Water‐Resistant Lead‐Free Perovskitoid Single Crystal for Efficient X‐Ray Detection

Abstract

Despite the rapid progress of hybrid organic-inorganic halide perovskites in optoelectronic applications, their water resistance is still limited because of the interaction of both the organic and inorganic components with water molecules. In this study, a cation engineering protocol to obtain a material with inherent high water resistance by incorporating benzamidinium (BAH) cations into the bismuth halide framework is developed. Analysis of the crystal structure indicates that (BAH)BiI 4 exhibits a molecular 1D perovskitoid structure with an edge-sharing mode and strong noncovalent interactions within the crystal, including I•••I interaction, hydrogen bonding, and π-π stacking between adjacent BAH cations. Such strong noncovalent interactions provide excellent water resistance, with negligible decomposition of crystals during water soaking for two months. The feasibility of the (BAH)BiI 4 crystal for X-ray detection, with a sensitivity as high as 1181.8 µC Gy air −1 cm −2 and a detection limit below 77 nGy air s −1 under 50 V bias is further demonstrated. Such good values are due mainly to efficient charge transport along the π-π stacking between neighboring BAH cations and I•••I interactions between adjacent inorganic chains. These findings provide a new approach to improve the water resistance of perovskite/perovskitoid optoelectronic devices.

One-dimensional lead-free perovskite single crystals with high X-ray response grown by liquid phase diffusion

“…20,[22][23][24][25] Therefore, bismuth-based hybrid halide perovskites, as a class of lead-free members, provides potential new players for high-performance detection materials as exemplified by (3-(aminomethyl)pyridine)BiI 5 , (benzamidinium)BiI 4 , MA 3 Bi 2 I 9 , (CH 3 NH 3 CH 2 CH 2 NH 3 CH 3 )BiI 5 and (N-methyl-1,3-diaminopropanium)BiI 5 . 17,[26][27][28][29][30] In addition to enriching the bismuthbased perovskite family, researchers have also made a lot of attempts in crystal growth methods. For example, using the antisolvent vapor-assisted method, centimeter-sized 1D (pentamethylenediamine)BiBr 5 single crystals (SCs) were obtained.…”

Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes

“…Ionizing radiations, especially X-ray radiation from natural and artificial sources, pose a variety of potential health risks if inappropriately used, which has aroused extensive attention from our society. − As such, the precise detection of X-ray radiation is highly desirable in the radiation biological study, environmental and cosmic radiation detection, and medical radiation treatment. − For these applications, the important requirements are high sensitivity, strong chemical, thermal and radiolytic stabilities, good X-ray absorption, outstanding resistance to fatigue, excellent detection performance, and mild operating conditions. − The currently used commercial detectors mainly focus on radio-photoluminescence (RPL) materials, scintillators, and semiconductors, which still face severe limitations in practical application due to their inherent vice. − For example, many radio-photoluminescence materials display limited luminescent stability after continuous high-dose X-ray radiation and scintillators can only record the instantaneous radiation, both of which require spectrophotometers to indirectly read the radiation signal when they are applied for X-ray detection, ,− while the semiconductors used as X-ray detection materials display several other disadvantages such as poor X-ray absorptivity, low detection efficiency, and harsh operating conditions. , Thus, these limitations call for the continued search for new efficient X-ray radiation detection materials.…”

Halide perovskites for sensitive, stable and scalable X-ray detection and imaging

“…53 The seed crystal was obtained first and was used as the nucleation point to carefully control the nucleation process of the crystal and then kept growing into a large single crystal. Due to its excellent crystal quality, the detector with a 74 326 241 NA (DMEDA)BiI 5 , SC 84 72.5 NA NA (H 2 MDAP)BiI 5 ,SC 75 1 N A N A (3-AMP)BiI 5 , SC 76 7.7 NA NA (BAH)BiI 4 , SC 77 1181. was obtained, and the detectors demonstrated stable operation even under high applied biases. Furthermore, no deterioration in detection performance was observed following sensing of an integrated X-ray irradiation dose of B23 800 mGy air , equivalent to 4200 000 times the dose required for a single commercial X-ray chest radiograph.…”

“…(e) Crystal structure of 1D (DMEDA)BiI 5 . 84 (f) Photographs of other-type single crystals: (H 2 MDAP)BiI 5 (1), reproduced with permission, 75 Copyright 2019, American Chemical Society, (3-AMP)BiI 5 (2), reproduced with permission, 76 Copyright 2022, John Wiley & Sons, and (BAH)BiI 4 (3), reproduced with permission, 77 Copyright 2022, John Wiley & Sons.…”

“…1(f) shows the photographs of some 1D SCs. Reported examples include (H 2 MDAP)BiI 5 , 75 (DMEDA)BiI 5 , 84 (BAH)BiI 4 77 and (3-AMP)BiI 5 . 76 Among them, except for (BAH)-BiI 4 , which reports excellent device properties, the properties of the remaining materials are not so satisfactory.…”