Abstract

The CsPbIBr<sub>2</sub> perovskite films deposited from the precursor solutions in air, usually suffer poor surface coverage and air-stability due to the uncontrolled nucleation and the existence of I<sup>–</sup> during the film formation, resulting in terrible photoelectric characteristics and reproducibility. At present, the high-quality CsPbIBr<sub>2</sub> films are prepared under nitrogen atmosphere, which results in the increase of the cost and thus impedes their applications in air. Here in this work, we propose a strategy for growing the perovskite films with low defect density and better stability in air via dual-ligand-assisted (ligand 1 (LP) and ligand 2 (NH<sub>4</sub>SCN)) solution strategy. These ligands contain some organic molecules which have strong interaction with ions on the surface of perovskite thin film in order to regulate the addition of precursor ions onto the films. The high-quality CsPbIBr<sub>2</sub> thin films are prepared in air with relative humidity of ≤60% by the spraying method. The results indicate that ligand 1 with hydrophilic group and hydrophobic group, a kind of surfactant, can effectively reduce the surface tension of perovskite precursor solution, improve the coverage of CsPbIBr<sub>2</sub> perovskite film, and form a block layer of water and oxygen. However, the addition of ligand 1 in precursor solution inevitably introduces many grain boundaries, which is unfavorable for carrier transport and collection. Thus, ligand 2 is employed to control the nucleation of perovskite film as another ligand, resulting in reducing the point defect formation. Their combination is beneficial to forming the uniform perovskite film with large-size crystal and low-density defect. The high-quality crystallization of the perovskite film is found to simultaneously enhance the response and the durability of photodetectors. Thus, the unpackaged photodetectors (ITO/CsPbIBr<sub>2</sub>/Au) based on this strategy yield the outstanding photoelectric response under the excitation of 405 nm laser. This device exhibits a low dark current density of 2 × 10<sup>–4</sup> mA/cm<sup>2</sup>, a fast response time of 20–21 µs, and high stability (81%, ≥70 d) in air with a relative humidity of 40%–60%. Hence, this study provides a simple method to prepare high-quality CsPbIBr<sub>2</sub> perovskite thin films with low-density defect and realize air-stable and charge-transport-layer-free CsPbIBr<sub>2</sub> photodetectors for practical applications in photoelectric detection field.

Highlights

  • 成新的防水层. 为此, 该团队利用硫脲 分子和铅离子之间的强相互作用, 改 善 了 CsPbIBr2 薄膜的表面形貌和稳定性, 器件表现出 较好的表面疏水性以及优异的电学稳定性 (在 10%RH 的大气环境下、56 天后, 初始值的 82.8%). 但目前为止, 高质量 CsPbIBr2 薄膜的制备和存储 仍然局限于超低湿度 (10% RH) 的大气环境或氮 气保护氛围中 [11,12,18]

  • 该器件 (ITO/CsPbIBr2/Au) 展现出微秒 量级的响应时间 (20, 21 μs) 和低暗电流密度 (2 × 10–4 mA·cm–2), 并具有出色的电学稳定性

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Summary

Introduction

为此, 本文提出了一种双配体 (卵磷脂 (L-a-phosphatidylcholine, LP) 和硫氰酸铵 (NH4SCN)) 策略, 可在相对 湿度不高于 60% 的大气环境下, 利用喷涂法制备出高结晶质量、结构稳定的钙钛矿薄膜. 这样, 制备出的未封装 CsPbIBr2 钙钛 矿光电探测器 (ITO/CsPbIBr2/Au) 具有低暗电流密度 (2×10–4 mA·cm–2)、 微秒级别的响应时间 (20, 21 μs) 和长效稳定性 (在相对湿度为 40%—60% 的大气环境下, 储存 70 天后, 仍能保持原光暗电流初始值的 81%) 等特性. 这样, 在 40%— 60% RH 的大气环境下, 未封装的 CsPbIBr2 钙钛 矿光电探测器 (ITO/CsPbIBr2/Au) 展示出较低的 暗电流密度 (10-4 mA·cm2)、微秒级别的响应时间 (20, 21 μs) 以及较好的电学稳定性 (在 40%—60% RH 的大气环境下、70 天后, 初始值的 81%). 实验用的化学原材料主要包括以下化学品: 溴 化铯 (CsI, 98%), 溴化铅 (PbBr2, 98%), 硫氰酸铵 (NH4SCN, 99.99%), 卵磷脂 (LP, 98%), 二甲基亚 砜 (DMSO, 99.9%), N, N-二甲基甲酰胺 (DMF, 99.9%).

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