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溶液法制备全无机钙钛矿太阳能电池的研究进展

王基铭 陈科 谢伟广 时婷婷 刘彭义 郑毅帆 朱瑞

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溶液法制备全无机钙钛矿太阳能电池的研究进展

王基铭, 陈科, 谢伟广, 时婷婷, 刘彭义, 郑毅帆, 朱瑞

Research progress of solution processed all-inorganic perovskite solar cell

Wang Ji-Ming, Chen Ke, Xie Wei-Guang, Shi Ting-Ting, Liu Peng-Yi, Zheng Yi-Fan, Zhu Rui
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  • 太阳能光伏技术, 能实现太阳能与电能的高效转换, 是实现人类文明可持续发展的关键绿色能源技术. 其中, 有机无机杂化钙钛矿太阳能电池具有优异的光电特性、低廉的制备成本、高效的转换效率, 已成为该领域的研究前沿. 虽然有机无机杂化钙钛矿太阳能电池的光电转换效率已约高达24%, 但其体系中的有机物组分易受环境中的光、热、潮等因素影响而分解, 致使器件稳定性存在严重的缺陷, 极大地限制了钙钛矿太阳能电池的产业化进程. 因此, 如何制备高效稳定的钙钛矿太阳能电池, 是目前该领域的研究热点与难点, 而发展具有更高环境稳定性的全无机钙钛矿太阳能电池具有重要意义. 本文回顾了近年来全无机钙钛矿太阳能电池领域的研究成果, 重点审视了钙钛矿薄膜的湿法制备工艺, 并探讨了器件在光热稳定性方面的改善, 为进一步推动钙钛矿太阳能电池的实用化进程提供可行性参考.
    Photovoltaic technology, which can converse solar illumination into electricity, is crucial to the sustainable development of human civilization. Among them, the organic-inorganic hybrid perovskite solar cell (OIPSC) has become a research front due to its excellent photoelectric characteristics, low production cost and high power conversion efficiency (PCE). Although the PCE of OIPSC has exceeded 24%, the organic components in the perovskite system are sensitive to the decomposion caused by either being exposed to light or heated in high temperature environment. The stability defects have greatly limited the commercialization of perovskite solar cells. Therefore, it is urgent to improve the stability of perovskite solar cells, especially to solve the material decomposition problem. All-inorganic perovskite photovoltaic material, composed of all-inorganic elements, exhibits excellent heat and moisture resistance. Therefore, the development of all-inorganic perovskite solar cells is of great significance for solving the current stability problems in perovskite photovoltaics. In this work, we review the recent research progress of all-inorganic perovskite solar cells, discuss the solution approaches to processing all-inorganic perovskite films, and explore the enhancement of device stability. Our work provides a guideline for further promoting the device stability and PCE.
      通信作者: 刘彭义, tlpy@jnu.edu.cn ; 郑毅帆, yifan.zheng@pku.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 11804117, 61674070)、中央高校基本科研业务费专项资金(暨南大学科研培育与创新基金)(批准号: 21618313)、广东省科技攻关计划(批准号: 2017B09090701)和博士后创新人才支持计划(批准号: 8206200013)资助的课题.
      Corresponding author: Liu Peng-Yi, tlpy@jnu.edu.cn ; Zheng Yi-Fan, yifan.zheng@pku.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11804117, 61674070), the Fundamental Research Funds for the Central Universities, China (Grant No. 21618313), the Key Science and Technology Program of Guangdong Province, China (Grant No. 2017B09090701), and the China Postdoctoral Innovation Talent Foundation (Grant No. 8206200013).
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  • 图 1  立方晶格钙钛矿结构ABX3

    Fig. 1.  Cubic perovskite structures of ABX3.

    图 2  (a)一步成膜法制备CsPbI3粉末及薄膜[38]; (b)多步成膜法制备CsPbBr3[49]; (c)喷涂[62]; (d)一步静电纺丝工艺[63]

    Fig. 2.  Schematic illustration of (a) the one-step solution-phase synthesis and powders and thin film fabrication of CsPbI3[38], (b) the multi-step fabrication process of the cesium lead bromide films[49]; (c) spray-coated[62]; (d) one-step electrospinning technique[63].

    图 3  (a) CsPbBr3, Cs0.98Li0.02PbBr3, Cs0.94Na0.06PbBr3, Cs0.92K0.08PbBr3和Cs0.91Rb0.09PbBr3薄膜的表面扫描电子显微镜(SEM)图像和不同碱金属阳离子掺杂全无机PSCs的伏安特性曲线[65]. (b) 各种金属离子对Pb2+的部分取代(掺杂或合金化), 改善正交CsPbBr3的热稳定性, 使α-CsPbI3稳定化[83]. 下图显示了Sn基全无机钙钛矿中随Br浓度变化的带隙变化曲线图: 从左到右为CsSnI3, CsSnI2Br, CsSnIBr2和CsSnBr3[84]. (c) 在FTO / c-TiO2/m-TiO2基底上制备的不同镧系元素掺杂的钙钛矿薄膜的SEM图像: CsPbBr3, Yb3+-CsPbBr3, Er3+-CsPbBr3, Ho3+-CsPbBr3, Tb3+-CsPbBr3, Sm3+-CsPbBr3[90]; (d)纯CsPbI3和CsPbI3–xClx的化学烧结薄膜的紫外-可见吸收光谱和Abs及PL (右侧, 吸收(细线)和光致发光(粗线))图谱[94,95]; (e) CsPbI3通过PEO进行相稳定的机制和薄膜制备流程[99]

    Fig. 3.  (a) Scanning electron microscope (SEM) images of the CsPbBr3, Cs0.98Li0.02PbBr3, Cs0.94Na0.06PbBr3, Cs0.92K0.08PbBr3, and Cs0.91Rb0.09PbBr3 films and J-V curves of different alkali metal cations doped PSCs under air mass 1.5 global[65]. (b) Schematic representation showing partial substitution (doping or alloying) of Pb2+ by various metal ions, which can lead to stabilization of α-CsPbI3 at room temperature and improved thermal stability of orthorhombic CsPbBr3[83]. The graphic is about band gap variation with respect to Br concentration in the Sn based all-inorganic perovskite: CsSnI3, CsSnI2Br, CsSnIBr2 and CsSnBr3 from left to right[84]. (c) The top SEM images of as-prepared perovskite films with different Lanthanide-doping on FTO/c-TiO2/m-TiO2 substrates CsPbBr3, Yb3+-CsPbBr3, Er3+-CsPbBr3, Ho3+-CsPbBr3, Tb3+-CsPbBr3, Sm3+-CsPbBr3[90]. (d) UV-vis absorbance spectra of chemically sintered thin films of pure CsPbI3 and CsPbI3−xClx, absorption spectra (thin lines) and photoluminescence (PL) spectra (thick lines) of CsPbX3 samples[94,95]. (e) PEO added in precursor colloidal solution to improve the stability of perovskite film and the fabrication process of CsPbI3[99].

    图 4  (a) α-CsPbI3 QDs PCSs的结构和基于μGR/ CsPbI3薄膜的PSCs的电荷传输过程和稳定机制的示意图[113]; (b) 基于CsPbI3钙钛矿纳米线的光电探测器装置的能带图, 其中铝和氧化铟锡(indium tin oxides, ITO)作为电极, 基于CsPbI3钙钛矿纳米线的器件的示意图, 具有面积为0.0314 cm2的ITO的顶部圆形电极[122]; (c) 合成2D超薄CsPbBr3纳米片高倍放大SEM图像[125]; (d) 分级界面的太阳能电池的结构示意图和SEM图像[133]

    Fig. 4.  (a) Architecture of the completed α-CsPbI3 device and the charge transport process and stabilization mechanism for the μGR/CsPbI3 film based PSCs[113]; (b) band diagram for CsPbI3 perovskite nanowires (NWs)-based photodetector device and CsPbI3 perovskite NWs based device with top circular electorode[122]; (c) 2D-CsPbBr3 nanosheets high-magnification SEM images[125]; (d) schematic structures of devices without and with a graded interface and SEM images of CsPbBrI2 film, CsPbBrI2 NSs/CsPbBrI2 film, CsPbBrI2 QDs/CsPbBrI2 film, and CsPbBrI2 QDs/CsPbBrI2 NSs/CsPbBrI2 film[133].

    图 5  (a) KPFM测量非老化和热老化的CsPbBr3振幅, 晶界上的形貌和功函数信号[135]; (b) CsPbI3在5 kV, 1 nA和点1, 2和3的CL光谱下的SEM图像[16]; (c)在光照射前后比较CsPbBr3和MAPbBr3之间的SEM图像的示意图[15]; (d) CsPbI3钙钛矿薄膜上的梯度Br掺杂和PTA有机阳离子表面钝化的示意图[27]

    Fig. 5.  (a) KPFM measurement on the non-aged and thermally aged CsPbBr3 amplitude, cross-sections of topography and work function signals over the grain boundary[135]; (b) SEM image of CsPbI3 under 5 kV, 1 nA, and CL spectra of points 1, 2 and 3 [16]; (c) schematic comparing SEM images between the CsPbBr3 and MAPbBr3 before and after illumination[15]; (d) gradient Br doping and PTA organic cation surface passivation on CsPbI3 perovskite thin film[27].

    表 1  溶液法及其他方法全无机PSCs性能

    Table 1.  Performance of all inorganic perovskite solar cells fabricated by solution or other process.

    电池结构制备方法VOC/VJsc/mA·cm–2FF/%PCE/%参考文献
    FTO/PEDOT:PSS/CsPbI3/PCBM/Al溶液法~0.931.7[26]
    FTO/c-TiO2/CsPbI3/Spiro-OMeTAD/Au溶液法0.8122.9[26]
    FTO/c-TiO2/m-TiO2/CsPbI3/Spiro-OMeTAD/Au溶液法~0.681.3[26]
    FTO/c-TiO2/CsPbI3/CuI/Au溶液法0.8916.0256.598.07[149]
    FTO/c-TiO2/CsPb0.96Bi0.04I3/CuI/Au溶液法0.9718.7672.5913.21[149]
    FTO/TiO2/CsPbI3/Spiro-OMeTAD/Ag溶液法0.6611.9252.474.13[39]
    FTO/c-TiO2/CsPbI3/Carbon溶液法0.6714.31484.65[38]
    FTO/c-TiO2/m-TiO2/CsPbI3/Carbon溶液法0.5813.74443.48[38]
    FTO/TiO2/AX-coatedCsPbI3-QDs/Spiro-OMeTAD/MoOx/Al溶液法1.1615.2476.6313.43[110]
    FTO/TiO2/CsPbI3 QDs/Spiro-OMeTAD/MoOx/Al溶液法1.2313.476510.77[23]
    MgF2/FTO/c-TiO2/m-TiO2/CsPb0.95Ca0.05I3/P3HT/Au溶液法0.9517.98013.5[78]
    ITO/PTAA/zwitterion-CsPb(I0.98Cl0.02)3/PCBM/C60/BCP/Al溶液法1.0914.97011.4[150]
    ITO/TiO2/CsPbBr3/Carbon溶液法0.645.3643.9[151]
    FTO/TiO2/CsPbI2Br-0.02MnCl2/PCBM/Ag溶液法1.17214.378013.47[85]
    FTO/TiO2/CsPbI2Br/PTAA/Au溶液法1.17714.2580.213.45[77]
    FTO/TiO2/CsPbI3 QDs/PTAA/Au溶液法1.19211.7578.310.97[77]
    FTO/c-TiO2/CsPbI3-0.05DETAI3/P3HT/Au溶液法1.0612.21617.89[101]
    FTO/TiO2/quasi-2D Cs0.9PEA0.1PbI3/Spiro-OMeTAD/Au溶液法0.83810.96625.7[128]
    FTO/NiOx/InCl3:CsPbI2Br/ZnO@C60/Ag溶液法1.1515.17813.57[91]
    FTO/NiOx/CsPbI2Br/ZnO@C60/Ag溶液法1.115.17812.92[91]
    FTO/TiO2/CsPbI3/Carbon溶液法0.7918.5659.5[37]
    FTO/TiO2/CsPbI3 QDs/PTB7/MoOx/Ag溶液法1.2712.398012.55[112]
    FTO/c-TiO2/BA2CsPb2I7/Spiro-OMeTAD/Au溶液法0.9578.88574.84[127]
    FTO/TiO2/CsPb0.995Mn0.005I1.01Br1.99/Carbon溶液法0.9913.15577.36[86]
    FTO/bl-TiO2/2 wt% Sn-TiO2/Cs2SnI4Br2/solid state Cs2SnI6 based HTM/LPAH溶液法0.5636.2257.72.025[52]
    FTO/TiO2/CsPbI2Br/CsPbI3 QDs/PTAA/Au溶液法1.20415.2578.714.45[77]
    FTO/c-TiO2/m-TiO2/CsPbBr3/MoS2 QDs/Carbon喷涂法1.3076.5579.46.80[152]
    FTO/c-TiO2/m-TiO2/CsPbIBr2/Spiro-OMeTAD/Au喷涂法1.1217.9706.2[59]
    FTO/SnO2 QDs/CsPbBr3/carbon溶液法1.5727.68759.15[50]
    ITO/PEDOT:PSS/CsPbBr3/PCBM/Ag溶液法0.9825.973.74.5[135]
    FTO/m-TiO2/CsPbBr3/CsBi2/3Br3/carbon溶液法1.5947.7580.910.0[50]
    FTO/SnO2 QDs/CsPbBr3/CsSnBr3 QDs/carbon溶液法1.6107.884.410.6[50]
    FTO/m-TiO2/Cs2AgBiBr6/Spiro-MeOTAD/Ag溶液法0.983.93632.43[76]
    FTO/TiO2/PTABrCsPbI3/Spiro-MeOTAD/Ag溶液法1.10419.1568.517.06[27]
    FTO/TiO2/CsPbI3/Spiro-MeOTAD/Ag溶液法1.05118.8968.513.61[27]
    PET/ITO/TiO2/CsPb0.96Bi0.04I3/Spiro-OMeTAD/Au溶液-气相辅助法1.0515.1172.3211.47[87]
    ITO/TiO2/CsPbI3/P3HT/Au气相法1.06313.871.610.5[142]
    ITO/TiO2/CsPbI3/Au气相法0.9598.7564.7[46]
    ITO/C60/CsPbI2Br/TAPC/MoO3/Ag气相法1.1515.26711.7[140]
    FTO/TiO2/CsPbI3/P3HT/Ag气相法0.7912..06726.79[146]
    下载: 导出CSV
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出版历程
  • 收稿日期:  2019-03-13
  • 修回日期:  2019-04-04
  • 上网日期:  2019-08-01
  • 刊出日期:  2019-08-05

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