异质结构在光伏型卤化物钙钛矿光电转换器件中的应用

郤育莺; 韩悦; 李国辉; 翟爱平; 冀婷; 郝玉英; 崔艳霞

doi:10.7498/aps.69.20200591

摘要

钙钛矿材料由于具有长的载流子扩散长度、较高的吸收系数和较低的缺陷态密度等优点在太阳电池、光电探测器、发光二极管等光电转换器件领域得到广泛应用. 同时, 层状二维材料、低维半导体纳米结构、金属纳米结构和绝缘材料等功能材料因它们特殊的化学、电学和物理性质而越来越受到人们的关注. 为了拓宽钙钛矿材料在光电转换器件的应用, 可将钙钛矿与这些功能材料进行组合, 形成异质结构, 集成两种材料的优点. 钙钛矿/功能材料异质结构可作为界面修饰层、电荷传输层、封装层等应用于卤化物钙钛矿光电转换器件中, 用来抑制光生载流子的复合损耗, 提升载流子的传输性能, 改善器件的稳定性等. 本文综述了钙钛矿与层状二维材料、低维半导体纳米结构、金属纳米结构和绝缘材料等形成的异质结构在光伏型光电转换器件中应用的最新研究进展, 并对该方向未来的发展做出了展望.

关键词:

Abstract

Perovskites are widely used in various kinds of optoelectronic devices, including solar cells, photodetectors, light-emitting diodes, etc., due to their excellent properties such as long carrier diffusion length, high absorption coefficient, low trap state density and so on. Functional materials such as layered two-dimensional materials (graphene, transition metal dichalcogenides, etc.),low-dimensional semiconductor nanostructures (nanoparticles, quantum dots, nanowires, nanotubes,nanorods,nanopieces,etc.), metallic nanostructures(Au,Ag, etc.) and insulating materials (insulating polymer, organic amine, inorganic insulating film, etc.) have attracted more and more attention due to their special chemical, electrical and physical properties.In order to broaden the application of perovskites in photovoltaic devices, perovskites can be combined with various functional materials to form heterostructures so as to combine the advantages of the two types of materials.The heterostructures of perovskites/functional materials can be used as the interface modification layer in halide perovskites photovoltaic devices, to improve the crystallinity of perovskite, effectively reduce the surface defects and suppress the carrier recombination loss at the interface. The heterostructures of perovskites/functional materials can be used as the charge transporting layer in halide perovskites photovoltaic devices, can match well with the perovskite energy levels, which is beneficial to the efficient extraction of holes and electrons. The heterostructures of perovskites/functional materials also can be used as encapsulation layer in halide perovskites photovoltaic devices, to reduce the contact between water and perovskite, it can effectively prevent the degradation of perovskite, to improve the device stability.In addition, the semiconductor with narrow bandgap or array structure can be used to broaden the spectral response and to improve the light absorption of the perovskite photovoltaic devices.In a word, the heterostructures of perovskites/functional materials are applied to devices is an effective way to obtain high performance and low cost photovoltaic devices.In this review, recent works on the applications of the heterostructures in halide perovskite photovoltaic devices are comprehensively presented and discussed. The progress and advantages of the heterostructures as the interface modification layer, charge transporting layers and encapsulation layer in halide perovskite photovoltaic devices are systemically reviewed. Finally, we summarize the whole paper and give a prospect for the development of heterostructures based perovskite photovoltaic devices in the future.

Keywords:

作者及机构信息

太原理工大学物理与光电工程学院, 太原　030024

通信作者: 李国辉, liguohui@tyut.edu.cn ; 崔艳霞, yanxiacui@gmail.com

Authors and contacts

College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, China

Corresponding author: Li Guo-Hui, liguohui@tyut.edu.cn ; Cui Yan-Xia, yanxiacui@gmail.com

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施引文献

图 1 (a) 基于GO:Spiro-OMe-TAD复合HTL的钙钛矿太阳电池的结构示意图和能级示意图^[20]; (b) 基于rGO:PCBM复合ETL的钙钛矿太阳电池的结构图^[22]; (c) 钙钛矿薄膜在不同基底(ITO/GO, ITO/PEDOT:PSS和ITO)上的SEM图像^[29]; (d) 有无Ag-rGO掺杂的钙钛矿太阳电池分别在相对湿度为45%—55%的室温下放置330 天后器件的PCE变化曲线^[38]

Fig. 1. (a)Structural diagram and energy level diagram of the perovskite solar cell based on the GO:Spiro-OMe-TAD composite HTL^[20]; (b)structural diagram of the perovskite solar cell based on the rGO:PCBM composite ETL^[22]; (c)SEM images of perovskite films on different substrates (ITO/GO, ITO/PEDOT:PSS, and bare ITO)^[29]; (d)PCE degradation trend for the perovskite solar cells with/without Ag-rGO after 330 days storage in 45%–55% relative humidity at room temperature^[38].

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图 2 (a) 基于MoS₂:Spiro-OMe-TAD复合HTL的钙钛矿太阳电池的结构图^[47]; (b) 基于MoS₂:Spiro-OMe-TAD复合HTL的钙钛矿太阳电池的能级图^[47]; (c) 基于TiO₂:MoS₂复合ETL的钙钛矿太阳电池的阻抗分析图(R_s代表串联电阻、R_sc代表电子选择性接触产生的并联电阻、R_rec代表与活性层相关的并联电阻)^[52]

Fig. 2. (a)Schematic diagram of the perovskite solar cell based on the MoS₂:Spiro-OMe-TAD composite HTL ^[47]; (b)energy level diagram of the perovskite solar cell based on the MoS₂:Spiro-OMe-TAD composite HTL^[47]; (c)impedance analysis spectrum of the perovskite solar cell based on the TiO₂:MoS₂ composite ETL (R_s: the series resistance, R_sc: the shunt resistance generated by electron selective contacts, and R_rec; the shunt resistance associated with the active layer)^[52].

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图 3 (a) ZnO纳米颗粒作ETL的钙钛矿太阳电池的能级图^[64]; (b) 基于CsPbBr₃:ZnO异质结构的光电探测器原理图^[65]; (c) 无机钙钛矿α-CsPbI₃量子点作为界面层应用在钙钛矿太阳电池中的示意图^[68]; (d) 不同薄膜的光学吸收谱(纯PbS QDs, 纯CH₃NH₃PbI₃, PbS QDs/CH₃NH₃PbI₃)^[69]; (e) TiO₂纳米管填充钙钛矿前后的电镜图对比图^[75]; (f) 不同薄膜(CH₃NH₃PbI₃/NiO-NP、CH₃NH₃PbI₃/NiO-NS、CH₃NH₃PbI₃/ZrO₂-NP)的时间分辨PL图^[77]

Fig. 3. (a)Energy level diagram of the perovskite solar cell based on the ZnO nanoparticles ETL ^[64]; (b)schematic diagram of the photodetector based on the CsPbBr₃:ZnO heterostructure ^[65]; (c)schematic diagram of the perovskite solar cell using α-CsPbI₃ quantum dots as the interface layer^[68]; (d)absorption spectra of different thin films (pristine PbS QDs, pristine CH₃NH₃PbI₃, and PbS QDs/CH₃NH₃PbI₃)^[69]; (e) SEM images of TiO₂ nanotubes before and after the perovskite deposition^[75]; (f)time-resolved photoluminescence decays of different thin films (CH₃NH₃PbI₃/NiO-NP, CH₃NH₃PbI₃/NiO-NS, and CH₃NH₃PbI₃/ZrO₂-NP)^[77].

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图 4 (a) 基于Au-NRs@SiO₂/CH₃NH₃PbI₃异质结构的钙钛矿太阳电池的原理图^[83]; (b) 与AuAg-NPs@SiO₂相结合的二维钙钛矿太阳电池的结构图和能级图^[86]; (c) CH₃NH₃PbI₃钙钛矿太阳电池的结构为FTO/Ag-NPs@compact-TiO₂/CH₃NH₃PbI₃:TiO₂/Au^[88]; (d) 不同薄膜的稳态PL谱(CH₃NH₃PbI₃, TiO₂/CH₃NH₃PbI₃, TiO₂:AuAg-NPs/CH₃NH₃PbI₃)^[92]

Fig. 4. (a)Schematic diagram of the perovskite solar cell with CH₃NH₃PbI₃/Au-NRs@SiO₂ heterostructure^[83]; (b)schematic diagram and energy level diagram of the quasi-2 D perovskite solar cell incorporated with AuAg-NPs@SiO₂^[86]; (c)schematic diagram of the perovskite solar cell with a configuration of FTO/Ag-NPs@compact-TiO₂/CH₃NH₃PbI₃:TiO₂/Au^[88]; (d)steady-state PL spectra of different films (CH₃NH₃PbI₃, TiO₂/CH₃NH₃PbI₃, and TiO₂:AuAg-NPs/CH₃NH₃PbI₃)^[92].

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图 5 (a) 含PS层的钙钛矿太阳电池的能级图和钙钛矿层与HTL层之间的电荷传输示意图^[95]; (b) PVP作界面层的钙钛矿太阳电池的结构图^[96]; (c) 有无PVP绝缘材料时钙钛矿薄膜表面的SEM对比图^[101]; (d) 有无PVP绝缘材料的钙钛矿太阳电池在相对湿度为50%的室温下储存30天后, 器件的PCE的变化曲线^[99]

Fig. 5. (a) Energy level diagram of the perovskite solar cell incorporated with a PS layer and schematic diagram illustrating the carrier transfer at the interface between the perovskite and HTL layers^[95]; (b) schematic diagram of the perovskite solar cell with a the PVP layer inserted between the perovskite and the HTL^[96]; (c)SEM images of the perovskite films with/without PVP ^[101]; (d) PCE degradation trend for perovskite solar cells devices with/without PVP after 30 days storage in 50% relative humidity at room temperature ^[99].

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异质结构在光伏型卤化物钙钛矿光电转换器件中的应用