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.     

Improved Performance and Stability of All‐Inorganic Perovskite Light‐Emitting Diodes by Antisolvent Vapor Treatment

All‐inorganic perovskite light‐emitting diodes (LEDs) reveal efficient luminescence with high color purity, but their modest brightness and poor stability are still critical drawbacks. Here, the luminescent efficiency and the stability of perovskite LEDs (PeLEDs) are boosted by antisolvent vapor treatment of CsPbBr₃ embedded in a dielectric polymer matrix of polyethylene oxide (PEO). A unique method is developed to obtain high quality CsPbBr₃ emitting layers with low defects by controlling their grain sizes. CsPbBr₃ in PEO matrix is post‐treated with antisolvent of chloroform (CF), leading to microcrystals with a size of ≈5 µm along the in‐plane direction with active emitting composite of 90%. A device based on CF post‐treatment (CsPbBr₃‐PEO‐CF) film displays a brightness of up to 51890 cd m^?2 with an external quantum efficiency of 4.76%. CsPbBr₃‐PEO‐CF PeLED still maintains 82% of its initial efficiency after 80 h continuous operation in ambient air, which indicates relatively good device stability. This work highlights that film quality is not only key to promoting fluorescence in CsPbBr₃, but also to achieving higher performance PeLEDs.     

Multifunctional Optoelectronic Device Based on an Asymmetric Active Layer Structure

A single device with a variety of capabilities is highly attractive for the increasing demands of complex and multifunctional optoelectronics. A hybrid heterojunction formed between CsPbBr₃ halide perovskite and chalcogenide quantum dots is demonstrated. The heterojunction served as an asymmetric active layer allows not only charge separation/exciton dissociation in a benign process, but also carrier injection/recombination with the suppression of bulk and interfacial nonradiative recombination. An individual device incorporating such a heterojunction is therefore implemented with an integration of proof‐of‐concept functions, including a voltage controllable multicolor light‐emitting diode, an exceptionally high photovoltage energy‐harvesting device, and an ultrafast photosensitive detector. The figures of merit of the light‐emitting diode remarkably surpass those of the corresponding single‐active‐layer device, particularly in terms of its bright electroluminescence and superior long‐term stability. The asymmetric active layer concept provides a feasible route to design efficient multifunctional and monofunctional devices in the future.     

Facile method for the preparation of high-performance photodetectors with a GQDs/perovskite bilayer heterostructure

A high-performance nitrogen doped graphene quantum dots (GQDs)/all-inorganic (CsPbBr₃) perovskite nanocrystals (NCs) heterostructure photodetector was fabricated on a quartz substrate, using the low cost spin coating technique followed by hot plate annealing. The GQDs/CsPbBr₃ NCs heterostructure photodetector exhibits a high overall performance with a photoresponsivity of 0.24 AW⁻¹, on/off ratio of 7.2 × 10⁴, and specific detectivity of up to 2.5 × 10¹² Jones. The on/off ratio of the hybrid device was improved by almost ten orders of magnitude, and the photoresponsivity was enhanced almost three times compared to the single layer perovskite NCs photodetector. The performance enhancement of the hybrid device was due to its highly efficient carrier separation at the GQDs/CsPbBr₃ NCs interface. This results from the coupling of the GQDs layer, which efficiently extracts and transports the photogenerated carriers, with the CsPbBr₃ NCs layer, which has a large absorption coefficient and high quantum efficiency. The interfacial charge transfer from the CsPbBr₃ NCs to the GQDs layer was demonstrated by the quenching in the photoluminescence (PL) spectra, and the fast-average decay time in the time-resolved photoluminescence (Trpl) spectra of the hybrid photodetector. Moreover, the performance-enhancement mechanism of the hybrid GQDs/CsPbBr₃ photodetector was elucidated by analyzing the band alignment of the GQDs and CsPbBr₃ under laser illumination.     

Localized Surface Plasmon Enhanced All‐Inorganic Perovskite Quantum Dot Light‐Emitting Diodes Based on Coaxial Core/Shell Heterojunction Architecture

This work presents a strategy of combining the concepts of localized surface plasmons (LSPs) and core/shell nanostructure configuration in a single perovskite light‐emitting diode (PeLED) to addresses simultaneously the emission efficiency and stability issues facing current PeLEDs' challenges. Wide bandgap n‐ZnO nanowires and p‐NiO are employed as the carrier injectors, and also the bottom/upper protection layers to construct coaxial core/shell heterostructured CsPbBr₃ quantum dots LEDs. Through embedding plasmonic Au nanoparticles into the device and thickness optimization of the MgZnO spacer layer, an emission enhancement ratio of 1.55 is achieved. The best‐performing plasmonic PeLED reaches up a luminance of 10 206 cd m^?2, an external quantum efficiency of ≈4.626%, and a current efficiency of 8.736 cd A^?1. The underlying mechanisms for electroluminescence enhancement are associated with the increased spontaneous emission rate and improved internal quantum efficiency induced by exciton–LSP coupling. More importantly, the proposed PeLEDs, even without encapsulation, present a substantially improved operation stability against water and oxygen degradation (30‐day storage in air ambient, 85% humidity) compared with any previous reports. It is believed that the experimental results obtained will provide an effective strategy to enhance the performance of PeLEDs, which may push forward the application of such kind of LEDs.     

All-Inorganic CsPbBr3 Perovskite Nanocrystals/2D Non-Layered Cadmium Sulfide Selenide for High-Performance Photodetectors by Energy Band Alignment Engineering

Perovskites have attracted intensive attention as promising materials for the application in various optoelectronic devices due to their large light absorption coefficient, high carrier mobility, and long charge carrier diffusion length. However, the performance of the pure perovskite nanocrystals-based device is extremely restricted by the limited charge transport capability due to the existence of a large number of the grain boundary between perovskite nanocrystals. To address these issues, a high-performance photodetector based on all-inorganic CsPbBr₃ perovskite nanocrystals/2D non-layered cadmium sulfide selenide heterostructure has been demonstrated through energy band engineering with designed typed-II heterostructure. The photodetector exhibits an ultra-high light-to-dark current ratio of 1.36 × 10⁵, a high responsivity of 2.89 × 10² A W⁻¹, a large detectivity of 1.28 × 10¹⁴ Jones, and the response/recovery time of 0.53s/0.62 s. The enhancement of the optoelectronic performance of the heterostructure photodetector is mainly attributed to the efficient charge carrier transfer ability between the all-inorganic CsPbBr₃ perovskites and 2D cadmium sulfide selenide resulting from energy band alignment engineering. The charge carriers’ transfer dynamics and the mechanism of the CsPbBr₃ perovskites/2D non-layered nanosheets interfaces have also been studied by state-state PL spectra, fluorescence lifetime imaging microscopy, time-resolved photoluminescence spectroscopy, and Kelvin probe force microscopy measurements.     

Reduced Efficiency Roll‐Off and Improved Stability of Mixed 2D/3D Perovskite Light Emitting Diodes by Balancing Charge Injection

Perovskite light emitting diodes (PeLEDs) have reached external quantum efficiencies (EQEs) over 21%. Their EQE, however, drops at increasing current densities (J) and their lifetime is still limited to just a few hours. The mechanisms leading to EQE roll‐off and device instability require thorough investigation. Here, improvement in EQE, EQE roll‐off, and lifetime of PeLEDs is demonstrated by tuning the balance of electron/hole transport into a mixed 2D/3D perovskite emissive layer. The mixed 2D/3D perovskite layer induces exciton confinement and beneficially influences the electron/hole distribution inside the perovskite layer. By tuning the electron injection to match the hole injection in such active layer, a nearly flat EQE for J = 0.1–200 mA cm^?2, a reduced EQE roll‐off until J = 250 mA cm^?2, and a half‐lifetime of ≈47 h at J = 10 mA cm^?2 is reached. A model is also proposed to explain these improvements that account for the spatial electron/hole distributions.     

Quasi‐2D Inorganic CsPbBr3 Perovskite for Efficient and Stable Light‐Emitting Diodes

Metal halide perovskites are rising as a competitive material for next‐generation light‐emitting diodes (LEDs). However, the development of perovskite LEDs is impeded by their fast carriers diffusion and poor stability in bias condition. Herein, quasi‐2D CsPbBr₃ quantum wells homogeneously surrounded by inorganic crystalline Cs₄PbBr₆ of large bandgap are grown. The centralization of carriers in nanoregion facilitates radiative recombination and brings much enhanced luminescence quantum yield. The external quantum efficiency and luminescence intensity of the LEDs based on this nanocomposite are one order of magnitude higher than the conventional low‐dimensional perovskite. Meanwhile, the use of inorganic nanocomposite materials brings much improved device operation lifetime under constant electrical field.     

Core/Shell Perovskite Nanocrystals: Synthesis of Highly Efficient and Environmentally Stable FAPbBr3/CsPbBr3 for LED Applications

Lead halide perovskite nanocrystals (PeNCs) are promising materials for applications in optoelectronics. However, their environmental instability remains to be addressed to enable their advancement into industry. Here the development of a novel synthesis method is reported for monodispersed PeNCs coated with all inorganic shell of cesium lead bromide (CsPbBr₃) grown epitaxially on the surface of formamidinium lead bromide (FAPbBr₃) NCs. The formed FAPbBr₃/CsPbBr₃ NCs have photoluminescence in the visible range 460–560 nm with narrow emission linewidth (20 nm) and high optical quantum yield, photoluminescence quantum yield (PLQY) up to 93%. The core/shell perovskites have enhanced optical stability under ambient conditions (70 d) and under ultraviolet radiation (50 h). The enhanced properties are attributed to overgrowth of FAPbBr₃ with all‐inorganic CsPbBr₃ shell, which acts as a protective layer and enables effective passivation of the surface defects. The use of these green‐emitting core/shell FAPbBr₃/CsPbBr₃ NCs is demonstrated in light‐emitting diodes (LEDs) and significant enhancement of their performance is achieved compared to core only FAPbBr₃‐LEDs. The maximum current efficiency observed in core/shell NC LED is 19.75 cd A^‐1 and the external quantum efficiency of 8.1%, which are approximately four times and approximately eight times higher, respectively, compared to core‐only devices.     

Self‐Powered UV–Vis–NIR Photodetector Based on Conjugated‐Polymer/CsPbBr3 Nanowire Array

Perovskite photodetectors have attracted intensive research interest due to promising applications in sensing, communication, and imaging. However, their performance is restricted by the narrow spectrum range, required power source, and instability in ambient environment. To address these issues, a self‐powered photodetector based on the inorganic CsPbBr₃ perovskite nanowire array/conjugated‐polymer hybrid structure is designed. The spectra response range of the device can be extended to 950 nm, along with outstanding stability, fast response speed (111/306 µs), and large detectivity (1.2 × 10¹³ Jones). The performance parameters are comparable to or even better than most reported CsPbBr₃ and conjugated‐polymer photodetectors. The excellent performance is mainly attributed to the efficient carrier generation, separation, and transport resulting from array structure and favorable band structure.     

Water-Stable CsPbBr3/Reduced Graphene Oxide Nanoscrolls for High-Performance Photoelectrochemical Sensing

Perovskite quantum dots (PQDs) have attracted much attention in the field of photoelectrochemical (PEC) sensors owing to their superb optical properties and efficient charge transport, but the inherent poor stability severely hinders their PEC applications. Herein, hydrolysis-resistant CsPbBr₃/reduced graphene oxide nanoscrolls (CsPbBr₃/rGO NSs) are obtained by solvent-assisted self-rolling process toward water-stable PEC sensors. CsPbBr₃ QDs embedded in rGO nanosheets can be prevented from water since the multilayer rGO shell layers, which maintains excellent optical properties. On account of strong interfacial interactions, rGO nanosheets are crimped spontaneously with CsPbBr₃ QDs, which offer access to superb structural and long-term storage stability. Moreover, appropriate band alignment and ultrafast interfacial carrier transfer enable CsPbBr₃/rGO NSs to exhibit greatly enhanced anode photocurrent response for subsequent PEC sensing. As a demonstration, the molecular imprinted PEC sensors for two kinds of mycotoxins (aflatoxin B1 or ochratoxin A) presents an ultra-high sensitivity and good anti-interference ability. Significantly, this work provides an inspirable and convenient route for hydrolysis-resistant PQDs-based optoelectronic and photoelectrocatalytic applications in aqueous ambience.     

High‐Throughput Combinatorial Optimizations of Perovskite Light‐Emitting Diodes Based on All‐Vacuum Deposition

Light‐emitting diodes (LEDs) based on lead halide perovskites demonstrate outstanding optoelectronic properties and are strong competitors for display and lighting applications. While previous halide perovskite LEDs are mainly produced via solution processing, here an all‐vacuum processing method is employed to construct CsPbBr₃ LEDs because vacuum processing exhibits high reliability and easy integration with existing OLED facilities for mass production. The high‐throughput combinatorial strategies are further adopted to study perovskite composition, annealing temperature, and functional layer thickness, thus significantly speeding up the optimization process. The best rigid device shows a current efficiency (CE) of 4.8 cd A^?1 (EQE of 1.45%) at 2358 cd m^?2, and best flexible device shows a CE of 4.16 cd A^?1 (EQE of 1.37%) at 2012 cd m^?2 with good bending tolerance. Moreover, by choosing NiO_x as the hole‐injection layer, the CE is improved to 10.15 cd A^?1 and EQE is improved to a record of 3.26% for perovskite LEDs produced by vacuum deposition. The time efficient combinatorial approaches can also be applied to optimize other perovskite LEDs.     

Deconvoluting Energy Transport Mechanisms in Metal Halide Perovskites Using CsPbBr3 Nanowires as a Model System

Understanding energy transport in metal halide perovskites is essential to effectively guide further optimization of materials and device designs. However, difficulties to disentangle charge carrier diffusion, photon recycling, and photon transport have led to contradicting reports and uncertainty regarding which mechanism dominates. In this study, monocrystalline CsPbBr₃ nanowires serve as 1D model systems to help unravel the respective contribution of energy transport processes in metal-halide perovskites. Spatially, temporally, and spectrally resolved photoluminescence (PL) microscopy reveals characteristic signatures of each transport mechanism from which a robust model describing the PL signal accounting for carrier diffusion, photon propagation, and photon recycling is developed. For the investigated CsPbBr₃ nanowires, an ambipolar carrier mobility of μ = 35 cm² V⁻¹ s⁻¹ is determined, and is found that charge carrier diffusion dominates the energy transport process over photon recycling. Moreover, the general applicability of the developed model is demonstrated on different perovskite compounds by applying it to data provided in previous related reports, from which clarity is gained as to why conflicting reports exist. These findings, therefore, serve as a useful tool to assist future studies aimed at characterizing energy transport mechanisms in semiconductor nanowires using PL.     

Band‐Edge Exciton Fine Structure and Exciton Recombination Dynamics in Single Crystals of Layered Hybrid Perovskites

2D perovskite materials have recently reattracted intense research interest for applications in photovoltaics and optoelectronics. As a consequence of the dielectric and quantum confinement effect, they show strongly bound and stable excitons at room temperature. Here, the band‐edge exciton fine structure and in particular its exciton and biexciton dynamics in high quality crystals of (PEA)₂PbI₄ are investigated. A comparison of bulk and surface exciton lifetimes yields a room temperature surface recombination velocity of 2 × 10³ cm s^?1 and an intrinsic lifetime of 185 ns. Biexciton emission is evidenced at room temperature, with a binding energy of ≈45 meV and a lifetime of 80 ps. At low temperature, exciton state splitting is observed, which is caused by the electron–hole exchange interaction. Transient photoluminescence resolves the low‐lying dark exciton state, with a bright/dark splitting energy estimated to be 10 meV. This work contributes to the understanding of the complex scenario of the elementary photoexcitations in 2D perovskites.     

Dual-Phase Stabilized Perovskite Nanowires for Reduced Defects and Longer Carrier Lifetime

1D perovskite materials are of significant interest to build a new class of nanostructures for electronic and optoelectronic applications. However, the study of colloidal perovskite nanowires (PNWs) lags far behind those of other established perovskite materials such as perovskite quantum dots and perovskite thin films. Herein, a dual-phase passivation strategy to synthesize all-inorganic PNWs with minimized surface defects is reported. The local phase transition from CsPbBr₃ to CsPb₂Br₅ in PNWs increases the photoluminescence quantum yield, carrier lifetime, and water-resistivity, owing to the energetic and chemical passivation effect. In addition, these dual-phase PNWs are employed as an interfacial layer in perovskite solar cells (PSCs). The enhanced surface passivation results in an efficient carrier transfer in PSCs, which is a critical enabler to increase the power conversion efficiency (PCE) to 22.87%, while the device without PNWs exhibits a PCE of 20.74%. The proposed strategy provides a surface passivation platform in 1D perovskites, which can lead to the development of novel nanostructures for future optoelectronic devices.     

Enhanced Optical Properties and Stability of CsPbBr3 Nanocrystals Through Nickel Doping

To improve the quantum efficiency and stability of perovskite quantum dots, the structural and optical properties are optimized by varying the concentration of Ni doping in CsPbBr₃ perovskite nanocrystals (PNCs). As Ni doping is gradually added, a blue shift is observed at the photoluminescence (PL) spectra. Ni-doped PNCs exhibit stronger light emission, higher quantum efficiency, and longer lifetimes than undoped PNCs. The doped divalent element acts as a defect in the perovskite structure, reducing the recombination rate of electrons and holes. A stability test is used to assess the susceptibility of the perovskite to light and moisture. For ultra-violet light irradiation, the PL intensity of undoped PNCs decreases by 70%, whereas that of Ni-doped PNCs decreases by 18%. In the water addition experiment, the PL intensity of Ni-doped PNCs is three times that of undoped PNCs. For CsPbBr₃ and Ni:CsPbBr₃ PNCs, a light emitting diode is fabricated by spin-coating. The efficiency of Ni:CsPbBr₃ exceeds that of CsPbBr₃ PNCs, and the results significantly differ based on the ratio. A maximum luminance of 833 cd m^–2 is obtained at optimum efficiency (0.3 cd A^–1). Therefore, Ni-doped PNCs are expected to contribute to future performance improvements in display devices.     

Direct Growth of Pyramid‐Textured Perovskite Single Crystals: A New Strategy for Enhanced Optoelectronic Performance

Even though there have been a few reports of substrate surface texturing of thin film perovskite solar cells to enhance their light trapping, there has been no direct texturing of the perovskite material, let alone perovskite single crystals (SCs). Herein, a method to prepare a pyramid‐structured perovskite CH₃NH₃PbX₃ (CH₃NH₃⁺ = MA, X = I, Br) SC surface with minimized light reflection and maximized incident light harvesting is reported. Specifically, a hard template is used to directly transfer the pyramidal texture onto the MAPbX₃ SC during its growth. A well‐shaped pyramidal texture is formed on the single‐crystal surface leading to improved light trapping. The textured MAPbBr₃ SC shows good crystallinity, prolonged carrier lifetime, and improved carrier mobility. Furthermore, the photodetector made from the textured SC shows enhanced responsivity of 321 A W^?1 and external quantum efficiency of 7191%, about two times higher than that of a control device. This method may be used to directly fabricate desired textures on general single crystal surfaces.     

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.     

Layered Ruddlesden–Popper Efficient Perovskite Solar Cells with Controlled Quantum and Dielectric Confinement Introduced via Doping

Layered Ruddlesden–Popper (RP) hybrid perovskite semiconductors have recently emerged as promising materials for photovoltaics application. However, the strong quantum and dielectric confinement of RP perovskite compounds increases their optical bandgap and binding energy of exciton, which limit their application in solar cells. Herein, the doping of RP‐based (BA)₂(MA)₃Pb₄I₁₃ perovskite materials by means of Li⁺ is reported for the first time, which can significantly help to reduce dielectric confinement and thus the exciton‐binding energy via reducing the dielectric constant difference between organic spacer cation and inorganic framework. Furthermore, the Li⁺ doping boosts the carrier mobility, reduces the trap density states, and thus allows to achieve power conversion efficiency of ≈15% via Li⁺‐(BA)₂(MA)₃Pb₄I₁₃‐based perovskite solar cell, which is the highest efficiency for layered perovskites (n = 4) so far. This work highlights the promising ionic doping engineering for further improvement of the layered perovskite materials.     

High‐Performance Flexible Broadband Photodetector Based on Organolead Halide Perovskite

Organolead halide perovskites have attracted extensive attentions as light harvesting materials for solar cells recently, because of its high charge‐carrier mobilities, high photoconversion efficiencies, low energy cost, ease of deposition, and so on. Herein, with CH₃NH₃PbI₃ film deposited on flexible ITO coated substrate, the first organolead halide perovskite based broadband photodetector is demonstrated. The organolead halide perovskite photodetector is sensitive to a broadband wavelength from the ultraviolet light to entire visible light, showing a photo‐responsivity of 3.49 A W^?1, 0.0367 A W^?1, an external quantum efficiency of 1.19×10³%, 5.84% at 365 nm and 780 nm with a voltage bias of 3 V, respectively. Additionally, the as‐fabricated photodetector exhibit excellent flexibility and robustness with no obvious variation of photocurrent after bending for several times. The organolead halide perovskite photodetector with high sensitivity, high speed and broad spectrum photoresponse is promising for further practical applications. And this platform creates new opportunities for the development of low‐cost, solution‐processed and high‐efficiency photodetectors.