氟取代有机空穴传输材料在钙钛矿太阳能电池中的应用研究进展

doi:10.6023/cjoc202307008

摘要/Abstract

钙钛矿太阳能电池(PSCs)因其性能优异、成本低廉和制备工艺简单, 在环境、生态和能源结构调整方面具有重要意义. 其中空穴传输材料(HTMs)有效调节电池界面势垒、促进空穴传输和收集、降低电荷复合、优化钙钛矿层与电极界面以及改善钙钛矿光吸收层的性质, 在PSCs中发挥重要的作用. 氟取代材料具有独特的电荷传输特性和光电性能, 向有机分子中引入具有诱导效应和共轭效应的氟原子可以降低分子能级, 提高HTMs的空穴迁移率, 进而提高PSCs的性能. 此综述对氟取代有机空穴传输材料对PSCs光电性能的影响及其作用机制进行了梳理和总结.

关键词: 钙钛矿太阳能电池, 空穴传输材料, 氟取代, 有机材料

Perovskite solar cells (PSCs) are of significant importance in the fields of environment, ecology, and energy structure adjustment due to their exceptional performance, cost-effectiveness, and straightforward preparation process. Among them, hole transport materials (HTMs) play a crucial role in PSCs by effectively regulating the battery interface barrier, facilitating hole transport and collection, reducing charge recombination, optimizing the perovskite layer-electrode interface, and enhancing the properties of perovskite light absorption layer. Fluorine-substituted materials possess unique charge transport and photoelectric properties. The introduction of fluorine atoms into organic molecules through induction and conjugation effects can lower molecular energy levels, improve HTM hole mobility thereby enhancing PSCs performance. This paper provides a comprehensive review and summary on the impact of fluorine-substituted organic hole transport materials on the photoelectric properties of PSCs as well as their underlying mechanisms.

Key words: perovskite solar cells, hole transport material, fluorine substitution, organic material

引用此文

刘冬, 张晓晔, 李战峰. 氟取代有机空穴传输材料在钙钛矿太阳能电池中的应用研究进展[J]. 有机化学, 2024, 44(4): 1197-1209.

Dong Liu, Xiaoye Zhang, Zhanfeng Li. Progress in the Application of Fluorine-Substituted Organic Hole Transport Materials for Perovskite Solar Cells[J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1197-1209.

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HTM	Device configuration	J_sc/(mA•cm^-2)	V_oc/V	FF/%	PCE/%	Ref.
n-i-p devices
SFX-p-2F	FTO/SnO₂/Cs_0.05(MA_0.13FA_0.87)_0.95Pb(I_0.83Br_0.17)₃/HTM/Au	22.23	1.14	61.46	16.33	[57]
SFX-m-2F	FTO/SnO₂/Cs_0.05(MA_0.13FA_0.87)_0.95Pb(I_0.83Br_0.17)₃/HTM/Au	22.64	1.16	71.85	18.86	[57]
B3	FTO/TiO₂/m-TiO₂/CH₃NH₃PbI₃/HTM/Au	20.90	0.91	64.00	12.10	[62]
CzPF	FTO/c-TiO₂/PCBM/MAPbI₃/HTM/Au	17.31	1.03	70.00	12.41	[60]
TPB-2F	FTO/c-TiO₂/MAPbI₃/HTM/Au	18.66	1.01	74.00	13.96	[54]
BDT2FMeDPA	FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85 (MAPbBr₃)_0.15/HTM/carbon	21.40	1.00	66.00	14.50	[20]
SF-DTBT	FTO/bl-TiO₂/mp-TiO_2/MAPbI₃/HTM/Au	22.80	0.97	70.00	15.50	[55]
DF-DTBT	FTO/bl-TiO₂/mp-TiO_2/MAPbI₃/HTM/Au	22.82	1.10	74.00	18.70	[55]
JY7	FTO/c-TiO₂/CH₃NH₃PbI_3-_xCl_x/HTM/Ag	20.58	1.05	73.00	15.71	[58]
JY6	FTO/c-TiO₂/CH₃NH₃PbI_3-_xCl_x/HTM/Ag	21.39	1.07	81.00	18.54	[58]
FOMePh	FTO/bl-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.95	0.98	72.53	17.08	[56]
DFBT(DTS-FBTTh₂)₂	FTO/TiO₂/MAPbI₃/HTM/Au	20.70	1.10	76.00	17.30	[52]
2FBTA-2	FTO/c-TiO₂/m-TiO₂/FA_1-_xMA_xPbI₃/HTM/Au	21.53	1.06	78.62	17.94	[61]
IDIDF	FTO/bl-TiO₂/mp-TiO₂/(FAPbI₃)_0.92(MAPbBr₃)_0.08/HTM/Au	23.55	1.04	77.20	19.05	[65]
p-DTS(FBTTh₂)₂	FTO/TiO₂/MAPbI₃/HTM/Au	20.60	1.10	79.40	18.00	[53]
CB-2	FTO/c-TiO₂/mp-TiO₂/SnO₂/[(FAPbI₃)_0.87(MAPbBr₃)_0.13]_0.92-(CsPbI₃)_0.08]/HTM/Au	23.19	1.02	76.70	18.23	[64]
tpa-t-FBTD	FTO/SnO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	22.40	1.08	78.10	18.90	[59]
3,6-SFY	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	23.17	1.08	76.00	19.02	[63]
2,7-SFY	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	23.73	1.08	80.00	20.29	[63]
Spiro-oF	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	26.34	1.16	80.15	24.50	[51]
Spiro-mF	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	26.35	1.16	80.90	24.82	[51]
p-i-n devices
D43	ITO/HTM/CH₃NH₃PbI₃/PC₆₁BM/BCP/Ag	17.67	1.00	68.40	12.13	[68]
DFTAB	ITO/HTM/CH₃NH₃PbI₃/PCBM/Ag	17.50	1.07	69.00	12.40	[72]
3-F-br-4C	ITO/HTM/MAPbI₃/C₆₀/BCP/Ag	20.20	1.06	80.00	17.20	[67]
H2	ITO/HTM/CH₃NH₃PbI₃/PCBM/BCP/Ag	22.93	1.06	76.90	18.69	[19]
INIC-1F	ITO/PEDOT:PSS/MAPbI_3-_xCl_x/HTM/PCBM/PDIN/Ag	22.80	1.01	81.50	18.80	[70]
INIC-2F	ITO/PEDOT:PSS/MAPbI_3-_xCl_x/HTM/PCBM/PDIN/Ag	23.10	1.01	82.70	19.30	[70]
n-i-p devices
DFBT-MTP	ITO/HTM/MAPbI_3-_xCl_x/C₆₀/BCP/Ag	23.01	1.10	79.70	20.15	[71]
HTM-F	ITO/HTM/(FAPbI₃)_1-_x(MAPbBr₃)_x/C₆₀/BCP/Ag	23.03	1.09	82.00	20.51	[69]

HTM	Device configuration	J_sc/(mA•cm^-2)	V_oc/V	FF/%	PCE/%	Ref.
n-i-p devices
SFX-p-2F	FTO/SnO₂/Cs_0.05(MA_0.13FA_0.87)_0.95Pb(I_0.83Br_0.17)₃/HTM/Au	22.23	1.14	61.46	16.33	[57]
SFX-m-2F	FTO/SnO₂/Cs_0.05(MA_0.13FA_0.87)_0.95Pb(I_0.83Br_0.17)₃/HTM/Au	22.64	1.16	71.85	18.86	[57]
B3	FTO/TiO₂/m-TiO₂/CH₃NH₃PbI₃/HTM/Au	20.90	0.91	64.00	12.10	[62]
CzPF	FTO/c-TiO₂/PCBM/MAPbI₃/HTM/Au	17.31	1.03	70.00	12.41	[60]
TPB-2F	FTO/c-TiO₂/MAPbI₃/HTM/Au	18.66	1.01	74.00	13.96	[54]
BDT2FMeDPA	FTO/c-TiO₂/mp-TiO₂/(FAPbI₃)_0.85 (MAPbBr₃)_0.15/HTM/carbon	21.40	1.00	66.00	14.50	[20]
SF-DTBT	FTO/bl-TiO₂/mp-TiO_2/MAPbI₃/HTM/Au	22.80	0.97	70.00	15.50	[55]
DF-DTBT	FTO/bl-TiO₂/mp-TiO_2/MAPbI₃/HTM/Au	22.82	1.10	74.00	18.70	[55]
JY7	FTO/c-TiO₂/CH₃NH₃PbI_3-_xCl_x/HTM/Ag	20.58	1.05	73.00	15.71	[58]
JY6	FTO/c-TiO₂/CH₃NH₃PbI_3-_xCl_x/HTM/Ag	21.39	1.07	81.00	18.54	[58]
FOMePh	FTO/bl-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.95	0.98	72.53	17.08	[56]
DFBT(DTS-FBTTh₂)₂	FTO/TiO₂/MAPbI₃/HTM/Au	20.70	1.10	76.00	17.30	[52]
2FBTA-2	FTO/c-TiO₂/m-TiO₂/FA_1-_xMA_xPbI₃/HTM/Au	21.53	1.06	78.62	17.94	[61]
IDIDF	FTO/bl-TiO₂/mp-TiO₂/(FAPbI₃)_0.92(MAPbBr₃)_0.08/HTM/Au	23.55	1.04	77.20	19.05	[65]
p-DTS(FBTTh₂)₂	FTO/TiO₂/MAPbI₃/HTM/Au	20.60	1.10	79.40	18.00	[53]
CB-2	FTO/c-TiO₂/mp-TiO₂/SnO₂/[(FAPbI₃)_0.87(MAPbBr₃)_0.13]_0.92-(CsPbI₃)_0.08]/HTM/Au	23.19	1.02	76.70	18.23	[64]
tpa-t-FBTD	FTO/SnO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	22.40	1.08	78.10	18.90	[59]
3,6-SFY	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	23.17	1.08	76.00	19.02	[63]
2,7-SFY	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	23.73	1.08	80.00	20.29	[63]
Spiro-oF	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	26.34	1.16	80.15	24.50	[51]
Spiro-mF	FTO/c-TiO₂/mp-TiO₂/FAPbI₃/HTM/Au	26.35	1.16	80.90	24.82	[51]
p-i-n devices
D43	ITO/HTM/CH₃NH₃PbI₃/PC₆₁BM/BCP/Ag	17.67	1.00	68.40	12.13	[68]
DFTAB	ITO/HTM/CH₃NH₃PbI₃/PCBM/Ag	17.50	1.07	69.00	12.40	[72]
3-F-br-4C	ITO/HTM/MAPbI₃/C₆₀/BCP/Ag	20.20	1.06	80.00	17.20	[67]
H2	ITO/HTM/CH₃NH₃PbI₃/PCBM/BCP/Ag	22.93	1.06	76.90	18.69	[19]
INIC-1F	ITO/PEDOT:PSS/MAPbI_3-_xCl_x/HTM/PCBM/PDIN/Ag	22.80	1.01	81.50	18.80	[70]
INIC-2F	ITO/PEDOT:PSS/MAPbI_3-_xCl_x/HTM/PCBM/PDIN/Ag	23.10	1.01	82.70	19.30	[70]
n-i-p devices
DFBT-MTP	ITO/HTM/MAPbI_3-_xCl_x/C₆₀/BCP/Ag	23.01	1.10	79.70	20.15	[71]
HTM-F	ITO/HTM/(FAPbI₃)_1-_x(MAPbBr₃)_x/C₆₀/BCP/Ag	23.03	1.09	82.00	20.51	[69]

HTM	Device configuration	J_sc/(mA•cm^-2)	V_oc/V	FF/%	PCE/%	Ref.
n-i-p devices
PBDT(T)[2F]T	FTO/SnO₂/MAPbI₃/HTM/Ag	16.60	1.03	68.00	11.60	[80]
PBDT[2F]T	FTO/SnO₂/MAPbI₃/HTM/Ag	22.60	1.06	72.60	17.50	[80]
R2	ITO/c-TiO₂/mp-TiO₂/MAPbBr₃/HTM/Au	23.10	0.88	66.20	13.57	[77]
P2-2F	ITO/c-TiO₂/mp-TiO₂/MAPbI₃/HTM/Au	20.17	1.04	70.65	14.94	[76]
R1	ITO/c-TiO₂/mp-TiO₂/MAPbBr₃/HTM/Au	23.70	0.98	68.30	15.88	[80]
PM6	ITO/SnO₂/ZnO/CsPbI₂Br/HTM/MoO₃/Ag	15.68	1.24	82.54	16.06	[75]
P6	ITO/c-TiO₂/mp-TiO₂/MAPbI₃/HTM/Au	20.74	1.09	75.78	17.28	[79]
PPDT2FBT	ITO/TiO₂/CH₃NH₃PbBr₃/HTM/Au	20.70	1.08	79.10	17.70	[82]
FEH	FTO/c-TiO₂/mp-TiO₂/CH₃NH₃PbI₃/FEH/Au	22.80	1.06	74.50	18.00	[83]
P3	FTO/meso-SnO₂/MAPbI₃/HTM/Au	22.90	1.11	0.80	20.30	[73]
2F-PTAA	FTO/d-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.40	1.13	70.30	18.60	[81]
1F-PTAA	FTO/d-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.40	1.14	82.30	21.20	[81]
PE8	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	23.90	1.12	77.60	20.80	[78]
PE9	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	24.10	1.15	78.20	21.70	[78]
PE10	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	24.10	1.16	79.80	22.30	[78]
p-i-n devices
FIAnF	ITO/HTM/(FA_0.79MA_0.16Cs_0.05)Pb(I_0.84Br_0.16)₃/C₆₀/BCP/Ag	20.67	1.04	58.00	12.19	[86]
CzAnF	ITO/HTM/(FA_0.79MA_0.16Cs_0.05)Pb(I_0.84Br_0.16)₃/C₆₀/BCP/Ag	20.73	1.03	80.00	16.81	[86]
BNo-F	ITO/HTM/MAPbI₃/PCBM/BCP/Ag	22.31	1.06	80.20	19.07	[85]
BNs-F	ITO/HTM/MAPbI₃/PCBM/BCP/Ag	22.78	1.08	83.40	20.56	[85]
PFDT-2F-COOH	ITO/HTM/FA_1–_xMA_xPbI₃/PCBM/C₆₀/BCP/Cu	24.86	1.11	78.50	21.68	[27]

HTM	Device configuration	J_sc/(mA•cm^-2)	V_oc/V	FF/%	PCE/%	Ref.
n-i-p devices
PBDT(T)[2F]T	FTO/SnO₂/MAPbI₃/HTM/Ag	16.60	1.03	68.00	11.60	[80]
PBDT[2F]T	FTO/SnO₂/MAPbI₃/HTM/Ag	22.60	1.06	72.60	17.50	[80]
R2	ITO/c-TiO₂/mp-TiO₂/MAPbBr₃/HTM/Au	23.10	0.88	66.20	13.57	[77]
P2-2F	ITO/c-TiO₂/mp-TiO₂/MAPbI₃/HTM/Au	20.17	1.04	70.65	14.94	[76]
R1	ITO/c-TiO₂/mp-TiO₂/MAPbBr₃/HTM/Au	23.70	0.98	68.30	15.88	[80]
PM6	ITO/SnO₂/ZnO/CsPbI₂Br/HTM/MoO₃/Ag	15.68	1.24	82.54	16.06	[75]
P6	ITO/c-TiO₂/mp-TiO₂/MAPbI₃/HTM/Au	20.74	1.09	75.78	17.28	[79]
PPDT2FBT	ITO/TiO₂/CH₃NH₃PbBr₃/HTM/Au	20.70	1.08	79.10	17.70	[82]
FEH	FTO/c-TiO₂/mp-TiO₂/CH₃NH₃PbI₃/FEH/Au	22.80	1.06	74.50	18.00	[83]
P3	FTO/meso-SnO₂/MAPbI₃/HTM/Au	22.90	1.11	0.80	20.30	[73]
2F-PTAA	FTO/d-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.40	1.13	70.30	18.60	[81]
1F-PTAA	FTO/d-TiO₂/mp-TiO₂/(FAPbI₃)_0.85(MAPbBr₃)_0.15/HTM/Au	23.40	1.14	82.30	21.20	[81]
PE8	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	23.90	1.12	77.60	20.80	[78]
PE9	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	24.10	1.15	78.20	21.70	[78]
PE10	ITO/SnO₂/(FA_0.85MA_0.15PbI₃)/HTM/MoO₃/Ag	24.10	1.16	79.80	22.30	[78]
p-i-n devices
FIAnF	ITO/HTM/(FA_0.79MA_0.16Cs_0.05)Pb(I_0.84Br_0.16)₃/C₆₀/BCP/Ag	20.67	1.04	58.00	12.19	[86]
CzAnF	ITO/HTM/(FA_0.79MA_0.16Cs_0.05)Pb(I_0.84Br_0.16)₃/C₆₀/BCP/Ag	20.73	1.03	80.00	16.81	[86]
BNo-F	ITO/HTM/MAPbI₃/PCBM/BCP/Ag	22.31	1.06	80.20	19.07	[85]
BNs-F	ITO/HTM/MAPbI₃/PCBM/BCP/Ag	22.78	1.08	83.40	20.56	[85]
PFDT-2F-COOH	ITO/HTM/FA_1–_xMA_xPbI₃/PCBM/C₆₀/BCP/Cu	24.86	1.11	78.50	21.68	[27]