Double Perovskite Single Crystals with High Laser Irradiation Stability for Solid-State Laser Lighting and Anti-counterfeiting.

Laser lighting devices, comprising an ultraviolet (UV) laser chip and a phosphor material, have emerged as a highly efficient approach for generating high-brightness light sources. However, the high power density of laser excitation may exacerbate thermal quenching in conventional polycrystalline or amorphous phosphors, leading to luminous saturation and the eventual failure of the device. Here, for the first time, we raise a single-crystal (SCs) material for laser lighting considering the absence of grain boundaries that scatter electrons and phonons, achieving high thermal conductivity (0.81 W m-1 K-1) and heat-resistance (575 °C). The SCs products exhibit a high photoluminescence quantum yield (89%) as well as excellent stability toward high-power lasers (>12.41 kW/cm2), superior to all previously reported amorphous or polycrystalline matrices. Finally, the laser lighting device was fabricated by assembling the SC with a UV laser chip (50 mW), and the device can maintain its performance even after continuous operation for 4 h. Double perovskite single crystals doped with Yb3+/Er3+ demonstrated multimodal luminescence with the irradiation of 355 and 980 nm lasers, respectively. This characteristic holds significant promise for applications in spectrally tunable laser lighting and multimodal anticounterfeiting.

Stereo-Hindrance Engineering of A Cation toward <110>-Oriented 2D Perovskite with Minimized Tilting and High-Performance X-Ray Detection.

2D <100>-oriented Dion-Jacobson or Ruddlesden-Popper perovskites are widely recognized as promising candidates for optoelectronic applications. However, the large interlayer spacing significantly hinders the carrier transport. <110>-oriented 2D perovskites naturally exhibit reduced interlayer spacings, but the tilting of metal halide octahedra is typically serious and leads to poor charge transport. Herein, a <110>-oriented 2D perovskite EPZPbBr4 (EPZ = 1-ethylpiperazine) with minimized tilting is designed through A-site stereo-hindrance engineering. The piperazine functional group enters the space enclosed by the three [PbBr6]4- octahedra, pushing Pb─Br─Pb closer to a straight line (maximum Pb─Br─Pb angle ≈180°), suppressing the tilting as well as electron-phonon coupling. Meanwhile, the ethyl group is located between layers and contributes an extremely reduced effective interlayer distance (2.22 Å), further facilitating the carrier transport. As a result, EPZPbBr4 simultaneously demonstrates high µτ product (1.8 × 10-3 cm2 V-1) and large resistivity (2.17 × 1010 Ω cm). The assembled X-ray detector achieves low dark current of 1.02 × 10-10 A cm-2 and high sensitivity of 1240 µC Gy-1 cm-2 under the same bias voltage. The realized specific detectivity (ratio of sensitivity to noise current density, 1.23 × 108 µC Gy-1 cm-1 A-1/2) is the highest among all reported perovskite X-ray detectors.

Reconfigurable perovskite X-ray detector for intelligent imaging.

X-ray detection is widely used in various applications. However, to meet the demand for high image quality and high accuracy diagnosis, the raw data increases and imposes challenges for conventional X-ray detection hardware regarding data transmission and power consumption. To tackle these issues, we present a scheme of in-X-ray-detector computing based on CsPbBr3 single-crystal detector with convenient polarity reconfigurability, good linear dynamic range, and robust stability. The detector features a stable trap-free device structure and achieves a high linear dynamic range of 106 dB. As a result, the detector could achieve edge extraction imaging with a data compression ratio of ~50%, and could also be programmed and trained to perform pattern recognition tasks with a high accuracy of 100%. Our research shows that in-X-ray-detector computing can be used in flexible and complex scenarios, making it a promising platform for intelligent X-ray imaging.

Rheological engineering of perovskite suspension toward high-resolution X-ray flat-panel detector.

Solution-processed polycrystalline perovskite film is promising for the next generation X-ray imaging. However, the spatial resolution of current perovskite X-ray panel detectors is far lower than the theoretical limit. Herein we find that the pixel level non-uniformity, also known as fixed pattern noise, is the chief culprit affecting the signal-to-noise ratio and reducing the resolution of perovskite detectors. We report a synergistic strategy of rheological engineering the perovskite suspensions to achieve X-ray flat panel detectors with pixel-level high uniformity and near-to-limit spatial resolution. Our approach includes the addition of methylammonium iodide and polyacrylonitrile to the perovskite suspension, to synergistically enhance the flowability and particle stability of the oversaturated solution. The obtained suspension perfectly suits for the blade-coating process, avoiding the uneven distribution of solutes and particles within perovskite films. The assembled perovskite panel detector exhibits greatly improved fixed pattern noise value (1.39%), high sensitivity (2.24 × 104 µC Gyair-1 cm-2), low detection limit (28.57 nGyair·s-1) as well as good working stability, close to the performance of single crystal detectors. Moreover, the detector achieves a near-to-limit resolution of 0.51 lp/pix.

Flexible and broadband colloidal quantum dots photodiode array for pixel-level X-ray to near-infrared image fusion.

Combining information from multispectral images into a fused image is informative and beneficial for human or machine perception. Currently, multiple photodetectors with different response bands are used, which require complicated algorithms and systems to solve the pixel and position mismatch problem. An ideal solution would be pixel-level multispectral image fusion, which involves multispectral image using the same photodetector and circumventing the mismatch problem. Here we presented the potential of pixel-level multispectral image fusion utilizing colloidal quantum dots photodiode array, with a broadband response range from X-ray to near infrared and excellent tolerance for bending and X-ray irradiation. The colloidal quantum dots photodiode array showed a specific detectivity exceeding 1012 Jones in visible and near infrared range and a favorable volume sensitivity of approximately 2 × 105 µC Gy-1 cm-3 for X-ray irradiation. To showcase the advantages of pixel-level multispectral image fusion, we imaged a capsule enfolding an iron wire and soft plastic, successfully revealing internal information through an X-ray to near infrared fused image.

Advances in the Application of Perovskite Materials.

Nowadays, the soar of photovoltaic performance of perovskite solar cells has set off a fever in the study of metal halide perovskite materials. The excellent optoelectronic properties and defect tolerance feature allow metal halide perovskite to be employed in a wide variety of applications. This article provides a holistic review over the current progress and future prospects of metal halide perovskite materials in representative promising applications, including traditional optoelectronic devices (solar cells, light-emitting diodes, photodetectors, lasers), and cutting-edge technologies in terms of neuromorphic devices (artificial synapses and memristors) and pressure-induced emission. This review highlights the fundamentals, the current progress and the remaining challenges for each application, aiming to provide a comprehensive overview of the development status and a navigation of future research for metal halide perovskite materials and devices.

One-dimensional scintillator film with benign grain boundaries for high-resolution and fast x-ray imaging.

Fast and high-resolution x-ray imaging demands scintillator films with negligible afterglow, high scintillation yield, and minimized cross-talk. However, grain boundaries (GBs) are abundant in polycrystalline scintillator film, and, for current inorganic scintillators, detrimental dangling bonds at GBs inevitably extend radioluminescence lifetime and increase nonradiative recombination loss, deteriorating afterglow and scintillation yield. Here, we demonstrate that scintillators with one-dimensional (1D) crystal structure, Cs5Cu3Cl6I2 explored here, possess benign GBs without dangling bonds, yielding nearly identical afterglow and scintillation yield for single crystals and polycrystalline films. Because of its 1D crystal structure, Cs5Cu3Cl6I2 films with desired columnar morphology are easily obtained via close space sublimation, exhibit negligible afterglow (0.1% at 10 ms) and high scintillation yield (1.2 times of CsI:Tl). We have also demonstrated fast x-ray imaging with 27 line pairs mm-1 resolution and frame rate up to 33 fps, surpassing most existing scintillators. We believe that the 1D scintillators can greatly boost x-ray imaging performance.

Growth mechanism of metal halide perovskite single crystals in solution.

Metal halide perovskite (MHP) single crystals (SCs) have been demonstrated to have significant potential in photodetectors and photovoltaic devices due to their exceptional optoelectronic properties. The most promising approach for large-scale fabrication of high-quality MHP SCs is the synthesis of MHP SCs in solution. To explain the mechanism and guide the crystal growth process, the classical nucleation-growth theory was established. However, it mainly focuses on zone melting systems and does not account for the interaction between perovskite and solvent. In this review, we specifically focus on the difference in the growth mechanism between MHP SCs in solution and traditional SCs synthesized by the melting method, which includes a discussion of the dissolution, nucleation, and growth processes. We then summarize recent advances in the preparation of MHP SCs based on the special growth mechanism of the perovskite system. The purpose of this review is to provide comprehensive information to offer targeted theoretical guidance as well as unified understanding for the preparation of high-quality MHP SCs in solution.

Direct Fast-Neutron Detection by 2D Perovskite Semiconductor.

Fast-neutrons play a critical role in a range of applications, including medical imaging, therapy, and nondestructive inspection. However, direct detecting fast-neutrons by semiconductors has proven to be challenging due to their weak interaction with most matter and the requirement of high carrier mobility-lifetime (µτ) product for efficient charge collection. Herein, a novel approach is presented to direct fast-neutron detection using 2D Dion-Jacobson perovskite semiconductor BDAPbBr4 . This material features a high fast-neutron caption cross-section, good electrical stability, high resistivity, and, most importantly, a record-high µτ product of 3.3 × 10-4 cm2 V-1 , outperforming most reported fast-neutron detection semiconductors. As a result, BDAPbBr4 detector exhibited good response to fast-neutrons, not only achieving fast-neutron energy spectra in counting mode, but also obtaining linear and fast response in integration mode. This work provides a paradigm-shifting strategy for designing materials that efficiently detect fast-neutrons and paves the way toward exciting applications in fast-neutron imaging and therapy.

Solution-Processed Hybrid Europium (II) Iodide Scintillator for Sensitive X-Ray Detection.

Lead halide perovskite nanocrystals have recently demonstrated great potential as x-ray scintillators, yet they still suffer toxicity issues, inferior light yield (LY) caused by severe self-absorption. Nontoxic bivalent europium ions (Eu2+) with intrinsically efficient and self-absorption-free d-f transition are a prospective replacement for the toxic Pb2+. Here, we demonstrated solution-processed organic-inorganic hybrid halide BA10EuI12 (BA denotes C4H9NH4+) single crystals for the first time. BA10EuI12 was crystallized in a monoclinic space group of P21/c, with photoactive sites of [EuI6]4- octahedra isolated by BA+ cations, which exhibited high photoluminescence quantum yield of 72.5% and large Stokes shift of 97 nm. These properties enable an appreciable LY value of 79.6% of LYSO (equivalent to ~27,000 photons per MeV) for BA10EuI12. Moreover, BA10EuI12 shows a short excited-state lifetime (151 ns) due to the parity-allowed d-f transition, which boosts the potential of BA10EuI12 for use in real-time dynamic imaging and computer tomography applications. In addition, BA10EuI12 demonstrates a decent linear scintillation response ranging from 9.21 µGyair s-1 to 145 µGyair s-1 and a detection limit as low as 5.83 nGyair s-1. The x-ray imaging measurement was performed using BA10EuI12 polystyrene (PS) composite film as a scintillation screen, which exhibited clear images of objects under x-ray irradiation. The spatial resolution was determined to be 8.95 lp mm-1 at modulation transfer function = 0.2 for BA10EuI12/PS composite scintillation screen. We anticipate that this work will stimulate the exploration of d-f transition lanthanide metal halides for sensitive x-ray scintillators.

Self-wavelength shifting in two-dimensional perovskite for sensitive and fast gamma-ray detection.

Lead halide perovskites have recently emerged as promising X/γ-ray scintillators. However, the small Stokes shift of exciton luminescence in perovskite scintillators creates problems for the light extraction efficiency and severely impedes their applications in hard X/γ-ray detection. Dopants have been used to shift the emission wavelength, but the radioluminescence lifetime has also been unwantedly extended. Herein, we demonstrate the intrinsic strain in 2D perovskite crystals as a general phenomenon, which could be utilized as self-wavelength shifting to reduce the self-absorption effect without sacrificing the radiation response speed. Furthermore, we successfully demonstrated the first imaging reconstruction by perovskites for application of positron emission tomography. The coincidence time resolution for the optimized perovskite single crystals (4 × 4 × 0.8 mm3) reached 119 ± 3 ps. This work provides a new paradigm for suppressing the self-absorption effect in scintillators and may facilitate the application of perovskite scintillators in practical hard X/γ-ray detections.

Mechanochemical Synthesis of High-Entropy Perovskite toward Highly Sensitive and Stable X-ray Flat-Panel Detectors.

Perovskites are attracting attention for optoelectronic devices. Despite their promise, the large-scale synthesis of perovskite materials with exact stoichiometry, especially high-entropy perovskites, has been a major challenge. Moreover, the difficulty in stoichiometry control also hinders the development of perovskite X-ray flat-panel detectors. Previous reports all employed simple MAPbI3 as the active layer, while the performance still falls short of optimized single-crystal-based single-pixel detectors. Herein, a scalable and universal strategy of a mechanochemical method is adopted to synthesize stoichiometric high-entropy perovskite powders with high quality and high quantity (>1 kg per batch). By utilizing these stoichiometric perovskites, the first FA0.9 MA0.05 Cs0.05 Pb(I0.9 Br0.1 )3 -based X-ray flat-panel detector with low trap density and large mobility-lifetime product (7.5 × 10-3 cm2 V-1 ) is reported. The assembled panel detector exhibits close-to-single-crystal performance (high sensitivity of 2.1 × 104 µC Gyair -1 cm-2 and ultralow detection limit of 1.25 nGyair s-1 ), high spatial resolution of 0.46 lp/pixel, as well as excellent thermal robustness under industrial standards. The high performance in the high-entropy perovskite-based X-ray FPDs has the potential to facilitate the development of new-generation X-ray-detection systems.

Sub-Nanosecond 2D Perovskite Scintillators by Dielectric Engineering.

Perovskite materials have demonstrated great potential for ultrafast scintillators with high light yield. However, the decay time of perovskite still cannot be further minimized into sub-nanosecond region, while sub-nanosecond scintillators are highly demanded in various radiation detection, including high speed X-ray imaging, time-of-flight based tomography or particle discrimination, and timing resolution measurement in synchrotron radiation facilities, etc. Here, a rational design strategy is showed to shorten the scintillation decay time, by maximizing the dielectric difference between organic amines and Pb-Br octahedral emitters in 2D organic-inorganic hybrid perovskites (OIHP). Benzimidazole (BM) with low dielectric constant inserted between [PbBr6 ]2- layers, resulting in a surprisingly large exciton binding energy (360.3 ± 4.8 meV) of 2D OIHP BM2 PbBr4 . The emitting decay time is shortened as 0.97 ns, which is smallest among all the perovskite materials. Moreover, the light yield is 3190 photons MeV-1 , which is greatly higher than conventional ultrafast scintillator BaF2 (1500 photons MeV-1 ). The rare combination of ultrafast decay time and considerable light yield renders BM2 PbBr4 excellent performance in γ-ray, neutron, α-particle detection, and the best theoretical coincidence time resolution of 65.1 ps, which is only half of the reference sample LYSO (141.3 ps).

Continuous and Scalable Production of Platinum Nanocubes with Uniform and Controllable Sizes in Air-Free Droplet Reactors.

Platinum (Pt) nanocrystals hold the key to a variety of catalytic applications, and those with a cubic shape are attractive as a reference catalyst due to their well-defined {100} facets on the surface. Here we demonstrate the use of droplet reactors as a viable platform for the continuous and scalable production of Pt nanocubes with uniform and controllable sizes. The synthesis was found to be sensitive to the O2 from air because of the oxidative etching associated with the O2/Br- pair. As such, either silicone oil or an inert gas had to be employed as the carrier phase to keep the droplets isolated from air. By controlling the amounts of the precursor and halide ions, the edge length of the Pt nanocubes could be tuned from 5-7 nm. In the setting of a millifluidic device, the droplet reactors could be used to achieve a production rate as high as 31.8 mg min-1, about 10-100 times greater than what has been reported in the literature. We also evaluated the electrocatalytic properties of the as-obtained Pt nanocubes toward the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). For the Pt nanocubes of 6 nm in edge length, they showed a specific activity of 0.27 mA cm-2 toward ORR at 0.9 V and a specific activity of 0.96 mA cm-2 toward MOR at the anodic potential.

Vertical matrix perovskite X-ray detector for effective multi-energy discrimination.

Multi-energy X-ray detection is sought after for a wide range of applications including medical imaging, security checking and industrial flaw inspection. Perovskite X-ray detectors are superior in terms of high sensitivity and low detection limit, which lays a foundation for multi-energy discrimination. However, the extended capability of the perovskite detector for multi-energy X-ray detection is challenging and has never been reported. Herein we report the design of vertical matrix perovskite X-ray detectors for multi-energy detection, based on the attenuation behavior of X-ray within the detector and machine learning algorithm. This platform is independent of the complex X-ray source components that constrain the energy discrimination capability. We show that the incident X-ray spectra could be accurately reconstructed from the conversion matrix and measured photocurrent response. Moreover, the detector could produce a set of images containing the density-graded information under single exposure, and locate the concealed position for all low-, medium- and high-density substances. Our findings suggest a new generation of X-ray detectors with features of multi-energy discrimination, density differentiation, and contrast-enhanced imaging.

Lead-Free Zero-Dimensional Organic-Copper(I) Halides as Stable and Sensitive X-ray Scintillators.

Low-dimensional organic-metal halides are regarded as an emerging class of X-ray scintillation materials, but most of the discovered compounds are confronted with challenges of toxicity and instability. To address these challenges, we herein report two lead-free zero-dimensional (0D) hybrid halides, (Bmpip)2Cu2Br4 and PPh4CuBr2 single crystals, grown by the low-cost solution-processing method. By single-crystal X-ray diffraction refinement, the crystal structures of (Bmpip)2Cu2Br4 and PPh4CuBr2 were determined to be orthorhombic and monoclinic crystal systems, respectively. (Bmpip)2Cu2Br4 and PPh4CuBr2 show broadband orange and yellow emissions peaking at 620 and 538 nm, respectively. Different from the emission nature of the recent reported Cu-based halide hybrids, both (Bmpip)2Cu2Br4 and PPh4CuBr2 emit from excitons bound to defects featuring spin-allowed transition, enabling them to possess fast scintillation decay time of tens of nanoseconds, respectively. In particular, the (Bmpip)2Cu2Br4 single crystal has a high photoluminescence quantum yield of 48.2%, a high scintillation yield of 16,000 photons/MeV, and a low detection limit of 710 nGyair/s. Due to the combination of nontoxicity, long-term stability, and decent detection performance, (Bmpip)2Cu2Br4 could be regarded as a promising X-ray scintillator.

Formamidinium Perovskitizers and Aromatic Spacers Synergistically Building Bilayer Dion-Jacobson Perovskite Photoelectric Bulk Crystals.

Two-dimensional (2D) multilayer Dion-Jacobson (DJ) phase organic inorganic hybrid perovskites (OIHPs) have attracted extensive research attention due to the high stability and excellent charge-transport properties in the optoelectronic field. However, the synthesis of 2D multilayer DJ OIHPs is still very challenging. Until now, only few multilayer DJ perovskites have been reported and most of them are based on volatile methylamine (MA) cations. Compared with MA-based OIHPs, the OIHPs constructed with formamidinium (FA) as perovskitizers not only improve the stability but also extend the light absorption range. Meanwhile, the introducing aromatic diamines as spacers could promote the electron-hole separation in such DJ hybrids. However, the DJ OIHP bulk single crystal constructed by using the advantages of FA as perovskitizers and aromatic diamines as spacers is still blank. Herein, we integrate the properties of organic cations and inorganic skeletons at a molecular-scale to construct a broadband-responsive 2D bilayer DJ perovskite (3AMPY)(FA)Pb2I7 [3AMPY = 3-(aminomethyl)pyridinium], which shows a fascinating detectivity from X-ray (5.23 × 104 µC Gyair-1 cm-2 at 200 V bias) and visible light (6 × 1012 jones at 637 nm) to the near-infrared region (2.6 × 109 jones at 780 nm). After an in-depth analysis of structure and optical properties, we found that the distortion degree of Pb-I-Pb bond angles between adjacent PbI6 octahedra plays a crucial role on optical properties; on the other hand, the interlayer spacer cations (3AMPY) and intralayer perovskitizers (FA) mutual participate in the contribution of the conduction band, making (3AMPY)(FA)Pb2I7 have a narrow optical band gap of 1.54 eV. Such a 2D perovskite material with a wide spectra response will be the preferred choice for photodetection under complex conditions.

Chemical Potential Diagram Guided Rational Tuning of Electrical Properties: A Case Study of CsPbBr3 for X-ray Detection.

Controlling the carrier polarity and concentration underlies most electronic and optoelectronic devices. However, for the intensively studied lead halide perovskites, the doping tunability is inefficient. In this work, taking CsPbBr3 as an example, it is revealed that the coexistence of metallic Pb or CsBr3 /Br2 , rather than the precursor ratio, can provide Pb-rich/Br-poor or Br-rich/Pb-poor chemical conditions, enabling the tunability of electrical properties from weak n-type, intrinsic, to moderate p-type. Experimentally, under Br2 -exposure treatment, a shift of the Fermi level as large as 1.00 eV is achieved, which is one of the highest value among all kinds of doping methods. The X-ray detector based on the intrinsic CsPbBr3 exhibits excellent performance, with a negligible dark-current drift of 7.1 × 10-4 nA cm-1 s-1 V-1 , a low detection limit of 103.6 nGyair s-1 , and a high sensitivity of 9085 µC Gyair -1 cm-2 . This work provides a critical understanding and guidance for tuning the electrical properties of lead halide perovskites, which establishes good foundations for achieving intrinsic perovskite semiconductors and also constructing potential homojunction devices.

Dark current modeling of thick perovskite X-ray detectors.

Metal halide perovskites (MHPs) have demonstrated excellent performances in detection of X-rays and gamma-rays. Most studies focus on improving the sensitivity of single-pixel MHP detectors. However, little work pays attention to the dark current, which is crucial for the back-end circuit integration. Herein, the requirement of dark current is quantitatively evaluated as low as 10-9 A/cm2 for X-ray imagers integrated on pixel circuits. Moreover, through the semiconductor device analysis and simulation, we reveal that the main current compositions of thick perovskite X-ray detectors are the thermionic-emission current (JT) and the generation-recombination current (Jg-r). The typical observed failures of p-n junctions in thick detectors are caused by the high generation-recombination current due to the band mismatch and interface defects. This work provides a deep insight into the design of high sensitivity and low dark current perovskite X-ray detectors.

Decreasing Structural Dimensionality of Double Perovskites for Phase Stabilization toward Efficient X-ray Detection.

Halide double perovskites have attracted substantial attention for optoelectronic applications owing to their low toxicity and high stability. However, double perovskites have strict requirements in terms of the halide type, thus rendering many of their properties unchangeable, including the band gap, atomic number, and carrier transport. By introducing long-chain organic amines, the chloride site of double perovskites can be completely replaced by bromide. Using this strategy, two dimensions silver-indium-bromide double perovskites (PEA)4AgInBr8 and (i-BA)4AgInBr8 were successfully synthesized [(PEA)+ = C6H5(CH2)2NH3+, (i-BA)+ = CH(CH3)2CH2NH3+]. Density functional theory calculations and spectroscopy characterizations were performed to unveil the semiconducting behaviors and photoluminescence properties of the title compounds. Electrical characterization confirms their good carrier-transport property (µτ product: 2.0 × 10-3 cm2 V-1) and low dark current. Moreover, the presence of heavy atoms, together with the ultrastable baseline contributes to a high X-ray detection sensitivity (185 µC Gyair-1 cm-2), greater than that of most previous double-perovskite detectors. Our work lays the foundation for broadening the family of potential double perovskites, creating a new path for the realization of long-sought perovskites with low toxicity and high stability that retain good optoelectronic performance.