转移法制备顶电极在钙钛矿太阳能电池中的应用

肖俊彦; 彭超; 程一兵

doi:10.13801/j.cnki.fhclxb.20211215.001

转移法制备顶电极在钙钛矿太阳能电池中的应用

doi: 10.13801/j.cnki.fhclxb.20211215.001

肖俊彦^{1, 2, ,},
彭超¹,
程一兵²

1.
武汉理工大学　材料科学与工程学院, 武汉 430070
2.
武汉理工大学　材料复合新技术国家重点实验室, 武汉 430070

基金项目: 国家自然科学基金 (52002303)；湖北省自然科学基金(2020CFB427)

详细信息

作者简介:
肖俊彦，武汉理工大学材料科学与工程学院副教授。2010年于南开大学化学学院和天津大学化工学院，分别获理学、工学学士学位。2015年于中国科学院物理研究所，获理学博士学位。2018年加入武汉理工大学材料科学与工程学院，目前讲授《材料工程基础》、《光电子材料》等专业课程。近十年来一直从事染料敏化太阳能电池、量子点太阳能电池、钙钛矿太阳能电池等新型光伏技术的研究，已发表相关论文30余篇。目前致力于低成本材料和环境友好工艺在新型太阳能电池中的应用研究

通讯作者:
肖俊彦，博士，副教授，硕士生导师，研究方向为新型太阳能电池材料与器件　E-mail: xiaojunyan@whut.edu.cn

中图分类号: TB34; TM914.4
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出版历程
- 收稿日期: 2021-10-28
- 修回日期: 2021-12-02
- 录用日期: 2021-12-04
- 网络出版日期: 2021-12-16
- 刊出日期: 2022-03-23

Application of transferred top electrode in perovskite solar cells

1.
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
2.
State Key Laboratory of Advanced Technologies for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

摘要

摘要: 钙钛矿太阳能电池因为其高效率、易制备和低成本等优点，近年来发展迅速。在钙钛矿器件的多层薄膜结构制备和调控中，研究者们关注最多的是钙钛矿吸光层和电荷传输层。而顶电极部分的问题，由于蒸镀Au电极作为实验室阶段标准研究方法的成功使用，而容易被人们忽略。然而，蒸镀贵金属电极的生产设备和原材料成本问题，在钙钛矿太阳能电池未来的大面积器件制备、大范围应用中将是难以避免的。为此，研究者开发了导电膜转移法、导电浆料涂布法等非蒸镀工艺，尝试解决这些问题。本综述针对这一现状，从工艺方法的角度出发，介绍包括金属、聚合物、碳等多种材料体系的顶电极的转移法应用进展，总结具有普遍性的原理、规律，讨论目前技术的缺陷、瓶颈问题和潜在的解决方案。
- 钙钛矿太阳能电池 /
- 顶电极 /
- 转移法 /
- 碳材料 /
- 导电聚合物 /
- 导电胶
Abstract: Recent years, perovskite solar cells have been developing rapidly because of the high efficiency, ease of preparation and low cost. To the preparation and optimization of multilayer structures for perovskite devices, researchers always pay most attention on the perovskite light absorber and charge-transporting layers. While in the case of the top electrode, evaporated Au electrodes can work well as a standard method at the current laboratory stage. Therefore, the top electrode issue is easily overlooked by researchers. However, the high cost of equipments and raw materials for evaporated precious metal electrodes will not be ignored in the large-area devices manufacturing and large-scale applications of perovskite solar cells. Several non-evaporation processes such as conductive film transferring or conductive paste coating have been developed to solve these problems. Herein, we addresses the current progress of transfer methods top electrodes from the perspective of process techniques. A variety of material systems including metals, polymers and carbon are compared to summarize some general principles. Also, the shortcomings of the transfer method, and bottlenecks of materials and potential solutions for ideal transfer electrodes are discussed.
- perovskite solar cells /
- top electrode /
- transfer method /
- carbon materials /
- conductive polymers /
- conductive adhesive

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图 1 钙钛矿太阳能电池中基于转移法的薄膜顶电极(a)和厚膜顶电极(b)制备流程示意图

Figure 1. Schematic diagrams of the transfer process for thin film (a) and thick film (b) top electrode for PSCs

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图 2 (a)基于转移法聚苯乙烯磺酸盐(PEDOT:PSS)顶电极的钙钛矿太阳能电池结构示意图；(b)彩色钙钛矿太阳能电池照片^[18]

Figure 2. (a) Device structure of transferred polystyrene sulfonate (PEDOT:PSS) electrode based PSCs; (b) Photographs of colorful PSCs^[18]

TCO—Transparent conductive oxide; ETL—Electron transporting layer; HTL—Hole transporting layer; PEDOT:PSS^T—Transferred PEDOT:PSS

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图 3 干法转印PEDOT∶PSS顶电极的流程图(a)、PEDOT:PSS转印顶电极(b)和半透明钙钛矿电池(c)的照片^[19]

Figure 3. Schematic diagrams of the dry stamping transfer process of the PEDOT:PSS layer for PSCs (a), photographs of transferred PEDOT:PSS top electrode layer onto the device (b) and semitransparent PSCs (c)^[19]

PUA—Polyurethane acrylate; PEI—Polyethyleneimine; ITO—Indium tin oxide

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图 4 (a)自支撑碳纳米管薄膜的照片；(b)基于转移碳纳米管薄膜电极的钙钛矿器件结构示意图^[8]

Figure 4. (a) Photograph of free-standing CNT film; (b) Device structure of PSC with transferred CNT film electrode^[8]

FTO—F-doped tin oxide; CNT—Carbon nanotube

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图 5 基于转移石墨烯电极的钙钛矿器件结构示意图、实物照片和J-V特性曲线^[9]

Figure 5. Device structure, photograph and J-V characteristics of transferred graphene electrode based PSCs^[9]

PDMS—Polydimethylsiloxane; PMMA—Polymethyl methacrylate

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图 6 基于转移法Cu纳米线网络电极的钙钛矿器件的结构示意图(a)和SEM截面图像(b)^[30]

Figure 6. Schematic structure (a) and SEM cross-sectional images (b) of a PSCs with transferred Cu-nanowire networks top electrode^[30]

CuNW—Cu-nanomire

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图 7 PTFE基底转印Au薄膜电极的流程示意图^[12]

Figure 7. Schematic diagrams of the PTFE substrate pressing transferred Au electrode on PSCs^[12]

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图 8 多孔Au箔电极在钙钛矿太阳能电池中的制备和循环使用示意图^[11]

Figure 8. Schematic flow of the fabrication and restoration process of the nanoporous Au electrode in PSCs^[11]

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图 9 带有PEDOT∶PSS导电胶涂层并嵌入Ni网的PET膜的SEM图像(a)和实物照片(b)以及相应的钙钛矿器件示意图 (c)^[14]

Figure 9. SEM image (a) and photograph (b) of PEDOT:PSS conducting adhesive applied to an PET embedded Ni grid and device structure of PSCs with the composite electrode (c)^[14]

TCA—Transparent conducting adhesive

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图 10 自粘性大孔碳膜的制备流程示意图(a)和孔隙形成机制示意图(b)^[35]，以及相应的钙钛矿器件截面SEM图像(c)^[37]

Figure 10. Schematic diagrams (a) and microscopic mechanism of self-adhesive macroporous carbon film electrode (b)^[35], and SEM cross-sectional image of a PSCs with transferred carbon film electrode (c)^[37]

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图 11 基于PEDOT∶PSS和各种导电基底的堆叠式钙钛矿太阳能电池结构示意图^[38]

Figure 11. PEDOT:PSS based stacking structured PSCs with various electrode substrates^[38]

c&m-TiO₂—Compact and mesoporous TiO₂ layers

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表 1 几种代表性的转移法顶电极技术总结

Table 1. Summary of several transferred top electrode techniques

Top electrode	Substrate	Transfer process	PCE/%	Device	Ref.
PEDOT:PSS	Plastic wrap (peel off)	Assisted with one drop of isopropanol	10.1 2.9 ^l	Conventional Semitransparent	[17]
PEDOT:PSS	PDMS(peel off)	Assisted with O₂ plasma for 5 s	15.1	Conventional Colorful	[18]
PEI doped PEDOT:PSS	PUA/PC (peel off)	Roll press under 100℃	13.6 ^{f, l}	Inverted Semitransparent	[19]
Doped CNT film	Membrane film(peel off)	Assisted with 200 μL spiro-OMeTAD	17.56	Conventional	[23]
CNT film	Si wafer	Assisted with droplets of chlorobenzene	11.9 ^f	Conventional	[21]
CNT film	Si wafer	Assisted with 100 μL PEI-isopropanol solution	10.8	Inverted	[25]
Graphene/ PEDOT:PSS	PDMS/PMMA	Roll press under 65℃	12.37	Conventional Semitransparent	[9]
Ag nanowire film	PET(peel off)	Ball bearing press under 500 g force	12.7	Conventional Semitransparent	[29]
Au	PTFE(peel off)	Roll press	17.14	Conventional	[12]
Nanoporous Au	Membrane ﬁlm(peel off)	Assisted with 200 μL anhydrous ethanol	19.0 17.3 ^f	Conventional	[11]
Ni particles in acrylic	Cu foil	Roll press under 70℃, 980 Pa	12.5	Inverted	[13]
PEDOT:PSS in acrylic	Ni mesh embedded PET	Press onto PEDOT:PSS covered semi-cell	15.5	Conventional Semitransparent	[14]
Carbon paste film		Flat press under 0.7 MPa	19.2	Conventional	[35]
Carbon paste film	Conductive cloth	Flat press	19.36 14.05 ^{f, l}	Conventional	[37]
PEDOT:PSS	Al foil, Cu foil, FTO etc.	Stack with PEDOT:PSS covered semi-cell	14.6	Conventional	[38]
Graphene	Al foil, FTO	Stack with graphene covered semi-cell	18.65 16.42 ^l	Conventional	[40]
Notes: Upper script "f" represents flexible device, and "l" represents large device area about 1 cm²; PDMS, PC, PET, PMMA, PTFE are abbreviations for common polymer materials.

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