Application of fullerenes in new-generation solar cells
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摘要: 新型太阳能电池包括有机太阳能电池、钙钛矿太阳能电池和量子点太阳能电池等，是一类十分有前景的光伏器件，目前有机太阳能电池和钙钛矿太阳能电池的能量转换效率分别超过了19%和25.6%。富勒烯材料具有较高的电子迁移率和良好的电子特性，被广泛应用于有机太阳能电池活性层、界面层，钙钛矿太阳能电池活性层和中间层等。在有机太阳能电池中，富勒烯材料作为活性层受体，可以提高器件电子传输能力；作为界面修饰层，可以有效降低接触电阻，抑制载流子的复合。在钙钛矿太阳能电池中，富勒烯材料作为活性层添加剂能钝化钙钛矿缺陷，抑制迟滞效应；作为中间层能优化界面形貌，促进电荷的提取与输运。本文综述了富勒烯材料在各个组成部分中的研究进展，并展望了富勒烯材料在各个组成部分中的发展前景，在此基础上，提出了未来的研究方向。Abstract: New-generation solar cells, including organic solar cells, perovskite solar cells and quantum dot solar cells, are pretty promising photovoltaic devices. At present, the energy conversion efficiency of organic solar cells and perovskite solar cells exceeds 19% and 25.6% respectively. Fullerenes are widely used in organic solar cells active layer and interface layer, perovskite solar cells active layer and intermediate layer due to their high electron mobility and good electronic properties. In organic solar cells, fullerenes act as the active layer receptors to improve the electron transport capacity of devices. As an interface modification layer, it can effectively reduce the contact resistance and inhibit the recombination of carriers. In perovskite solar cells, fullerene materials act as active layer additive to passivate perovskite defect and restrain hysteresis effect. As an intermediate layer, the interface morphology can be optimized and charge extraction and transport can be promoted. In this paper, the research progress of fullerene materials in each component is reviewed, and the development prospect of fullerene materials in each component is prospected, and the future research direction is proposed.
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图 1 传统(a)和倒置(b)有机太阳能电池结构示意图
Figure 1. Schematic diagram of the device structures of conventional (a) and inverted (b) organic solar cells
图 2 正置(a)和倒置(b)钙钛矿太阳能电池结构示意图
Figure 2. Schematic diagram of the device structure of n-i-p (a) and p-i-n (b) perovskite solar cells
HTL—Hole transport layer; ETL—Electron transport layer
图 3 在有机太阳能电池中作为活性层受体的富勒烯材料分子结构
Figure 3. Molecular structures of fullerene materials as active layer receptors in organic solar cells
图 4 在有机太阳能电池中作为中间层的富勒烯材料分子结构
Figure 4. Molecular structures of fullerene materials as intermediate layers in organic solar cells
图 5 在钙钛矿太阳能电池中作为活性层添加剂的富勒烯材料分子结构
Figure 5. Molecular structures of fullerene materials as active layer additives in perovskite solar cells
图 6 在钙钛矿太阳能电池中作为中间层的富勒烯材料分子结构
Figure 6. Molecular structures of fullerene materials as intermediate layers in perovskite solar cells
表 1 富勒烯在有机太阳能电池中作为活性层受体的性能参数
Table 1. Performance parameters of organic solar cells with fullerene materials as active layer receptors
Active layer $ {V}_{\mathrm{O}\mathrm{C}} $/V $ {J}_{\mathrm{S}\mathrm{C}} $/(mA·cm−2) FF PCE/% Ref. PC71BM:MDMO-PPV 0.77 7.60 0.51 3.00 [24] PffBT4T-C9C13:PC71BM 0.78 20.20 0.74 11.70 [25] Lu3N@C80-PCBH:P3HT 0.81 8.64 0.61 4.20 [27] OQThC59N:P3HT 0.78 7.57 0.69 4.09 [28] DPC59N:P3HT 0.58 8.39 0.50 2.42 [29] bis-PC61BM:P3HT 0.72 9.14 0.68 4.50 [30] IC60BA:P3HT 0.84 9.67 0.67 5.44 [31] IC70BA:P3HT 0.87 11.35 0.75 7.40 [32] NC60BA:P3HT 0.82 9.88 0.67 5.37 [33] NC70BA:P3HT 0.83 10.71 0.67 5.95 [34] bis-TOQC:P3HT 0.86 7.70 0.66 5.10 [35] bis-OQMF70:P3HT 0.95 7.40 0.58 4.09 [36] PBDB-TF:Y6:PC61BM 0.85 25.40 0.77 16.50 [44] PM6:Y6:PC71BM 0.86 25.10 0.77 16.70 [45] PTQ10:Y6:PC71BM 0.85 25.32 0.75 16.07 [46] BTR-Cl:Y6:ICBA 0.84 23.55 0.74 14.70 [47] Notes: $ {V}_{\mathrm{O}\mathrm{C}} $—Open circuit voltage; $ {J}_{\mathrm{S}\mathrm{C}} $—Short-circuit current density; FF—Fill factor; PCE—Power conversion efficiency; MDMO-PPV—Poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene]; PffBT4 T-C9C13—Poly[(5,6-difluoro-2,1,3-benzothiadiazole-4,7-diyl)-alt-(3,3′′′-di(2-nonyltridecyl)-2,2′,5′,2′′,5′′,2′′′-quaterthiophen-5,5′′′-diyl)]; P3HT—Poly(3-hexylthiophene); bis-TOQC—Thieno-o-quinodimethane bisadducts; bis-OQMF70—64π bis-o-quinodimethane-methano[70]fullerene; PBDB-TF—Poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2 b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′c′]dithiophene-4,8-dione)]; PM6—Poly[[4,8-bis[5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-1,3-diyl]-2,5-thiophenediyl]; Y6—(2,2′-((2 Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2′′,3′′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))-bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile); PTQ10—Poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)]; BTR-Cl—Chlorinated benzodithiophene terthiophene rhodanine. 
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表 2 富勒烯在有机太阳能中作为中间层的性能参数
Table 2. Performance parameters of organic solar cells with fullerene materials as intermediate layers
Intermediate layer/Active layer $ {V}_{\mathrm{O}\mathrm{C}} $/V $ {J}_{\mathrm{S}\mathrm{C}} $/(mA·cm-2) FF PCE/% Ref. F-PCBM/P3HT:PCBM 0.57 9.51 0.70 3.79 [49] PEGN-C60/PBDTTT-C-T:PC71BM 0.79 14.79 0.64 7.45 [50] C60-SB/PTB7:PC71BM(Ag) 0.75 16.89 0.68 8.57 [51] bis-FPI/PIDT-PhanQ:PC71BM 0.83 11.40 0.56 5.26 [52] FPI-PEIE/PBDTT-TT:PC71BM 0.81 16.26 0.73 9.62 [52] ZnO:PCBM/PTB7-F20:PC71BM 0.68 17.04 0.66 7.70 [53] PCMI:K+/PTB7-Th:PC71BM 0.79 19.57 0.67 10.30 [54] C60-4TPB/PTB7:PC71BM 0.73 16.84 0.66 8.07 [55] ZnO:C60-2DPE/PTB7:PC71BM 0.80 17.94 0.64 9.21 [55] ZnO:C60-PEHBS/PTB7-Th:PC71BM 0.79 17.27 0.63 8.56 [56] ZnO:C60-2EHTPB/PTB7:PC71BM 0.79 17.70 0.64 9.00 [56] Notes: PBDTTT-C-T—(Poly(4,8-bis(5-(2-ethylhexyl)-thiophene-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-alt-alkylcarbonylthieno[3,4-b]thiophene)); PTB7—Poly{[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]}; PIDT-PhanQ—Poly(indacenodithiophene-co-phananthrene-quinoxaline); FPI—Amphiphilic fulleropyrrolidinium iodide; PEIE—Ethoxylated polyethyleneimine; PBDTT-TT—Poly{4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-4,6-thieno[3,4-b]thiophen-2-yl-2-ethylhexan-1-one}; PTB7-F20—Poly(thienothiophene-co-benzodithiophenes)7-F20; PTB7-Th— Poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophene-4,6-diyl}; C60-2DPE—[6,6]-Phenyl-C61-butyricacid-2-(4-(9,9-bis(2-(dimethylamino)ethyl)-9H-fluoren-2-yl)-phenyl)ethan-1-ol; C60-PEHBS—[6,6]-Phenyl-C61-butyricacid-potassium 4,4′-(9′,9′-bis(2-(2-ethoxyethoxy)ethyl)-7′-(4-(2-hydroxyethy)phenyl)-9 H,9′H-[2,2′-bifluorene]-9,9-diyl)-bis-(butane-1-sulfonate); C60-2 EHTPB—[6,6]-Phenyl-C61-butyricacid-2-(4-(9′,9′-bis(3-bromopropyl)-9,9-bis(2-(2-ethoxyethoxy)-ethyl)-9H,9′H-[2,2′-bifluoren]-7-yl)phenyl-9H,9′H-[2,2′-bifluoren]-9-yl)-N,N,N-trimethylpropan-1-aminium.
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表 3 富勒烯衍生物作为钙钛矿太阳能电池活性层添加剂的性能参数
Table 3. Performance parameters of perovskite solar cells with fullerene materials as active layer additives
Active layer $ {V}_{\mathrm{O}\mathrm{C}} $/V $ {J}_{\mathrm{S}\mathrm{C}} $/(mA·cm−2) FF PCE/% Ref. MAPb0.75Sn0.25I3:C60 0.74 23.50 0.79 13.70 [57] MAPbI3:C70 1.07 20.44 0.72 15.71 [58] MAPbI3:PC61BM 1.08 18.00 0.75 14.40 [59] MAPbI3:1D-PC61BM 0.90 22.88 0.74 15.30 [60] MAPbI3:IC60BA 1.09 21.59 0.77 18.14 [61] MAPbI3:PCBB-OEG 1.07 23.65 0.80 20.20 [62] MAPbI3:PCBPEG 1.07 21.28 0.77 17.31 [63] MAPbI3:C60-PyP 1.10 22.47 0.79 19.82 [64] MAPbI3:C60-PyF15 1.07 23.14 0.81 20.12 [65] MAPbI3:PC61BM(GHJ) 1.07 21.90 0.78 18.21 [66] MAPbI3:PC71BM 1.01 23.50 0.65 15.50 [67] MAPbI3:α-bis-PCBM 1.13 23.95 0.77 20.80 [69] MAPbI3:C60(QM)2 1.08 22.40 0.76 18.40 [70] MAPbI3:C60-PEG 1.05 20.60 0.82 17.71 [71] Notes: MA—CH3NH3+; GHJ—Graded heterojunction.
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表 4 富勒烯衍生物作为钙钛矿太阳能电池中间层的性能参数
Table 4. Performance parameters of perovskite solar cells with fullerene materials as intermediate layers
Intermediate layer/Active layer $ {V}_{\mathrm{O}\mathrm{C}} $/V $ {J}_{\mathrm{S}\mathrm{C}} $/(mA·cm−2) FF PCE/% Ref. C60:C70/MAPbI3 1.03 24.30 0.73 18.00 [72] C60-3-BPy/CsFAMA 1.07 20.44 0.72 18.22 [73] HMB-C60/MAPbI3 1.06 22.59 0.67 16.04 [74] Crosslinked PCBM/MAPbI3 0.99 20.00 0.75 14.90 [75] PyCEE/MAPbI3 1.05 22.95 0.76 18.27 [76] PCBM-F4/MAPbI3 0.90 20.60 0.79 14.60 [77] NMPFP/MAPbI3 1.05 19.48 0.68 13.83 [78] PCBM-5a/MAPbI3 1.09 23.70 0.80 20.70 [79] FM/MAPbI3 1.02 22.60 0.73 16.90 [80] C60-PDI-I/MAPbI3 1.07 21.92 0.78 18.29 [81] CF3-PC61BM:PCBM/MAPbI3 1.06 22.25 0.78 18.37 [82] C6F13-PC61BM:PCBM/MAPbI3 1.06 22.13 0.75 17.71 [82] TBA-Azo:PCBM/MAPbI3 1.10 23.40 0.76 19.60 [83] PCPB:PCBM/MAPbI3 1.08 22.67 0.74 18.19 [84] DPP:PCBM/MAPbI3 1.01 23.40 0.69 16.40 [85] TiO2:C60NH2/MAPbI3 1.08 22.39 0.75 18.34 [86] SnO2:C9/(FAPbI3)x(MAPbBr3)1-x 1.12 24.10 0.79 21.30 [87] SnO2:CPTA/MAPbI3 1.07 22.39 0.77 18.36 [88] SnO2:DPC60//MAPbI3 1.14 23.00 0.78 20.40 [89] Spiro-OMeTAD:[Li@C60]TFSI/(FAPbI3)0.85(MAPbBr3)0.15 1.01 22.90 0.72 16.80 [90] Spiro-OMeTAD:[Li@C60]TFSI/CsFAMA 1.09 23.10 0.68 17.20 [91] Spiro-OMeTAD-Sc3N@C80/MAPbI3 1.15 23.06 0.78 20.77 [92] Notes: FA—HC(NH2)2+; HMB—Hexamethonium bromide; NMPFP—N-Methyl-2-pentyl-[60]fullerene pyrrolidine; FM—Fullerene mixture (C60:C70=1:1); TBA-Azo—3,4,5-Tris(n-dodecyloxy) benzoylamide with an azobenzene moiety; DPP—Pyrrolo[3,4-c]pyrrole-1,4-dione; Spiro-OMeTAD—2,2′,7,7′-Tetrakis(N, N-di-p-methoxyphenylamine)-9,9′-spirobifluorene; TFSI—Bis(trifluoromethanesulfonyl)imide.
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