目的 提高宽带隙卤化铅钙钛矿薄膜的光电转换性能和湿稳定性。方法 在前驱体溶液中掺杂15%（物质的量分数）甲基氯化胺（MACl）,在薄膜表面旋涂丁基溴化胺（BABr）、己基溴化胺（HABr）及辛基溴化胺（OABr）。结果 掺杂MACl后,薄膜的晶粒尺寸增大,薄膜晶界处PbI2缺陷减少,薄膜体相的载流子传输得到改善。薄膜在埋底界面的浸润性提升,薄膜的光致发光强度降低,光生空穴在薄膜埋底界面的传输过程得到优化,薄膜的光电转换性能得以提升。长链烷基溴化物对薄膜进行表面处理后,钙钛矿薄膜及电子传输层薄膜的表面电势均有所降低,OABr处理后的钙钛矿薄膜与电子传输层薄膜之间的表面电势差最小,说明光生电子在界面传输时的能量损失最小。此外,长链烷基溴化物还可以提升钙钛矿薄膜表面的浸润性,OABr处理后的薄膜表面浸润性最好。同时,经OABr处理后,薄膜的光电转换性能和湿稳定性得以提升。结论 经过MACl体相掺杂和OABr表面处理后,宽带隙卤化铅钙钛矿薄膜的光电转换性能和湿稳定性显著提升。在基于ITO/MeO-2PACz/MACl掺杂及OABr表面处理的宽带隙卤化铅钙钛矿薄膜（1.79 eV）/ PCBM/BCP/Ag结构的反型钙钛矿太阳能电池器件中,实现了1.26 V的开路电压和17.47%的能量转换效率。
Abstract
In this paper, the doping modification of conventional bandgap lead halide perovskite films is introduced into wide bandgap lead halide perovskite films to improve the wettability of the films' buried interface and surface as an innovative point to enhance the photoelectric conversion performance and wet stability of the films. Two-dimensional perovskite ultrathin modification layers are grown in situ by first doping 15 mol% MACl in wide bandgap lead halide perovskite films and then spin-coating long chain alkyl bromides onto the surface of the films to construct a two-dimensional/three-dimensional perovskite heterostructure. The MACl-doped and long chain alkyl bromide surface-treated wide bandgap lead halide perovskite film is used as the light absorbing layer, MeO-2PACz as the hole transporting layer, and PCBM as the electron transporting layer, to prepare p-i-n wide bandgap lead halide perovskite solar cells.
The surface morphology of the wide bandgap lead halide perovskite films is observed with a scanning electron microscope (Hitachi SU-70), and it is found that MACl is able to increase the grain size of the films and reduce the holes on the surface of the films as well as the PbI2 defects at the grain boundaries. The crystal structure of the wide bandgap lead halide perovskite films is characterized with an X-ray diffractometer (Bruker D8 Advance), and it is found that the characteristic peaks of the PbI2 phase disappear after doping with MACl. The PL spectra of wide bandgap lead halide perovskite films on MeO-2PACz substrates are tested with a fluorescence spectrometer (Edinburgh FLS920), and the attenuation of the PL intensity suggests that doping with MACl improves the carrier transport of the films at the buried interface. The surface potentials of the perovskite and PCBM films before and after treatment with long chain alkyl bromides are tested with a Kelvin probe force microscope (Bruker MultiMode 8), and it is found that alkyl bromide treatment is able to reduce the surface potentials of perovskite and PCBM films, and that the difference in the surface potentials between OABr-treated perovskite and PCBM films is the smallest, indicating that the energy loss of photogenerated electrons is minimized when they are transported at this interface. The contact angle of the perovskite precursor solution at the buried interface before and after MACl doping, the contact angle of PCBM solution on the surface of perovskite film before and after treatment with long chain alkyl bromide, and the contact angle of water are measured with a contact angle measuring instrument (Dataphysics OCA). The contact angle of the perovskite precursor solution at the buried interface decreases by 8° after MACl doping, and this enhancement of wettability reduces the amount of precursor solution used in the spin-coating process. In addition, the contact angle of the PCBM solution on the film surface decreases with the increase of the chain length of alkyl bromides, and the water contact angle on the film surface increases with the increase of the chain length of alkyl bromides, indicating that the treatment of long chain alkyl bromides can enhance the wettability and hydrophobicity of the PCBM solution on the film surface.
Based on the wide bandgap lead halide perovskite thin films obtained via this synergistic optimization strategy, an inverted solar cell with structure of ITO/MeO-2PACz/OABr and MACl passivated wide bandgap lead halide perovskite film (1.79 eV)/ PCBM/BCP/Ag is synthesized, which achieves an open-circuit voltage of 1.26 V and 17.47% power conversion efficiency.
关键词
卤化铅钙钛矿薄膜 /
半导体薄膜 /
宽带隙半导体 /
表面和界面 /
光电转换
Key words
lead halide perovskite films /
semiconductor thin films /
wide bandgap semiconductor /
surface and interface /
photoelectronic conversion
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基金
辽宁省自然科学基金面上项目（2021MS008）
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