskite Light‐Emitting Diodes Based on Perovskite Nanocrystals with Organic–Inorganic Mixed Cations

Organic–inorganic hybrid perovskite materials with mixed cations have demonstrated tremendous advances in photovoltaics recently, by showing a significant enhancement of power conversion efficiency and improved perovskite stability. Inspired by this development, this study presents the facile synthesis of mixed‐cation perovskite nanocrystals based on FA_{(1?x )}Cs_x PbBr₃ (FA = CH(NH₂)₂). By detailed characterization of their morphological, optical, and physicochemical properties, it is found that the emission property of the perovskite, FA_{(1?x )}Cs_x PbBr₃, is significantly dependent on the substitution content of the Cs cations in the perovskite composition. These mixed‐cation perovskites are employed as light emitters in light‐emitting diodes (LEDs). With an optimized composition of FA_0.8Cs_0.2PbBr₃, the LEDs exhibit encouraging performance with a highest reported luminance of 55 005 cd m^?2 and a current efficiency of 10.09 cd A^?1. This work provides important instructions on the future compositional optimization of mixed‐cation perovskite for obtaining high‐performance LEDs. The authors believe this work is a new milestone in the development of bright and efficient perovskite LEDs.     

Thermoresponsive Emission Switching via Lower Critical Solution Temperature Behavior of Organic–Inorganic Perovskite Nanoparticles

Lead halide perovskites have shown much promise for high‐performing solar cells due to their inherent electronic nature, and though the color of bright‐light emitters based on perovskite nanoparticles can be tuned by halide mixing and/or size control, dynamic switching using external stimuli remains a challenge. This article reports an unprecedented lower critical solution temperature (LCST) for toluene solutions containing methylammonium lead bromide (MAPbBr₃), oleic acid, alkylamines, and dimethylformamide. The delicate interplay of these molecules and ions allows for the reversible formation and decomposition of MAPbBr₃ nanoparticles upon heating and cooling, which is accompanied by green and blue photoemissions at each state. An intermediate 1D crystal with PbBr₂‐amine coordination is found to play pivotal role in this, and a mechanistic insight is provided based on a three‐state model. In addition to a high quantum yield (up to 85%), this system allows for control over the cloud point (30?80 °C) through compositional engineering and the luminescent color (blue to red) via halogen exchange, thus making it a versatile solution for developing functional molecular organic–inorganic LCST quantum dots.     

Ultrathin Ruddlesden–Popper Perovskite Heterojunction for Sensitive Photodetection

Thanks to their unique optical and electric properties, 2D materials have attracted a lot of interest for optoelectronic applications. Here, the emerging 2D materials, organic–inorganic hybrid perovskites with van der Waals interlayer interaction (Ruddlesden–Popper perovskites), are synthesized and characterized. Photodetectors based on the few‐layer Ruddlesden–Popper perovskite show good photoresponsivity as well as good detectivity. In order to further improve the photoresponse performance, 2D MoS₂ is chosen to construct the perovskite–MoS₂ heterojunction. The performance of the hybrid photodetector is largely improved with 6 and 2 orders of magnitude enhancement for photoresponsivity (10⁴ A W^?1) and detectivity (4 × 10¹⁰ Jones), respectively, which demonstrates the facile charge separation at the interface between perovskite and MoS₂. Furthermore, the contribution of back gate tuning is proved with a greatly reduced dark current. The results demonstrated here will open up a new field for the investigation of 2D perovskites for optoelectronic applications.     

Tunable Spin Characteristic Properties in Spin Valve Devices Based on Hybrid Organic–Inorganic Perovskites

The hybrid organic–inorganic perovskites (HOIPs) form a new class of semiconductors which show promising optoelectronic device applications. Remarkably, the optoelectronic properties of HOIP are tunable by changing the chemical components of their building blocks. Recently, the HOIP spintronic properties and their applications in spintronic devices have attracted substantial interest. Here the impact of the chemical component diversity in HOIPs on their spintronic properties is studied. Spin valve devices based on HOIPs with different organic cations and halogen atoms are fabricated. The spin diffusion length is obtained in the various HOIPs by measuring the giant magnetoresistance (GMR) response in spin valve devices with different perovskite interlayer thicknesses. In addition spin lifetime is also measured from the Hanle response. It is found that the spintronic properties of HOIPs are mainly determined by the halogen atoms, rather than the organic cations. The study provides a clear avenue for engineering spintronic devices based on HOIPs.     

High‐Performance Flexible Photodetectors based on High‐Quality Perovskite Thin Films by a Vapor–Solution Method

Organometal halide perovskites are new light‐harvesting materials for lightweight and flexible optoelectronic devices due to their excellent optoelectronic properties and low‐temperature process capability. However, the preparation of high‐quality perovskite films on flexible substrates has still been a great challenge to date. Here, a novel vapor–solution method is developed to achieve uniform and pinhole‐free organometal halide perovskite films on flexible indium tin oxide/poly(ethylene terephthalate) substrates. Based on the as‐prepared high‐quality perovskite thin films, high‐performance flexible photodetectors (PDs) are constructed, which display a nR value of 81 A W^?1 at a low working voltage of 1 V, three orders higher than that of previously reported flexible perovskite thin‐film PDs. In addition, these flexible PDs exhibit excellent flexural stability and durability under various bending situations with their optoelectronic performance well retained. This breakthrough on the growth of high‐quality perovskite thin films opens up a new avenue to develop high‐performance flexible optoelectronic devices.     

High‐Efficiency Solution‐Processed Inorganic Metal Halide Perovskite Light‐Emitting Diodes

This paper reports highly bright and efficient CsPbBr₃ perovskite light‐emitting diodes (PeLEDs) fabricated by simple one‐step spin‐coating of uniform CsPbBr₃ polycrystalline layers on a self‐organized buffer hole injection layer and stoichiometry‐controlled CsPbBr₃ precursor solutions with an optimized concentration. The PeLEDs have maximum current efficiency of 5.39 cd A^?1 and maximum luminance of 13752 cd m^?2. This paper also investigates the origin of current hysteresis, which can be ascribed to migration of Br^? anions. Temperature dependence of the electroluminescence (EL) spectrum is measured and the origins of decreased spectrum area, spectral blue‐shift, and linewidth broadening are analyzed systematically with the activation energies, and are related with Br^? anion migration, thermal dissociation of excitons, thermal expansion, and electron–phonon interaction. This work provides simple ways to improve the efficiency and brightness of all‐inorganic polycrystalline PeLEDs and improves understanding of temperature‐dependent ion migration and EL properties in inorganic PeLEDs.     

Polyoxometalate‐Based Organic–Inorganic Hybrids as Antitumor Drugs

Polyoxometalates (POMs) have shown encouraging antitumor activity. However, their cytotoxicity in normal cells and unspecific interactions with biomolecules are two major obstacles that impede the practical applications of POMs in clinical cancer treatment. Derivatization of POMs with more biocompatible organic ligands is expected to cause a synergetic effect and achieve improved bioactivity and biospecificity. Herein, the synthesis of an amphiphilic organic–inorganic hybrid is reported by grafting a long‐chain organoalkoxysilane lipid onto a POM. The amphiphilic POM hybrid could spontaneously assemble into the vesicles and exhibits enhanced antitumor activity for human colorectal cancer cell lines (HT29) compared to that of parent POMs. This detailed study reveals that the amphiphilic nature of POM hybrids enables the as‐formed vesicles to easily bind to the cell membranes and then be uptaken by the cells, thus leading to a substantial increase in antitumor activity. Such prominent antitumor action is mostly accomplished via cell apoptosis, which ultimately results in cell death. Our finding demonstrates that novel POM hybrids‐based drugs with increased bioactivity could be obtained by decorating POMs with selective organic ligands.     

Enhanced Electroluminescence from Organic Light‐Emitting Diodes with an Organic–Inorganic Perovskite Host Layer

The development of host materials with high performance is essential for fabrication of efficient and stable organic light‐emitting diodes (OLEDs). Although host materials used in OLEDs are typically organics, in this study, it is shown that the organic–inorganic perovskite CH₃NH₃PbCl₃ (MAPbCl₃) can be used as a host layer for OLEDs. Vacuum‐evaporated MAPbCl₃ films have a wide band gap of about 3 eV and very high and relatively balanced hole and electron mobilities, which are suitable for the host material. Photoluminescence and electroluminescence take place through energy transfer from MAPbCl₃ to an organic emitter in films. Incorporation of an MAPbCl₃ host layer into OLEDs leads to a reduction of driving voltage and enhancement of external quantum efficiency as compared to devices with a conventional organic host layer. Additionally, OLEDs with an MAPbCl₃ host layer demonstrate very good operational stability under continuous current operation. These results can be extensively applied to organic‐ and perovskite‐based optoelectronics.     

FA‐Assistant Iodide Coordination in Organic–Inorganic Wide‐Bandgap Perovskite with Mixed Halides

Mixed‐halide wide‐bandgap perovskites are key components for the development of high‐efficiency tandem structured devices. However, mixed‐halide perovskites usually suffer from phase‐impurity and high defect density issues, where the causes are still unclear. By using in situ photoluminescence (PL) spectroscopy, it is found that in methylammonium (MA⁺)‐based mixed‐halide perovskites, MAPb(I_0.6Br_0.4)₃, the halide composition of the spin‐coated perovskite films is preferentially dominated by the bromide ions (Br^?). Additional thermal energy is required to initiate the insertion of iodide ions (I^?) to achieve the stoichiometric balance. Notably, by incorporating a small amount of formamidinium ions (FA⁺) in the precursor solution, it can effectively facilitate the I^? coordination in the perovskite framework during the spin‐coating and improve the composition homogeneity of the initial small particles. The aggregation of these homogenous small particles is found to be essential to achieve uniform and high‐crystallinity perovskite film with high Br^? content. As a result, high‐quality MA_0.9FA_0.1Pb(I_0.6Br_0.4)₃ perovskite film with a bandgap (E_g) of 1.81 eV is achieved, along with an encouraging power‐conversion‐efficiency of 17.1% and open‐circuit voltage (V_oc) of 1.21 V. This work also demonstrates the in situ PL can provide a direct observation of the dynamic of ion coordination during the perovskite crystallization.     

Improving All‐Inorganic Perovskite Photodetectors by Preferred Orientation and Plasmonic Effect

All‐inorganic perovskites have high carrier mobility, long carrier diffusion length, excellent visible light absorption, and well overlapping with localized surface plasmon resonance (LSPR) of noble metal nanocrystals (NCs). The high‐performance photodetectors can be constructed by means of the intrinsic outstanding photoelectric properties, especially plasma coupling. Here, for the first time, inorganic perovskite photodetectors are demonstrated with synergetic effect of preferred‐orientation film and plasmonic with both high performance and solution process virtues, evidenced by 238% plasmonic enhancement factor and 10⁶ on/off ratio. The CsPbBr₃ and Au NC inks are assembled into high‐quality films by centrifugal‐casting and spin‐coating, respectively, which lead to the low cost and solution‐processed photodetectors. The remarkable near‐field enhancement effect induced by the coupling between Au LSPR and CsPbBr₃ photogenerated carriers is revealed by finite‐difference time‐domain simulations. The photodetector exhibits a light on/off ratio of more than 10⁶ under 532 nm laser illumination of 4.65 mW cm^?2. The photocurrent increases from 0.67 to 2.77 μA with centrifugal‐casting. Moreover, the photocurrent rises from 245.6 to 831.1 μA with Au NCs plasma enhancement, leading to an enhancement factor of 238%, which is the most optimal report among the LSPR‐enhanced photodetectors, to the best of our knowledge. The results of this study suggest that all‐inorganic perovskites are promising semiconductors for high‐performance solution‐processed photodetectors, which can be further enhanced by Au plasmonic effect, and hence have huge potentials in optical communication, safety monitoring, and biological sensing.