Precise arraying of perovskite single crystals through droplet-assisted self-alignment.

Patterned arrays of perovskite single crystals can avoid signal cross-talk in optoelectronic devices, while precise crystal distribution plays a crucial role in enhancing device performance and uniformity, optimizing photoelectric characteristics, and improving optical management. Here, we report a strategy of droplet-assisted self-alignment to precisely assemble the perovskite single-crystal arrays (PSCAs). High-quality single-crystal arrays of hybrid methylammonium lead bromide (MAPbBr3) and methylammonium lead chloride (MAPbCl3), and cesium lead bromide (CsPbBr3) can be precipitated under a formic acid vapor environment. The crystals floated within the suspended droplets undergo movement and rotation for precise alignment. The strategy allows us to deposit PSCAs with a pixel size range from 200 to 500 micrometers on diverse substrates, including indium tin oxide, glass, quartz, and poly(dimethylsiloxane), and the area can reach up to 10 centimeters by 10 centimeters. The PSCAs exhibit excellent photodetector performance with a large responsivity of 24 amperes per watt.

Preferred Orientation and Phase Distribution of Quasi-2D Perovskite for Bifunctional Light-Emitting Photodetectors.

In traditional optical wireless communication (OWC) systems, the simultaneous use of multiple sets of light-emitting diodes (LEDs) and photodetectors (PDs) increases the system complexity and instability. Here we report bifunctional light-emitting photodetectors (LEPDs) fabricated with quasi-2D perovskite (F-PEA)2Cs4Pb5I11Br5 as light-emitting/detecting layers for efficient, miniaturized, and intelligent bidirectional OWC. By simply changing the solvent composition of the precursor solution and using antisolvent engineering, we manipulated the crystal orientation and phase distribution of (F-PEA)2Cs4Pb5I11Br5, realizing high irradiance (4.36 µW cm-2) and a -3 dB refresh rate (0.21 MHz) of electroluminescence in LED mode as well as low noise (below 1 pA Hz-1/2) and high responsivity (0.1 A W-1) in PD mode. The rapid and accurate OWC process was demonstrated through interaction of LEPDs. We also demonstrated the high-fidelity compression and digitization of high-resolution (256 × 256 pixels) color images using the four-step phase shift method to realize intelligent encrypted image OWC.

Arising 2D Perovskites for Ionizing Radiation Detection.

2D perovskites have greatly improved moisture stability owing to the large organic cations embedded in the inorganic octahedral structure, which also suppresses the ions migration and reduces the dark current. The suppression of ions migration by 2D perovskites effectively suppresses excessive device noise and baseline drift and shows excellent potential in the direct X-ray detection field. In addition, 2D perovskites have gradually emerged with many unique properties, such as anisotropy, tunable bandgap, high photoluminescence quantum yield, and wide range exciton binding energy, which continuously promote the development of 2D perovskites in ionizing radiation detection. This review aims to systematically summarize the advances and progress of 2D halide perovskite semiconductor and scintillator ionizing radiation detectors, including reported alpha (α) particle, beta (ß) particle, neutron, X-ray, and gamma (γ) ray detection. The unique structural features of 2D perovskites and their advantages in X-ray detection are discussed. Development directions are also proposed to overcome the limitations of 2D halide perovskite radiation detectors.

Differential perovskite hemispherical photodetector for intelligent imaging and location tracking.

Advanced photodetectors with intelligent functions are expected to take an important role in future technology. However, completing complex detection tasks within a limited number of pixels is still challenging. Here, we report a differential perovskite hemispherical photodetector serving as a smart locator for intelligent imaging and location tracking. The high external quantum efficiency (~1000%) and low noise (10-13 A Hz-0.5) of perovskite hemispherical photodetector enable stable and large variations in signal response. Analysing the differential light response of only 8 pixels with the computer algorithm can realize the capability of colorful imaging and a computational spectral resolution of 4.7 nm in a low-cost and lensless device geometry. Through machine learning to mimic the differential current signal under different applied biases, one more dimensional detection information can be recorded, for dynamically tracking the running trajectory of an object in a three-dimensional space or two-dimensional plane with a color classification function.

Cation-π interactions enabled water-stable perovskite X-ray flat mini-panel imager.

Sensitive and stable perovskite X-ray detectors are attractive in low-dosage medical examinations. The high sensitivity, tunable chemical compositions, electronic dimensions, and low-cost raw materials make perovskites promising next-generation semiconductors. However, their ionic nature brings serious concerns about their chemical and water stability, limiting their applications in well-established technologies like crystal polishing, micro-processing, photolithography, etc. Herein we report a one-dimensional tryptamine lead iodide perovskite, which is stable in water for several months as the strong cation-π interactions between organic cations. The one-dimensional and two-dimensional tryptamine lead iodide perovskite tablets are switchable through thermal-annealing or water-soaking treatments to relax microstrains. The water-stable and microstrain-free one-dimensional perovskite tablets yield a large sensitivity of 2.5 × 106 µC Gyair-1 cm-2 with the lowest detectable dose rate of 5 nGyair s-1. Microelectrode arrays are realized by surface photolithography to construct high-performance X-ray flat mini-panels with good X-ray imaging capability, and a record spatial resolution of 17.2 lp mm-1 is demonstrated.

Robust Organogel Scintillator for Self-healing and Ultra-flexible X-ray Imaging.

Metal halide scintillators serve as promising candidates for X-ray detection due to their high attenuation coefficients, high light yields, and low-cost solution-processable characteristics. However, the issues of humidity/thermal quenching and mechanical fragility, remain obstacles to the broad and diversified development of metal halide scintillators. Here, this work reports a lead-free, water-stable, stretchable, and self-healing (ethylenebis-triphenylphosphonium manganese (II) bromide (C38H34P2)MnBr4 organogel scintillator that meets X-ray imaging in complex scenarios. The robust organogel scintillator can be stretched with elongation up to 1300% while maintaining the scintillation properties. Activated by the dynamic hydrogen bonds and coordination bonds design, the organogel scintillator exhibits excellent self-healing properties at room temperature to alleviate the vignetting problem of the rigid scintillator films, the X-ray imaging resolution can reach 16.7 lp mm-1. The organogel scintillator can also realize flexible and self-healing X-ray imaging in water, providing a design path for portable devices in harsh conditions.

Reductant Engineering in Stable and High-Quality Tin Perovskite Single Crystal Growth for Heterojunction X-Ray Detectors.

Tin perovskites have emerged as a promising alternative material to address the toxicity of lead perovskites and the low bandgap of around 1.1 eV is also compatible with tandem solar cell applications. Nevertheless, the optoelectronic performance of solution-processed tin perovskite single-crystal counterparts still lags behind because of the tin instability under ambient conditions during crystal growth and limited reductants to protect the Sn2+ ions from oxidation. Here, the reductant engineering to grow high-quality tin perovskite single crystals under ambient conditions is studied. Oxalic acid (H2 C2 O4 ) serves as an excellent reductant and sacrificial agent to protect Sn2+ ions in methanol due to its suitable redox potential of -0.49 V, and the CO2 as the oxidation product in the gas state can be easily separated from the solution. The FPEA2 SnI4 single crystal grown by this strategy exhibits low trap density perovskite surface by constructing an FPEA2 PbI4 -FPEA2 SnI4 (FPI-FSI) single crystal heterojunction for X-ray detection. An improved X-ray sensitivity of 1.7 × 105 µC Gy-1 cm-2 is realized in the heterojunction device, outperforming the control FPEA2 PbI4 counterpart.

LoyalDE: Improving the performance of Graph Neural Networks with loyal node discovery and emphasis.

Recent years have witnessed an increasing focus on graph-based semi-supervised learning with Graph Neural Networks (GNNs). Despite existing GNNs having achieved remarkable accuracy, research on the quality of graph supervision information has inadvertently been ignored. In fact, there are significant differences in the quality of supervision information provided by different labeled nodes, and treating supervision information with different qualities equally may lead to sub-optimal performance of GNNs. We refer to this as the graph supervision loyalty problem, which is a new perspective for improving the performance of GNNs. In this paper, we devise FT-Score to quantify node loyalty by considering both the local feature similarity and the local topology similarity, and nodes with higher loyalty are more likely to provide higher-quality supervision. Based on this, we propose LoyalDE (Loyal Node Discovery and Emphasis), a model-agnostic hot-plugging training strategy, which can discover potential nodes with high loyalty to expand the training set, and then emphasize nodes with high loyalty during model training to improve performance. Experiments demonstrate that the graph supervision loyalty problem will fail most existing GNNs. In contrast, LoyalDE brings about at most 9.1% performance improvement to vanilla GNNs and consistently outperforms several state-of-the-art training strategies for semi-supervised node classification.

Rational adjustment to interfacial interaction with carbonized polymer dots enabling efficient large-area perovskite light-emitting diodes.

Film uniformity of solution-processed layers is the cornerstone of large-area perovskite light-emitting diodes, which is often determined by the 'coffee-ring effect'. Here we demonstrate a second factor that cannot be ignored is the solid-liquid interface interaction between substrate and precursor and can be optimized to eliminate rings. A perovskite film with rings can be formed when cations dominate the solid-liquid interface interaction; whereas smooth and homogeneous perovskite emitting layers are generated when anions and anion groups dominate the interaction. This is due to the fact that the type of ions anchored to the substrate can determine how the subsequent film grows. This interfacial interaction is adjusted using carbonized polymer dots, who also orient the perovskite crystals and passivate their buried traps, enabling a 225 mm2 large-area perovskite light-emitting diode with a high efficiency of 20.2%.

Low Bandgap 2D Perovskite Single Crystal with Anomalous-large Charges/ions Collection Ratio for Ultra-sensitive and Stable X-ray Detectors.

The low-dimensional halide perovskites have attracted increasing attention due to their improved moisture stability, reduced defects, and suppressed ions migration in many optoelectronic devices such as solar cells, light-emitting diodes, X-ray detectors, and so on. However, they are still limited by their large band gap and short charge carriers' diffusion length. Here, we demonstrate that the introduction of metal ions into organic interlayers of two-dimensional (2D) perovskite by cross-linking the copper paddle-wheel cluster-based lead bromide ([Cu(O2 C-(CH2 )3 -NH3 )2 ]PbBr4 ) perovskite single crystals with coordination bonds can not only significantly reduce the perovskite band gap to 0.96 eV to boost the X-ray induced charge carriers, but can also selectively improve the charge carriers' transport along the out-of-plane direction and blocking the ions motion paths. The [Cu(O2 C-(CH2 )3 -NH3 )2 ]PbBr4 single-crystal device can reach a record charges/ions collection ratio of 1.69×1018 ±4.7 % µGyair -1 s, and exhibit a large sensitivity of 1.14×105 ±7% µC Gyair -1 cm-2 with the lowest detectable dose rate of 56 nGyair s-1 under 120 keV X-rays irradiation. In addition, [Cu(O2 C-(CH2 )3 -NH3 )2 ]PbBr4 single-crystal detector exposed to the air without any encapsulation shows excellent X-ray imaging capability with long-term operational stability without any attenuation of 120 days.

Prominent Free Charges Tunneling Through Organic Interlayer of 2D Perovskites.

The diversity of organic cations greatly enriches the species of 2D perovskites; traditional 2D Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) perovskites are synthesized by two different organic amines. Here, according to the difference in pKa values between conjugated acids of monoprotonated and biprotonated 4-(2-Aminoethyl)pyridine (4AEPy) ions, the 2D perovskites of RP (4AEPy)2 PbI4 and DJ (4AEPy)PbI4 from same organic amine is reported, which can realize reversible transformation under the treatment of HI and NH3 , respectively. The interaction of N-H···N hydrogen bond between adjacent organic molecules in (4AEPy)2 PbI4 leads to the bending conformation of ethylamine groups, which results in a 2.4 Å reduction in layer spacing compared to typical phenylethylamine lead iodine ((PEA)2 PbI4 ) 2D perovskite. Besides, the ethylamine groups of organic layers in (4AEPy)PbI4 are deeply inserted into octahedral cavities and directly participate in the construction of the conduction band minimum, which leads to a small exciton binding energy of 27.3 meV to generate free charges. The stronger coupling between the organic and inorganic layers and the minor exciton binding energy can promote the DJ phase to possess a more stable structure and better optoelectronic properties. Thus the (4AEPy)PbI4 device displays better light response and X-ray detection capability with a high sensitivity of 5627 µC Gyair -1 cm-2 and the lowest detectable dose rate of 20 nGyair s-1 .

Carbonized polymer dots enhanced stability and flexibility of quasi-2D perovskite photodetector.

Quasi-2D perovskites have been demonstrated to be competitive materials in the photodetection fields due to the enhanced moisture stability by large organic cations. However, as the increasing demands of modern technology, it is still challenging to combine the flexibility with the capability of weak light detection in a low-cost way. Here, amides, carboxylic acids, and anhydrides groups-rich carbonized polymer dots (CPDs) were employed to fill in the perovskite grain boundaries, which can passivate the point defects of perovskite by coordinating with the unbonded Pb atoms, and reduce the leakage current. Weak light detection capability was demonstrated by directly resolving light with an intensity of 10.1 pW cm-2. More importantly, the stretchable polymer chains on CPDs strongly interact with perovskite ions through multiple supramolecular interactions, and extend the stretchable properties to the perovskite/CPDs composites, which can maintain the integral structure stability during the deformation of perovskite crystals and restricted any crack by releasing the film strain. Our fabricated devices show extraordinary flexible stability in the bending-dependent response tests. The viscoelasticity of CPDs improves the bending stability of the flexible quasi-2D perovskite photodetectors, and device performance shows no degradation after bending 10000 times, comparable or even outperforming the dominating flexible photodetectors.

Spray-coated perovskite hemispherical photodetector featuring narrow-band and wide-angle imaging.

Sphere imagers featuring specific wavelength recognition and wide-angle imaging are required to meet the fast development of modern technology. However, it is still challenging to deposit high-quality photosensitive layers on sphere substrates from low-cost solution processes. Here we report spray-coated quasi-two-dimensional phenylethylammonium/formamidinium lead halide (PEA2FAn-1PbnX3n+1) perovskite hemispherical photodetectors. The crystallization speed is manipulated by perovskite compositions, and the film thickness can be controlled by spray-coating cycles and solution concentration from tens of nanometers to hundreds of micrometers with a fast velocity of 1.28 × 10-4 cm3 s-1. The lens-free hemispherical photodetectors allow light response at a wide incident angle of 180°. Simultaneously, the wavelength selective response from visible to the near-infrared range is achieved with full width at half maximums (FWHMs) of ~20 nm, comparable to single-crystal devices. Wide-angle and wavelength-selective imaging are also demonstrated, which can find potential applications in intelligent recognition and intraoperative navigated surgery.

Perovskite Dimensional Evolution Through Cations Engineering to Tailor the Detection Limit in Hard X-ray Response.

Halide perovskites with various compositions are potential candidates in low-dosage X-ray detection due to their large sensitivity and tunable optoelectronic properties. Here, cations engineering induced dimensional evolution of halide perovskites between 0D, 2D, and 3D is reported. Centimeter-sized 2D lead-free perovskite single-crystal of 4-fluorophenethylammonium antimony iodide (FPEA3 SbI6 ) is synthesized. In contrast to the 0D phenethylammonium antimony iodide (PEA3 Sb2 I9 ), face-shared [Sb2 I9 ]3- of the bi-octahedral structure of PEA3 Sb2 I9 is split into corner-shared [SbI6 ]3- by intermolecular interactions and steric hindrance of FPEA+ ions in 2D FPEA3 SbI6 . Two Sb3+ ions share three octahedral [SbI6 ]3- , leaving one-third of Sb3+ vacancies in the framework of FPEA3 SbI6 . Furthermore, Sn2+ ions can be filled into the vacancies to form continuous 2D frameworks to tune the anisotropic conductivity and device sensitivity to hard X-rays. The dimensional evolution of perovskite single-crystals from 3D to 2D or 0D to 2D maximizes the signal/noise ratio to facilize the adjustability of detection limit in hard X-ray detection, which is determined by both device sensitivity and device noise current. A record low detection limit coefficient of 0.65 is achieved in the 2D FPEA3 SbSn0.5 I7 single-crystal sample, which results from selective charges collection over mobile ions/noise current in the 2D perovskite structure.

Organic Amine-Bridged Quasi-2D Perovskite/PbS Colloidal Quantum Dots Composites for High-Gain Near-Infrared Photodetectors.

Near-infrared (NIR) II detection at weak flux intensity is required in medical imaging and is especially urgent in light of the low quantum efficiency of NIR-II dyes. The low responsivity of traditional photodetectors in this region limits image quality. Here, we report a NIR-II photodetector with high gain based on perovskite coupled PbS colloidal quantum dots (CQDs). Tailoring the trap density of CQDs by designing surface ligands with dual functionality contributed to control over trap-induced charge-injection upon light illumination. As a result, a detector with high gain is realized, showing external quantum efficiency of 1260% at 1200 nm and achieving the lowest detectable light intensity, that is, as low as 0.67 pW cm-2 with a linear dynamic range of 200 dB. Devices maintain over 90% of responsivity after 150 days of storage. We acquired images of a butterfly wing, showing the skeleton texture with a maximum spatial resolution of 3.9 lp/mm.

Energy Transfer Assisted Fast X-ray Detection in Direct/Indirect Hybrid Perovskite Wafer.

Metal halide perovskite scintillators encounter unprecedented opportunities in indirect ionizing radiation detection due to their high quantum yields. However, the long scintillation lifetime of microseconds upon irradiation, known as the afterglow phenomenon, obviously limits their fast development. Here, a new type of hybrid X-ray detector wafer combining direct methylamine lead iodide (MAPbI3 ) semiconductor and indirect zero-dimensional cesium copper iodide (Cs3 Cu2 I5 ) scintillator through low-cost fast tableting processes is reported. Due to the fast energy transfer from Cs3 Cu2 I5 to MAPbI3 , the device response time to X-rays is dramatically reduced by nearly 30 times to 36.6 ns, which enables fast X-ray detection capability by a large area detector arrays within 1 s. Moreover, Cs3 Cu2 I5 exists at the grain boundaries of MAPbI3 crystals, and blocks the paths of mobile ions of perovskite, leading to the lowest detectable dose rate of hybrid X-ray detector is thus reduced by 1.5 times compared with control MAPbI3 direct-type semiconductor, and 10 times compared with the Cs3 Cu2 I5 indirect-type scintillator. The direct/indirect hybrid wafer also exhibits improved operation stability at ambient conditions without any encapsulation. This new kind of hybrid X-ray detectors provides strong competitiveness by combining the advantages of both direct perovskite semiconductors and indirect perovskite scintillators for next-generation products.

Oriented 2D Perovskite Wafers for Anisotropic X-ray Detection through a Fast Tableting Strategy.

2D perovskite single crystals have emerged as excellent optoelectronic materials owing to their unique anisotropic properties. However, growing large 2D perovskite single crystals remains challenging and time-consuming. Here, a new composition of lead-free 2D perovskite-4-fluorophenethylammonium bismuth iodide [(F-PEA)3 BiI6 ] is reported. An oriented bulk 2D wafer with a large area of 1.33 cm2 is obtained by tableting disordered 2D perovskite powders, resulting in anisotropic resistivities of 5 × 1010 and 2 × 1011  Ω cm in the lateral and vertical directions, respectively. Trivalent Bi3+ ions are employed to achieve a stronger ionic bonding energy with I- ions, which intrinsically suppress the ion-migration effect. Thus, the oriented wafer presents good capabilities in both charge collection and ion-migration suppression under a large applied bias along the out-of-plane direction, making it suitable for low-dosage X-ray detection. The large-area wafer shows a sensitive response to hard X-rays operated at a tube voltage of 120 kVp with the lowest detectable dose rate of 30 nGy s-1 . Thus, the fast tableting process is a facile and effective strategy to synthesize large-area, oriented 2D wafers, showing excellent X-ray detection performance and operational stability that are comparable to those of 2D perovskite single crystals.

Polyhydroxy Ester Stabilized Perovskite for Low Noise and Large Linear Dynamic Range of Self-Powered Photodetectors.

Solution-processed perovskites as emerging semiconductors have achieved unprecedented milestones in sensor optoelectric devices. Stability along with the device noise issues are the major obstacle for photodetectors to compete with the traditional devices. Here, we demonstrated that l-ascorbic acid (l-AA) as a polyhydroxy ester can coordinate with the amino group of formamidine cations (FA+) through multiple hydrogen bond interactions to stabilize the perovskite, which protect the FA+ ions from nucleophile attack and effectively suppress the degradation of FA+ ions, improving the perovskite stability and suppressing the device noise to below 0.3 pA Hz-1/2 with a large linear dynamic range of 239 dB. The dual functions of l-AA enable the perovskite photodetector to have a high detectivity of 1012 Jones. The self-powered device works with no energy consumption and maintains an undegraded performance over 1200 h of inspection at ambient conditions, which is promising for infrastructure construction, signal sensing, and real-time information delivery.

Fine-control-valve of halide perovskite single crystal quality for high performance X-ray detection.

Halide perovskite single crystals (HPSCs) provide a unique platform to study the optoelectronic properties of such emerging semiconductor materials, while the temperature induced crystal growth method often has an increased solute integration speed and/or unavoidable solute consumption, resulting in a soaring or slumping crystal growth rate of HPSCs. Here, we developed a universal and facile solvent-volatilization-limited-growth (SVG) strategy to finely control the crystal growth rate by the fine-control-valve for high quality crystal grown through solution processes. The grown HPSCs by SVG method exhibited a record low trap density of 2.8 × 108 cm-3 and a high charge carrier mobility-lifetime product (µτ product) of 0.021 cm2/V, indicating the excellent crystal quality. The crystal surface defects were further passivated by oxygen suppliers as Lewis base, which led to a reduction of surface leakage current by two times when using for low dose rate X-ray detection. Such HPSC X-ray detector displayed a high sensitivity of 1274 µC/(Gyair cm2) with a lowest detectable dose rate of 0.56 µGyair/s under 120 keV hard X-ray. Further applications including alloy composition analysis and metal flaw detection by HPSC detectors were also demonstrated, which not only shows the bright future for product quality inspection and non-destructive materials analysis, but also paves the way for growing high quality single crystals and fabricating polycrystalline films.