倒置结构全无机钙钛矿太阳能电池的界面层研究进展

束倩文; 李一宵; 冯莱

doi:10.13801/j.cnki.fhclxb.20220120.003

倒置结构全无机钙钛矿太阳能电池的界面层研究进展

doi: 10.13801/j.cnki.fhclxb.20220120.003

苏州大学　能源学院，苏州 215006

基金项目: 国家自然科学基金 (52172050; 51772195); 江苏省六大高峰人才计划(XCL-078); 国家重点研发计划项目(2020YFB1506401)与苏州市先进碳材料与可穿戴能源重点实验室

详细信息

作者简介:
冯莱，江苏省特聘教授，博士生导师。1997和2000年毕业于大连理工大学，获学士、硕士学位；2003年获北京大学理学博士学位。2003–2007年先后作为日本学术振兴会(JSPS)外国人特别研究员在日本筑波大学(University of Tsukuba)工作，及洪堡学者在埃尔兰根大学（Friedrich-Alexander-University of Erlangen-Nürnberg）访问工作。2007–2012年先后作为副研究员在中科院化学所工作以及作为外国人研究员在日本筑波大学筑波前沿研究联盟中心工作。在Acc. Chem. Res., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Small, J. Mater. Chem. A, Appl. Catal. B Environ.等国际重要学术期刊发表论文90余篇，合作编写三部英文专著各一章节，获授权专利10件

通讯作者:
冯莱，博士，教授，博士生导师，研究方向为钙钛矿太阳能电池　E-mail: fenglai@suda.edu.cn

中图分类号: TM914.4
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出版历程
- 收稿日期: 2021-11-18
- 修回日期: 2021-12-20
- 录用日期: 2021-12-26
- 网络出版日期: 2022-01-20
- 刊出日期: 2022-03-23

Recent progress of interfacial layers for inverted inorganic perovskite solar cells

School of Energy, Soochow University, Suzhou 215006, China

摘要

摘要: 铯基无机钙钛矿(CsPbX₃)因其耐热性好、低成本和带隙可调等优点，近年来备受关注，并广泛用于制备新型薄膜太阳能电池。目前，虽然具有倒置结构的无机钙钛矿太阳能电池(PSC)更稳定且有望应用于构筑叠层电池的顶电池，其性能仍落后于正置结构的电池。因此，倒置电池的结构，特别是其界面层亟待进一步优化。近年来，研究者们设计和开发了一系列有机、无机界面层(包括空穴传输层和电子传输层)，尝试优化基于无机钙钛矿的倒置电池。本综述针对这一现状，从材料和制备工艺的角度出发，综述了基于有机、无机材料体系的多种界面层的制备和应用进展，总结各类界面层材料的特点，讨论目前界面层的瓶颈问题和潜在的解决方案。
- 无机钙钛矿 /
- 倒置结构的太阳能电池 /
- 电子/空穴传输层 /
- 有机/无机材料 /
- 光伏性能 /
- 稳定性
Abstract: In recent years, cesium based inorganic perovskites (CsPbX₃) are of great interest due to their high thermal resistance, low cost and tunable bandgap, which have been used as absorbers to for the development of novel thin-film solar cells. Currently, the photovoltaic performance of inverted perovskite solar cells (PSC) still leg behind that of regular solar cells, though the inverted solar cells are more stable and more promising as top layer of tandem solar cells. Therefore, the device structure of inverted solar cell remains to be further optimized. To approach this aim, researchers have developed a series of organic and inorganic interfacial layers, including hole-transport-layer and electron-transport-layer, with the aim of optimizing the inverted inorganic perovskite solar cells. Herein, we address the recent progress of organic and inorganic interfacial layers from the perspective of materials and processing techniques. A variety of material systems are compared to summarize their features. This work also discuss their bottlenecks and try to provide potential solutions for achieving ideal interfacial layers.
- inorganic perovskite /
- inverted solar cells /
- electron/hole transport layer /
- organic/inorganic materials /
- photovoltaic property /
- stability

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图 1 正置(a)和倒置(b)钙钛矿太阳能电池的结构示意图

Figure 1. Device structures of conventional n-i-p (a) and inverted p-i-n (b) perovskite solar cells

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图 2 有机界面层材料单元的结构示意图

Figure 2. Schematic structures of the unit of organic interfacial materials

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图 3 (a)基于Spiro-OMeTAD/TS-CuPc的倒置电池结构示意图；((b)~(c)) 在不同基底层上生长的CsPbI₂Br薄膜的深度依赖的GIXRD图谱；(d) 从 CsPbI₂Br (100)晶面获得的晶面间距随掠入角变化的点及拟合曲线；(e) CsPbI₂Br和无掺杂的Spiro-OMeTAD的晶格间距随XRD测试温度变化的线性图；(f) 在HTL/CsPbI₂Br界面上的应力释放示意图^[8]

Figure 3. (a) Schematic diagram of the inverted CsPbI₂Br PSC with Spiro-OMeTAD/TS-CuPc based HTL; ((b)-(c)) Depth-dependent GIXRD patterns of CsPbI₂Br (100) plane deposited on different underlayers; (d) Plot of d-spacing values derived from CsPbI₂Br (100) plane versus incidence angle; (e) Plot of d-spacing values of CsPbI₂Br perovskite and dopant-free Sipro-OMeTAD versus temperature for XRD measurement; (f) Schematic illustration of the strain release at the HTL/CsPbI₂Br interface^[8]

Bphen—4,7-Diphenyl-1,10-phenanthroline; ITO—Indium tin oxide

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图 4 (a)基于PEDOT:PSS和CsPbI₃的倒置电池能带图；(b) 基于β-CsPbI₃和γ-CsPbI₃电池的J-V曲线^[10]；(c) 基于P3CT-N和CsPbI₃的倒置电池的结构示意图；(d) 最优电池的J-V曲线^[11]

Figure 4. (a) Proposed energy band diagram exhibiting charge carriers transportation under illumination for PEDOT:PSS/β-CsPbI₃ or γ-CsPbI₃ based inverted PSC; (b) J-V curves of the champion devices based on β-CsPbI₃ or γ-CsPbI₃^[10]; (c) Schematic diagram of the inverted CsPbI₃ PSC with P3CT-N based ETL; (d) J-V curves of the champion device^[11]

BCP—2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline

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图 5 (a) 二维c-Nb₂O₅纳米片的AFM高度图；(b) 基于c-Nb₂O₅/PC₆₁BM电子传输层的倒置电池结构示意图^[16]；(c) 二维Nano-Eu₂O₃纳米片的AFM高度图；(d) 基于Nano-Eu₂O₃/PC₆₁BM电子传输层的倒置电池能带分布示意图^[17]

Figure 5. (a) AFM height image of 2D c-Nb₂O₅ nanosheets; (b) Schematic illustration of inverted perovskite solar cell based on c-Nb₂O₅/PC₆₁BM ETL ^[16]; (c) AFM height image of 2D Nano-Eu₂O₃ nanosheets; (d) Schematic illustration of band alignment for inverted perovskite solar cell based on Nano-Eu₂O₃/PC₆₁BM ETL ^[17]

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图 6 无机ETL的制备路线示意图^[24]

Figure 6. Schematic diagram of the fabrication of efficient inorganic ETLs on top of perovskite layers^[24]

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表 1 近期文献报道的倒置无机钙钛矿太阳能电池(PSC)的结构和性能

Table 1. Structure and performance of inverted inorganic perovskite solar cells (PSC) reported in recent literature

Device structure	Key improvement	V_OC/V	J_SC /(mA·cm⁻² )	FF/%	PCE/%	Ref.
ITO/PTAA/CsPb(I_0.98Cl_0.02)₃/PC₆₁BM/C₆₀/BCP/Al	Sulfobetaine zwitterions were used as additives in CsPbI₃ precursor solution to stabilize the α phase of CsPbI₃ films	1.09	14.9	70	11.4	[5]
ITO/PTAA/γ-CsPbI₃/PC₆₁BM/BCP/Ag	Tuning the crystallization of γ-CsPbI₃ by co-evaporating the phenethylammonium iodide (PEAI) along with CsI and PbI₂	1.09	17.33	79.41	15.00	[6]
ITO/SpiPA_II/CsPbI₂Br/ZnO@C₆₀/Ag	Dopant-free mixture (SpiPA) of Spiro-OMeTAD and PTAA was applied as HTL	1.14	14.30	76.43	12.52	[7]
ITO/PEDOT:PSS/CsPbI₃/C₆₀/BCP/Al	Preparation of β-CsPbI₃ film at low temperature on PEDOT:PSS HTL	0.96	11.34	67.2	7.3	[10]
FTO/P3CT-N/CsPbI₃/PC₆₁BM/C₆₀/BCP/Ag	Doping perovskite with Si-Cl to improve its humidity stability	1.176	20.1	80.04	18.93	[11]
ITO/PEDOT:PSS/CsPbI₃/PC₆₁BM/BCP/LiF/Al	Using PEDOT:PSS as HTL	0.87	8.17	69	4.88	[12]
FTO/P3CT-N/CsPbI₂Br/PC₆₁BM/C₆₀/BCP/Ag	Surface treatment with FABr followed by a high-temperature annealing	1.223	16.35	79.62	15.92	[13]
ITO/NiO_x/CsPbI₂Br/c−Nb₂O₅/PC₆₁BM/Bphen/Ag	Introducing 2D c−Nb₂O₅ to the CsPbI₂Br/PC₆₁BM interface for inverted PeSCs	1.06	14.13	78.4	11.74	[16]
ITO/NiO_x/CsPbI₂Br/Nano-Eu₂O₃/PC₆₁BM/ Bphen/Ag	Use the solution-processed nano-Eu₂O₃ as the buffer layer between CsPbI₂Br and PC₆₁BM films	1.17	15.50	77.9	14.09	[17]
FTO/NiO_x/CsPbI₂Br/ZnO@C₆₀/Ag	Construction of all-inorganic PSCs with inverted configuration	1.14	15.2	77	13.3	[19]
SLG/FTO/NiO_x/CsPbI₂Br/ZnO@C₆₀/Ag	NiO_x HTL prepared by direct current (DC) reactive magnetron sputtering	1.1	15.1	75.6	12.6	[20]
FTO/NiO_x/CsPbI₂Br/c-Nb₂O₅/PC₆₁BM/Bphen/Ag	Doping CsPbI₂Br perovskite with S₈	1.16	15.91	78.35	14.46	[21]
FTO/NiO_x/CsPbI₂Br/ZnO@C₆₀/Ag	Doping CsPbI₂Br perovskite with Cr-MOF	1.30	16.51	79	17.02	[22]
ITO/NiMgLiO/MAPbI₃/PC₆₁BM/(Ti)NbO_x/Ag	Preparation of NiMgLiO HTL by spray thermal decomposition	1.072	20.62	74.8	16.2	[24]
FTO/NiMgLiO/CsPbI₂Br/PC₆₁BM/BCP/Ag	Inverted inorganic PSCs based on NiMgLiO	0.98	14.18	66	9.14	[25]
FTO/NiMgLiO/CsPbI₂Br/C-MOX/Ag	Carbon-coated metal oxide nanocrystals (C-MOX) as ETL	1.26	14.72	76	14.00	[26]
FTO/NiO_x/CsPbI₂Br/ZnO@C₆₀/ Ag	Doping ZnO@C₆₀ ETL with TPFPB and LiClO₄	1.23	15.87	78	15.19	[27]
ITO/P3CT/CsPbI₂Br/ZnO@C₆₀/ Ag	Modifying ZnO layer with Zwitterionic molecules TPPPS	1.228	15.51	76.83	14.62	[28]
Notes: HTL—Hole transport layer; ETL—Electron transport layer; PEAI—2-Phenylethylamine hydroiodide; SpiPA_II—Spiro-OMeTAD:PTAA; FABr—Formamidinium bromide; FTO—Fluorine-doped tin oxide; SLG—Soda-lime glass; Cr-MOF—Terpyridyl chromium; C-MOX—Carbon-coated metal oxide; TPPPS—3-Triphenylphosphaniumylpropane-1-sulfonate; TPFPB—Tris(pentafluoro-phenyl)borane; V_OC—Open-circuit voltage; J_SC—Short-circuit current density; FF—Fill factor; PCE—Power conversation efficiency.

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