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.     

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.     

Reversible Transformation between CsPbBr3 Perovskite Nanowires and Nanorods with Polarized Optoelectronic Properties

CsPbX₃ (X = Cl, Br, I) perovskite nanowires and nanorods are important 1D and quasi 1D semiconductor nanomaterials. They have shown significant prospect in optic and optoelectronic applications, especially for their adaptability to flexible devices, good carrier transport performance, polarized absorption, and emission properties. Due to the high dependence of the property to the morphology, it is crucial to develop synthesis methods with continuous diameter and length tunability of the 1D/quasi 1D perovskites. In this report, a feasibly room temperature synthesis method was developed for ultrathin CsPbX₃(X = Cl, Br, I) perovskite nanowires. By aging the CsPbBr₃ nanowires (≈2*500 nm) under ambient condition with proper concentration and time, the nanowires are transformed to nanorods with controllable diameter and length. Reversibly, the nanorods can be transformed back to nanowires. Equilibrium mechanism is adopted to understand the morphology evolution, and hopefully could be generally applied to many other nano materials. The polarized optoelectronic properties of the nanowires and nanorods are interpreted by a model based on the two-channel anisotropies measurement. Polarized light detectors constructed by oriented assembled nanowires are fabricated to demonstrate their application potentials.     

Surface Ligands Stabilized Lead Halide Perovskite Quantum Dot Photocatalyst for Visible Light‐Driven Hydrogen Generation

Solar hydrogen conversion represents a clean and economic approach to addressing global energy and environmental issues, for which efficient photocatalysts are heavily pursued. Lead halide perovskites are promising candidates for efficient phtocatalysts in solar hydrogen generation due to their attractive properties in light absorption, photogenerated charge transportation, and utilization. However, photocatalytic applications of lead halide perovskites are limited owing to their poor stability in the presence of water or other polar solvent environment. This work presents the rational control of surface ligands in achieving a good balance between stability and photocatalytic activity of CsPbBr₃ quantum dots (QDs). Detailed studies reveal that the deliberate surface ligands engineering is crucial for maximizing the photocatalytic activity of CsPbBr₃ QDs while maintaining good QD stability. A certain amount of surface ligands protect the CsPbBr₃ QDs from decomposition in moisture during the photocatalytic reaction while still enabling efficient charge transfer for photocatalytic reactions on the surface of QDs. The well‐controlled CsPbBr₃ photocatalyst shows efficient visible light‐driven H₂ generation with outstanding stability (≥160 h).     

Centimeter-Sized Single Crystals of Two-Dimensional Hybrid Iodide Double Perovskite (4,4-Difluoropiperidinium)4AgBiI8 for High-Temperature Ferroelectricity and Efficient X-Ray Detection

Ferroelectricity and X-ray detection property have been recently implemented for the first time in hybrid bromide double perovskites. It sheds a light on achieving photosensitive and ferroelectric multifunctional materials based on 2D lead-free hybrid halide double perovskites. However, the low T_c, small P_s, and relatively low X-ray sensitivity in the reported bromide double perovskites hinder practical applications. Herein, the authors demonstrate a novel 2D lead-free iodide double perovskite (4,4-difluoropiperidinium)₄AgBiI₈ (1) for high-performance X-ray sensitive ferroelectric devices. Centimeter-sized single crystal of 1 is obtained and exhibits an excellent ferroelectricity including a high T_c up to 422 K and a large P_s of 10.5 μC cm⁻². Moreover, due to a large X-ray attenuation and efficient charge carrier mobility (μ)–charge carrier lifetime (τ) product, the crystal 1 also exhibits promising X-ray response with a high sensitivity up to 188 μC·Gy_air⁻¹ cm⁻² and a detection limit below 3.13 μGy_air·s⁻¹. Therefore, this finding is a step further toward practical applications of lead-free halide perovskite in high-performance photoelectronic devices. It will afford a promising platform for exploring novel photosensitive ferroelectric multifunctional materials based on lead-free double perovskites.     

Origin of high fill factor in polymer solar cells from semiconducting polymer with moderate charge carrier mobility

The fill factor of polymer bulk heterojunction solar cells (PSCs), which is mainly governed by the processes of charge carrier generation, recombination, transport and extraction, and the competition between them in the device, is one of the most important parameters that determine the power conversion efficiency of the device. We show that the fill factor of PSCs based on thieno[3,4-b]-thiophene/benzodithiophene (PTB7):[6,6]-phenyl C₇₁-butyric acid methylester (PC₇₁BM) blend that only have moderate carrier mobilities for hole and electron transport, can be enhanced to 76% by reducing the thickness of the photoactive layer. A drift–diffusion simulation study showed that reduced charge recombination loss is mainly responsible for the improvement of FF, as a result of manipulating spatial distribution of charge carrier in the photoactive layer. Furthermore, the reduction of the active layer thickness also leads to enhanced built-in electric field across the active layer, therefore can facilitate efficient charge carrier transport and extraction. Finally, the dependence of FF on charge carrier mobility and transport balance is also investigated theoretically, revealing that an ultrahigh FF of 80–82% is feasible if the charge mobility is high enough (∼10⁻³–10⁻¹ cm²/V s).     

Pure Blue Electroluminescence by Differentiated Ion Motion in a Single Layer Perovskite Device

Blue electroluminescence is highly desired for emerging light-emitting devices for display applications and optoelectronics in general. However, saturated, efficient, and stable blue emission has been challenging to achieve, particularly in mixed-halide perovskites, where intrinsic ion motion and halide segregation compromises spectral purity. Here, CsPbBr_3−xCl_x perovskites, polyelectrolytes, and a salt additive are leveraged to demonstrate pure blue emission from single-layer light-emitting electrochemical cells (LECs). The electrolytes transport the ions from salt additives, enhancing charge injection and stabilizing the inherent perovskite emissive lattice for highly pure and sustained blue emission. Substituting Cl into CsPbBr₃ tunes the perovskite luminescence from green through blue. Sky blue and saturated blue devices produce International Commission on Illumination coordinates of (0.105, 0.129) and (0.136, 0.068), respectively, with the latter meeting the US National Television Committee standard for the blue primary. Likewise, maximum luminances of 2900 and 1000 cd m⁻², external quantum efficiencies (EQEs) of 4.3% and 3.9%, and luminance half-lives of 5.7 and 4.9 h are obtained for sky blue and saturated blue devices, respectively. Polymer and LiPF₆ inclusion increases photoluminescence efficiency, suppresses halide segregation, induces thin-film smoothness and uniformity, and reduces crystallite size. Overall, these devices show superior performance among blue perovskite light-emitting diodes (PeLEDs) and general LECs.     

Double Charge Transfer Dominates in Carrier Localization in Low Bandgap Sites of Heterogeneous Lead Halide Perovskites

Heterogeneous organic-inorganic halide perovskites possess inherent non-uniformities in bandgap that are sometimes engineered and exploited on purpose, like in quasi-2D perovskites. In these systems, charge carrier and excitation energy migration to lower-bandgap sites are key processes governing luminescence. The question, which of them dominates in particular materials and under specific experimental conditions, still remains unanswered, especially when charge carriers comprise excitons. In this study transient absorption (TA) and transient photoluminescence (PL) techniques are combined to address the excited state dynamics in quasi-2D and other heterogeneous perovskite structures in broad temperature range, from room temperature down to 15 K. The data provide clear evidence that charge carrier transfer rather than energy migration dominates in heterogeneous quasi-2D perovskite films.     

In Situ Embedding Synthesis of Highly Stable CsPbBr3/CsPb2Br5@PbBr(OH) Nano/Microspheres through Water Assisted Strategy

The disappointing stability of perovskites, especially in water, remains a key issue hindering their further commercialization. Here, CsPbBr₃/CsPb₂Br₅@PbBr(OH) (PQDs@PbBr(OH)) nano/microspheres with superior stability and outstanding photoluminescence quantum yield (PLQY, ≈98%) are fabricated through a water-assisted process. The nano/microspheres can maintain excellent photoluminescence (PL) intensity and high PLQY (≈90%) when immersed in water for more than 18 months. By changing the water content in the reaction mixture, the phase, particle size, and PL peaks of the nano/microspheres will change. Compared with CsPbBr₃/Cs₄PbBr₆ nanocrystals synthesized without water, PQDs@PbBr(OH) nano/microspheres exhibit better thermal stability, photostability, and superior stability in water. Based on the first-principles calculations, the enhanced stability results from PbBr(OH) with high decomposition enthalpy in water, which can effectively prevent water from contacting PQDs embedded in it. Moreover, white light-emitting diodes are fabricated by mixing green-emitting PQDs@PbBr(OH) powder and K₂SiF₆:Mn⁴⁺ (KSF) red phosphor on a 460 nm blue chip and the device shows a high luminous efficacy of 101.27 lm W⁻¹ at 10 mA. This work not only provides a reliable method for the facile preparation of ultrastable perovskites, but also has great potentials for future practical applications.     

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.     

Recycling Lead (II) Management in Metal Organic Framework-Perovskite Luminescent Composites

Colloidal lead halide perovskites face challenges in practical optoelectronic applications due to the toxicity of lead (II). To overcome this issue, a novel approach using metal-organic frameworks (MOFs) for recycling lead (II) management in perovskite materials, is developed. Through surface-functionalization of MOF-808 and pH tuning, the MOF achieves recyclable adsorption-desorption of lead (II), confining the lead source within the MOF-808 template or the perovskites. This controllable transformation between lead (II) chelation and perovskites prevents lead (II) leakage. Additionally, separated lead (II) ions from decomposed perovskite can be adsorbed by MOF-808, facilitating recycling. The resulting MOF-808-EDTA@CsPbBr₃ composite exhibits comparable optical performance to pure CsPbBr₃ powder, but with improved stabilities, effectively preventing lead (II) leakage. Hierarchical desorption of lead (II) in the MOF-808-EDTA@Pb²⁺ complex enables reversible on/off fluorescence signal switching. Detached lead (II) from decomposed MOF-808-EDTA@CsPbBr₃ composite can be re-adsorbed by MOF-808-EDTA, enabling the construction of CsPbBr₃ nanocrystals in a new cycle. This approach is economically attractive and environmentally friendly. This study addresses the challenge of lead (II) leakage and offers the potential for optical anti-counterfeiting in perovskite materials with a sustainable approach.     

Synthesis and Room‐Temperature Ultraviolet Photoluminescence Properties of Zirconia Nanowires

This paper reports the synthesis of tetragonal zirconia nanowires using template method. An as‐prepared sample was characterized by scanning and transmission electron microscopy. It was found that the as‐prepared materials were tetragonal zirconia nanowires with average diameters of ca. 80 nm and length of over 10 μm. The Raman spectrum showed peaks at 120, 461, and 629 cm^–1, which are attributed to the E_g, E_g, and B_1g phonon modes of the tetragonal zirconia structure, respectively. The UV‐vis absorption spectrum showed an absorption peak at 232.5 nm (5.33 eV in photon energy). Photoluminescence (PL) spectra of zirconia nanowires showed a strong emission peak at ca. 388 nm at room temperature, which is attributed to the ionized oxygen vacancy in the zirconia nanowires system.     

Amplifying Surface Energy Difference toward Anisotropic Growth of All-Inorganic Perovskite Single-Crystal Wires for Highly Sensitive Photodetector

It is a great challenge to directly grow super long all-inorganic perovskite monocrystalline wires due to the weak surface energy difference among the low index facets. Here, a one-pot solution process to grow the aspect ratio over 10⁵ of monocrystalline CsPbBr₃ perovskite wires (PWs) and yield up to 70% is reported. A chemical potential dependent surface energy difference amplification strategy is proposed to regulate the surface energy of growing and grown surfaces accordingly to the anisotropic growth of CsPbBr₃. The anisotropic growth of wires is derived from the regulation of anti-solvent diffusion kinetic and the mass transfer kinetic control of the metal halide salts. This experiment demonstrates a 50 times amplification of surface energy difference. As-produced PWs present a high photodetection responsivity up to 4923 A W⁻¹, external quantum efficiency exceeding 13 784%, and detectivity over 3.6 × 10¹³ Jones. This work not only reveals the mechanism of surface energy dominated anisotropic growth for CsPbBr₃ PWs, but also elucidates the important role of kinetics regulation during the growth process, which may open a new window for the low-dimensional crystal growth of ionic compounds.     

J-Type Self-Assembled Supramolecular Polymers for High-Performance and Fast-Response n-Type Organic Electrochemical Transistors

To date, high-performance organic electrochemical transistors (OECTs) are almost all based on conjugated polymers. Small molecules can be synthesized with high purity without batch-to-batch variations. However, small molecules require highly crystalline films and good molecular packings to achieve high charge carrier mobilities. Such features make their films unsuitable for ion diffusion or make their molecular packing distorted due to ion diffusion, resulting in poor ion/charge carrier transport properties and slow response speed. Herein, it is proposed to construct small-molecule-based supramolecular polymers to address these issues. A molecule, namely TDPP-RD-G7 is designed, which exhibits J-type self-assembling behaviors and can form supramolecular polymers in solution and conjugated-polymer-like networks in solid state. More importantly, the porous supramolecular polymer networks allow fast ion diffusion and greatly increase the device response speeds. As a result, the TDPP-RD-G7 exhibits record fast response speeds (τ_on/τ_off) of 10.5/0.32 ms with high figure-of-merit (µC*) of 5.88 F cm⁻¹ V⁻¹ s⁻¹ in small-molecule OECTs. This work reveals the possible reasons that hinder the response speeds in small-molecule OECTs and demonstrates a new “supramolecular polymer” approach to high-performance and fast-response small-molecule-based OECTs.     

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.     

First-Principles Optimization of Out-of-Plane Charge Transport in Dion–Jacobson CsPbI3 Perovskites with π-Conjugated Aromatic Spacers

Quasi-2D CsPbI₃ perovskites have emerged as excellent candidates for advanced photovoltaic technologies due to their fundamentally enhanced stability than conventional 3D counterparts. However, the applications of quasi-2D perovskites are plagued with their poor out-of-plane carrier mobility induced by the intercalated insulating organic layers. In this work, a new strategy is explored to significantly enhance the out-of-plane charge transport in quasi-2D Dion–Jacobson (DJ) CsPbI₃ perovskites via leveraging the intercalation of aromatic diamine cations (p-phenylenediamine, PPDA) with unique π-conjugated bond based on the first-principles calculations. The strong interactions between PPDA²⁺ cations and inorganic Pb-I framework (i.e., I–I interaction, p-π coupling, and H-bonds) provide three carrier pathways to facilitate the out-of-plane charge transport. Furthermore, the restricted in-plane and out-of-plane structural distortion induced by the π-conjugated bond could improve the electronic coupling and charge mobility along the out-of-plane direction with reduced bandgaps. As a proof of concept, the calculated average photovoltaic conversion efficiency of such engineered DJ CsPbI₃ perovskite solar cells is ≈17%, which is very close to the certificated champion efficiency of 3D α-CsPbI₃, underscoring their potential for solar cell applications.     

Centimeter-Sized Molecular Perovskite Crystal for Efficient X-Ray Detection

Molecular perovskites have demonstrated great potential for ferroelectrics and nonlinear optics; however, their charge transport properties for optoelectronics have rarely been explored. Here, understanding of charge transport behavior of molecular perovskite under X-ray excitation based on centimeter-scale TMCM-CdCl₃ (TMCM⁺, trimethylchloromethyl ammonium) single crystal is demonstrated. The crystal is fabricated from an aqueous solution and exhibits a large bandgap of 5.51 eV, with the valence band maximum mainly dominated by the Cl-p/Cd-d states and the conduction band minimum primarily by Cd-s/Cl-p states. Charge mobility exceeding 40 cm² V⁻¹ s⁻¹ and mobility–lifetime (µτ) product on the order of 10⁻⁴ cm² V⁻¹ for the crystal are observed. These excellent optoelectronic properties translate to an efficient photoresponse under X-ray excitation, with the sensitivity reaching 128.9 ± 4.64 µC Gy_air⁻¹ cm⁻² [fivefold higher than that of the commercialized amorphous selenium (α-Se)] and a low detection limit of 1.06 μC Gy_air⁻¹ s⁻¹ (10 V bias). This work pioneers a superior metal-based molecular perovskite single-crystal based paradigm for optoelectronic investigation, which may lead to the discovery of a new generation of X-ray detection and imaging materials.     

Enhanced performance of inverted CsPbBr3 nanocrystal LEDs via Zn(II) doping

Perovskite lighting-emitting diodes (PeLEDs) with inverted structure have been considered as promising display technology due to their suitable driving schemes with n-type thin-film transistors. However, the defects and imbalanced charge carriers in the CsPbBr₃ nanocrystal (NC) PeLED are key hurdles, limiting the performance. Herein, we have successfully doped Zn²⁺ ions into CsPbBr₃ NCs by ligand-assisted reprecipitation method, exhibiting an 85% enhancement of the photoluminescence quantum yield (PLQY). In addition, the optimized energy level alignment via Zn doping facilitates the carrier balance in the devices, improving the efficiencies. The obtained CsPbBr₃:Zn-based PeLED reaches a high luminance of 3124 cd/m² and a maximum external quantum efficiency (EQE) of 0.85%, which are superior to those of CsPbBr₃-based PeLED (luminance = 564 cd/m², EQE = 0.09%). The results demonstrate that Zn doping significantly enhances the performance of PeLED, which increases the potential of these inverted PeLEDs connected with n-type TFTs towards practical applications.     

Delocalized Electron Accumulation at Nanorod Tips: Origin of Efficient H2 Generation

Photocatalytic hydrogen (H₂) evolution requires efficient electron transfer to catalytically active sites in competition with charge recombination. Thus, controlling charge‐carrier dynamics in the photocatalytic H₂ evolution process is essential for optimized photocatalyst nanostructures. Here, the efficient delocalization of electrons is demonstrated in a heterostructure consisting of optimized MoS₂ tips and CdS nanorods (M‐t‐CdS Nrs) synthesized by amine‐assisted oriented attachment. The heterostructure achieves photocatalytic H₂ activity of 8.44 mmol h^?1 g^?1 with excellent long‐term durability (>23 h) without additional passivation under simulated solar light (AM 1.5, 100 mW cm^?2). This activity is nearly two orders of magnitude higher than that of pure CdS Nrs. The impressive photocatalytic H₂ activity of M‐t‐CdS Nrs reflects favorable charge‐carrier dynamics, as determined by steady‐state PL and time‐correlated single photon counting correlation analysis at low temperature. The MoS₂ cocatalysts precisely located at the end of the CdS Nrs exhibit ultrafast charge transfer and slow charge recombination via spatially localized deeper energy states, resulting in a highly efficient H₂ evolution reaction in lactic acid containing an electrolyte.     

2D Derivative Phase Induced Growth of 3D All Inorganic Perovskite Micro–Nanowire Array Based Photodetectors

A large number of derivative phases in inorganic perovskites are reported with special structures and extraordinary performances in photoelectronic device applications. The reverse phase transition between derivative phases and perovskites usually induces recrystallization or forms mixed components. In this work, derivative phase‐induced growth of the CsPbBr₃ micro–nanowire (MW) array by utilizing phase transition of the 2D CsPb₂Br₅ phase is reported. Owing to its layered structure and phase transition, annealing of CsPb₂Br₅ at a temperature of 550 °C combined with solvent quenching leads to a templating effect to form a high‐quality CsBr MW array. Subsequent PbBr₂ deposition and the second annealing are employed to form aligned CsPbBr₃ MW arrays. Based on this method, a CsPbBr₃ MW array‐based photodetector is fabricated. The large grain size, less grain boundaries, and lower surface potential of the CsPbBr₃ MW array lead to high device performance with a responsivity of 7.66 A W^?1, a detectivity of ≈10¹² Jones, and long‐term operational stability over 1900 min.