No abstract

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)3BiI6] 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.

Methylammonium lead tribromide perovskite single crystals have been demonstrated to be good candidates as sensitive X-ray detectors in direct detection mode in recent years. However, its X-ray detection performance based on the orientation of different facets is still not clear. Here, we developed a facile strategy to chemically expose the [110] facet of single crystals from low-cost solution processes by tailoring the nonstoichiometry of feeding ions to selectively suppress the growth of the [100] facet. In contrast to physically cutting and sawing single-crystal ingots, this avoids damage to the fragile single crystals as well as orientation errors, more suitable for the naturally soft lattice. Compared to the [100] facet, the exposed [110] facet of perovskite single crystals exhibits a smaller trap density and excellent charge carrier transportation properties, leading to an improved sensitivity of 3928.3 μC/Gy air / cm 2 to 120 keV hard X-rays, which potentially outperforms the currently dominating CsI scintillator of a commercial digital radiography (DR) medical imager for a routine health check.

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.

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 (MAPbI 3 ) semiconductor and indirect zero-dimensional cesium copper iodide (Cs 3 Cu 2 I 5 ) scintillator through low-cost fast tableting processes is reported. Due to the fast energy transfer from Cs 3 Cu 2 I 5 to MAPbI 3 , 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, Cs 3 Cu 2 I 5 exists at the grain boundaries of MAPbI 3 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 MAPbI 3 direct-type semiconductor, and 10 times compared with the Cs 3 Cu 2 I 5 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.