低成本、高性能钙钛矿电池有机小分子空穴传输材料

doi:10.6023/cjoc202009033

摘要/Abstract

钙钛矿太阳能电池由于其高能量转换效率(最高报道认证效率为25.2%)、低成本和易于制造等特点, 成为下一代光伏技术的关注焦点. 虽然钙钛矿材料本身可以传导空穴, 但其效率比较低. 空穴传输材料的使用成为有效提取电荷和提高钙钛矿型太阳能电池效率的关键因素. 总结了近期报道的低成本、高性能有机小分子空穴传输材料(效率大于19%), 从螺环结构、噻吩衍生物以及其它结构进行介绍, 并从合成策略和化学修饰等角度评估结构-性能的构效关系及其对器件效率和稳定性的影响, 最后对有机小分子空穴传输材料的发展趋势进行了展望.

关键词: 钙钛矿太阳能电池, 空穴传输材料, 有机功能分子, 三芳胺, 能量转换效率

Perovskite solar cells (PSCs) have become the focus of interest among next-generation photovoltaic technologies attributed to their outstanding power conversion efficiency (PCE) (the highest certified PCE of 25.2% being achieved to date), low cost and fabrication feasibility. Perovskite itself is hole-conductive, albeit with a low efficiency. The use of hole transporting material (HTM) remains indispensable for the efficient charge extraction in high-performance PSCs. The recent design and development of low-cost organic small molecules as HTMs in high-performance PSCs with a PCE over 19% are summarized. These HTMs are categorized into materials with spiro core structures, thiophene derivatives, and others, on the basis of their structural features. The relationship between molecular structure and device performance is discussed from the perspective of synthetic strategy and chemical modification. Finally, an outlook is given on the future development of small molecular HTMs.

Key words: perovskite solar cell, hole transporting material, organic functional molecule, triarylamine, power conversion efficiency

引用此文

邵将洋, 钟羽武. 低成本、高性能钙钛矿电池有机小分子空穴传输材料[J]. 有机化学, 2021, 41(4): 1447-1465.

Jiang-Yang Shao, Yu-Wu Zhong. Low-Cost, High-Performance Organic Small Molecular Hole-Transporting Materials for Perovskite Solar Cells[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1447-1465.

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参考文献 57

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Device configuration	HOMO/ eV	Hole mobility/ (cm²?V^–1?s^–1)	V_oc/V	J_sc/(mA?cm^–2)	FF	PCE/%	Ref.
FTO/c-TiO₂/mp-TiO₂/FAPbI₃:xMDACl₂/Spiro-OMeTAD (1)/Au	–5.22	5.31×10^–5	1.15	26.1	0.79	23.7	[11]
]FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/DM (2)/Au	–5.27	NR^a	1.11	24.8	0.81	23.2	[13]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/FDT (3)/Au	–5.16	NR^a	1.15	22.7	0.76	20.2	[14]
ITO/DFH(4)/MA_0.9FA_0.1PbI_3–_xCl_x/C₆₀/BCP/Ag	–5.27	1×10^–3	1.10	22.6	0.83	20.6^b	[15]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/X60 (5)/Au	NR^a	1.9×10^–4	1.14	24.2	0.71	19.84	[16]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/X59 (6)/Au	–5.13	5.5×10^–5	1.13	23.4	0.73	19.8	[17]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/X55 (7)/Au	–5.23	6.81×10^–4	1.15	23.4	0.77	20.8	[18]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/X26 (8)/Au	–5.08	2.79×10^–4	1.11	24.3	0.75	20.2	[19]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.095(MAPbBr₃)_0.05/SFXDAnCBZ (9)/Au	–4.95	4.28×10^–4	1.09	23.1	0.83	20.87	[20]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/G2 (10)/Au	–5.22	3.58×10^–4	1.13	23.5	0.76	20.2	[21]
FTO/c-TiO₂/mp-TiO₂/CsMAFA/HTM-1 (11)/Au	–5.01	4.5×10^–4	1.10	24.7	0.77	21.0	[22]
FTO/TiO₂/MAPbI₃/SCZF-5 (12)/MoO₃/Ag	–5.17	4.69×10^–4	1.11	24.4	0.74	20.1	[24]
FTO/SnO₂/CsFAMA/spiro-CN-OMeTAD (13)/Au	–5.16	1.04×10^–4	1.16	22.0	0.78	19.9	[26]

Device configuration	HOMO/ eV	Hole mobility/ (cm²?V^–1?s^–1)	V_oc/V	J_sc/(mA?cm^–2)	FF	PCE/%	Ref.
FTO/c-TiO₂/mp-TiO₂/FAPbI₃:xMDACl₂/Spiro-OMeTAD (1)/Au	–5.22	5.31×10^–5	1.15	26.1	0.79	23.7	[11]
]FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/DM (2)/Au	–5.27	NR^a	1.11	24.8	0.81	23.2	[13]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/FDT (3)/Au	–5.16	NR^a	1.15	22.7	0.76	20.2	[14]
ITO/DFH(4)/MA_0.9FA_0.1PbI_3–_xCl_x/C₆₀/BCP/Ag	–5.27	1×10^–3	1.10	22.6	0.83	20.6^b	[15]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/X60 (5)/Au	NR^a	1.9×10^–4	1.14	24.2	0.71	19.84	[16]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/X59 (6)/Au	–5.13	5.5×10^–5	1.13	23.4	0.73	19.8	[17]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/X55 (7)/Au	–5.23	6.81×10^–4	1.15	23.4	0.77	20.8	[18]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/X26 (8)/Au	–5.08	2.79×10^–4	1.11	24.3	0.75	20.2	[19]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.095(MAPbBr₃)_0.05/SFXDAnCBZ (9)/Au	–4.95	4.28×10^–4	1.09	23.1	0.83	20.87	[20]
FTO/c-TiO₂/mp-TiO₂/[HC(NH₂)₂]_0.85(CH₃NH₃)_0.15Pb(I_0.85Br_0.15)₃/G2 (10)/Au	–5.22	3.58×10^–4	1.13	23.5	0.76	20.2	[21]
FTO/c-TiO₂/mp-TiO₂/CsMAFA/HTM-1 (11)/Au	–5.01	4.5×10^–4	1.10	24.7	0.77	21.0	[22]
FTO/TiO₂/MAPbI₃/SCZF-5 (12)/MoO₃/Ag	–5.17	4.69×10^–4	1.11	24.4	0.74	20.1	[24]
FTO/SnO₂/CsFAMA/spiro-CN-OMeTAD (13)/Au	–5.16	1.04×10^–4	1.16	22.0	0.78	19.9	[26]

Device configuration	HOMO/eV	Hole mobility/ (cm²?V^–1?s^–1)	V_oc/V	J_sc/ (mA?cm^–2)	FF	PCE/%	Ref.
FTO/c-TiO₂/mp-TiO₂/CsMAFA/Z3 (14)/Au	–5.24	2.4×10^–4	1.12	25.1	0.75	20.84	[21]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/Z26 (15)/Au	–5.16	1.34×10^–4	1.13	23.6	0.75	20.10	[29]
FTO/c-TiO₂/MAPbI₃/EDOT-Amide-TPA (16)/Au	–5.23	3.9×10^–5	1.16	22.7	0.77	20.30	[30]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/YK1 (17)/Au	–5.19	6.68×10^–4	1.11	23.55	0.77	20.13	[31]
ITO/SnO₂/(FAPbI₃)_0.95(MAPbBr₃)_0.05/TTE-2 (18)/Au	–5.30	6.18×10^–4	1.11	23.26	0.77	20.04^a	[32]
ITO/SnO₂/CsMAFA/OMe-TATPyr (19)/Au	–5.4	2.28×10^–4	1.10	23.3	0.81	20.60	[34]
FTO/SnO₂/C₆₀/MA_0.7FA_0.3Pb(I_0.925Br_0.075)₃/DTP-C6Th (20)/Au	–4.94	4.18×10^–4	1.16	22.76	0.80	21.04^a	[35]
FTO/SnO₂/C₆₀/FA_1–_xMA_xPb(I_1–_yBr_y)₃/PMMA/DTPC8-ThDTPA (21)/Au	–4.85	6.5×10^–5	1.14	23.02	0.74	19.42^a	[36]
ITO/SnO₂/CsMAFA/M129 (22)/Au	–5.15	4.23×10^–4	1.12	23.3	0.78	20.35	[37]
ITO/DBTMT (23)/MAPbI₃/C₆₀/BCP/Ag	–5.02	Not reported	1.12	22.7	0.83	21.12	[38]
ITO/SnO₂/CsFAMA/BTTI-C6 (24)/Au	–5.25	2.19×10^–4	1.10	23.41	0.75	19.69^a	[39]
ITO/BDT-POZ (25)/MAPbI₃/PCBM/BCP/Ag	–4.83	2.1×10^–4	1.04	22.56	0.82	19.16^a	[40]
ITO/SnO₂/FA_0.85MA_0.15PbI₃/SM2 (26)/MoO₃/Ag	–5.42	4.51×10^–4	1.07	24.5	0.79	20.56	[41]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/KR321 (27)/Au	–5.24	2.6×10^–4	1.13	21.7	0.78	19.03	[42]

Device configuration	HOMO/eV	Hole mobility/ (cm²?V^–1?s^–1)	V_oc/V	J_sc/ (mA?cm^–2)	FF	PCE/%	Ref.
FTO/c-TiO₂/mp-TiO₂/CsMAFA/Z3 (14)/Au	–5.24	2.4×10^–4	1.12	25.1	0.75	20.84	[21]
FTO/c-TiO₂/mp-TiO₂/FA_1–_xMA_xPb(I_1–_yBr_y)₃/Z26 (15)/Au	–5.16	1.34×10^–4	1.13	23.6	0.75	20.10	[29]
FTO/c-TiO₂/MAPbI₃/EDOT-Amide-TPA (16)/Au	–5.23	3.9×10^–5	1.16	22.7	0.77	20.30	[30]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/YK1 (17)/Au	–5.19	6.68×10^–4	1.11	23.55	0.77	20.13	[31]
ITO/SnO₂/(FAPbI₃)_0.95(MAPbBr₃)_0.05/TTE-2 (18)/Au	–5.30	6.18×10^–4	1.11	23.26	0.77	20.04^a	[32]
ITO/SnO₂/CsMAFA/OMe-TATPyr (19)/Au	–5.4	2.28×10^–4	1.10	23.3	0.81	20.60	[34]
FTO/SnO₂/C₆₀/MA_0.7FA_0.3Pb(I_0.925Br_0.075)₃/DTP-C6Th (20)/Au	–4.94	4.18×10^–4	1.16	22.76	0.80	21.04^a	[35]
FTO/SnO₂/C₆₀/FA_1–_xMA_xPb(I_1–_yBr_y)₃/PMMA/DTPC8-ThDTPA (21)/Au	–4.85	6.5×10^–5	1.14	23.02	0.74	19.42^a	[36]
ITO/SnO₂/CsMAFA/M129 (22)/Au	–5.15	4.23×10^–4	1.12	23.3	0.78	20.35	[37]
ITO/DBTMT (23)/MAPbI₃/C₆₀/BCP/Ag	–5.02	Not reported	1.12	22.7	0.83	21.12	[38]
ITO/SnO₂/CsFAMA/BTTI-C6 (24)/Au	–5.25	2.19×10^–4	1.10	23.41	0.75	19.69^a	[39]
ITO/BDT-POZ (25)/MAPbI₃/PCBM/BCP/Ag	–4.83	2.1×10^–4	1.04	22.56	0.82	19.16^a	[40]
ITO/SnO₂/FA_0.85MA_0.15PbI₃/SM2 (26)/MoO₃/Ag	–5.42	4.51×10^–4	1.07	24.5	0.79	20.56	[41]
FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/KR321 (27)/Au	–5.24	2.6×10^–4	1.13	21.7	0.78	19.03	[42]

HTM	HOMO/eV	Hole mobility/ (cm²?V^–1?s^–1)	V_oc/V	J_sc/ (mA?cm^–2)	FF	PCE/%	Ref.
ITO/TPE-S (28)/FA_0.9Cs_0.1PbI₃/PCBM/ZnO/Ag	–5.29	1.2×10^–5	1.13	23.3	0.80	21.0^b	43
ITO/FMT (29)/MAPbI₃/PCBM/Al	–4.89	2.28×10^–6	1.07	22.52	0.79	19.06^b	44
FTO/c-TiO₂/mp-TiO₂/MAPbI₃/CJ-03 (30)/Au	–5.18	6.47×10^–5	1.11	22.89	0.79	20.06	45
ITO/SnO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/Py-OMe (31)/Au	–5.40	4.4×10^–3	1.11	22.82	0.76	19.28	46
ITO/SnO₂/MAPbI₃/TFAP (32)/Au	–5.27	4.5×10^–3	1.11	22.63	0.74	19.74	47
FTO/c-TiO₂/mp-TiO₂/CsMAFA/KR374 (33)/Au	–5.06	1.2×10^–6	1.09	23.15	0.76	19.26	48
FTO/c-TiO₂/mp-TiO₂/CsMAFA/DBC-OMeDPA (34)/Au	–5.26	8.8×10^–4	1.13	24.8	0.79	22.0	50
FTO/TiO₂/MAPbI₃/pPh-2MODPACz (35)/Au	–5.22	9.05×10^–5	1.09	23.22	0.78	19.74	51
FTO/c-TiO₂/CH₃NH₃PbI_3–_xCl_x/JY8 (36)/Ag	–5.19	9.65×10^–4	1.08	21.9	0.81	19.14	52
FTO/c-TiO₂/SnO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/PDO2 (37)/Au	–5.24	5.93×10^–4	1.15	23.9	0.74	20.2	53
FTO/TiO₂/MAPbI3/DCZ-OMeTAD (38)/MoO₃/Ag	–5.27	6.5×10^–4	1.06	25.14	0.81	21.66	54
ITO/C₆₀/MAPbI_xCl_3–_x/FBA3 (39)/MoO₃/Ag	–5.07	2.12×10^–4	1.09	22.12	0.80	19.27^b	55
FTO/SnO₂/FA_0.83Cs_0.17Pb(I_0.9Br_0.1)₃/V1091 (40)/Au	–5.17	1.3×10^–5	1.11	22.5	0.81	20.2	56
FTO/SnO₂/Cs_0.17FA_0.83Pb(I_0.9Br_0.1)₃/TAT-^tBuSty (41)/Au	NR^a	NR^a	1.15	22.1	0.80	20.3	47