CN116574106B - 一种空穴传输材料及太阳能电池 - Google Patents
一种空穴传输材料及太阳能电池 Download PDFInfo
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- 230000005525 hole transport Effects 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
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- 239000012298 atmosphere Substances 0.000 claims description 2
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- 125000003118 aryl group Chemical group 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
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- 229910052759 nickel Inorganic materials 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 16
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000032258 transport Effects 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- -1 methoxy, methylthio Chemical group 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001894 space-charge-limited current method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 1
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
发明涉及太阳能电池技术领域,具体为一种空穴传输材料及太阳能电池,其结构式如下式Ⅰ所示:式Ⅰ中R1为锌、铜、铁或镍中的任意一种;R2为式Ⅱ基团:Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的C6‑C60芳香族或其衍生物基团,使用本发明空穴传输材料作为空穴传输层所制备的太阳能电池具有良好的光电性能。
Description
技术领域
本发明涉及太阳能电池技术领域,具体为一种空穴传输材料及太阳能电池。
背景技术
钙钛矿太阳能电池的典型结构由3部分组成:
①用于吸光的钙钛矿层:其中激子产生并分离成电子和空穴;
②载流子传输层,包括电子传输层(将电子从钙钛矿层提取并传输到阴极)以及空穴传输层(将空穴从钙钛矿层提取并传输到阳极);
③电极,包括阳极和阴极,主要由ITO、FTO以及金属(金、银)等构成。
空穴传输层将钙钛矿层产生的空穴传输到阳极,是一种有选择性的高速率传输空穴的材料,性能好的空穴传输材料能够单一地传输空穴并阻挡电子。目前空穴传输材料主要有无机、高分子聚合物以及有机小分子三大类。其中,有机小分子由于设计灵活、能级易于调控且易溶于有机溶剂、便于器件的加工而受到广泛关注。
2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(spiro-OMeTAD)是应用于钙钛矿太阳能电池最成功的芳胺类空穴传输材料,但其空穴迁移率和导电率都比较低,需要加入P型锂盐及4-叔丁基吡啶(TBP)等掺杂剂来提高其空穴迁移率,而该类添加剂会腐蚀钙钛矿层,影响太阳能电池使用寿命。
发明内容
发明目的:针对上述技术问题,本发明提出了一种空穴传输材料及太阳能电池。
所采用的技术方案如下:
一种空穴传输材料,其结构式如下式Ⅰ所示:
;
式Ⅰ中R1为锌、铜、铁或镍中的任意一种;
R2为式Ⅱ基团;
;
Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的C6-C60芳香族或其衍生物基团;
取代基选自氘、甲氧基、甲硫基、C1-C6烷基、C1-C6氘代烷基、C1-C6卤代烷基、C3-C10环烷基、C3-C10氘代环烷基、C3-C10卤代环烷基、C6-C60芳香族基团、C6-C60氘代芳香族基团或C6-C60卤代芳香族基团中的一种或一种以上。
进一步地,Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的苯基、联苯基、蒽基、萘基、菲基、咔唑基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、9,9-二苯基芴基、9,9'-螺二芴基;
取代基选自氘、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基、联苯基。
进一步地,Ar1、Ar2、Ar3、Ar4各自独立的为以下基团:
;
进一步地,R1为锌。
进一步地,所述空穴传输材料,具体为以下化合物中的任意一种或多种:
;
;
。
进一步地,所述空穴传输材料的制备方法如下:
将化合物A与化合物B溶于THF中,再依次加入碳酸钾、四(三苯基膦)钯,加热至回流反应,得到化合物C,在于保护性气体氛围下,将化合物C与金属有机盐在DMF中加热至120-140℃反应,即得到所述空穴传输材料;
;
所述金属有机盐为醋酸锌、醋酸铜、醋酸铁或醋酸镍中的任意一种。
本发明还提供了一种太阳能电池,包括FTO层、电子传输层、钙钛矿层、空穴传输层和金属电极层,所述空穴传输层包括上述的空穴传输材料。
进一步地,所述电子传输层为SnO2、TiO2、ZnO中的任意一种或多种组合。
进一步地,所述钙钛矿层包括CH3NH3PbI3、CH(NH2)2PbI3、CH3CH2NH3PbI3中的任意一种或多种组合。
进一步地,所述太阳能电池的制备方法如下:
S1:利用旋涂法在所述FTO层上生成所述电子传输层;
S2:利用旋涂法在所述电子传输层上生成钙钛矿层;
S3:将所述空穴传输材料溶解于氯苯中得到前驱体溶液,取前驱体溶液滴加至钙钛矿层表面,以3000-5000rpm的转速旋涂30-50s后于加热板上120-150℃退火10-30min得到空穴传输层;
S4:最后再于所述空穴传输层上生成金属电极层,即可获得所述太阳能电池。
本发明的有益效果:
本发明提供了一种空穴传输材料,具有更强的卟啉分子间作用力,使得空穴传输层分子排列更加有序,从而有效提升了电荷传输性能,不需要额外再加入掺杂剂来提高其空穴迁移率,避免了掺杂剂对钙钛矿层的腐蚀,并且具有良好的空穴传输性能以及电子阻挡性能,有利于空穴的有效的选择性传输,成膜性能良好,能够有效实现钙钛矿层与空穴传输层良好的界面接触,所制备的太阳能电池具有良好的光电性能。
附图说明
图1为本发明中太阳能电池的结构示意图;
图2为本发明实施例及对比例所制备太阳能电池的SEM图。
具体实施方式
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。本发明未提及的技术均参照现有技术,除非特别指出,以下实施例和对比例为平行试验,采用同样的处理步骤和参数。
实施例1
一种空穴传输材料,其结构式如下所示:
;
其制备方法如下:
;
S1:将化合物1-a(79mg,790.02g/mol,0.1mmo1)和化合物1-b(303.55mg,674.56g/mol,0.45mmo1)加入20mL的四氢呋喃中并搅拌溶解,再加入溶于5mL水中的碳酸钾(34.55mg,138.2g/mol,0.25mmo1)和四(三苯基膦)钯(1.16mg,1155.56g/mol,0.001mmo1),搅拌升温至70℃,反应4h后加入20mL水,搅拌分液,有机相以饱和氯化钠溶液洗涤后干燥,过滤,减压蒸馏除去溶剂得到粗产物,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚:二氯甲烷=1:3),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到化合物1-c,产率为59.3%。
S2:将化合物1-c(149.47mg,2989.34g/mol,0.05mmo1)和醋酸锌(45.87mg,183.48g/mol,0.25mmo1)加入到20mL DMF中,并在氮气保护条件下130℃搅拌反应10h,反应结束后减压去除溶剂后,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚/乙酸乙酯=4/1),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到目标产物TM,产率为62.5%,ESI-MS(m/z)(M+H+):理论值3052.7,实测值3053.1,元素分析结果(分子式C200H120N24O8Zn):理论值C, 78.69; H, 3.96; N,11.01; O, 4.19; Zn, 2.14;实测值C, 78.89; H, 3.95; N, 11.12; O, 4.25; Zn,2.20。
使用空间电荷限制电流法测得目标产物TM的空穴迁移率为1.96×10–4 cm2/(V·s)。
实施例2
一种空穴传输材料,其结构式如下所示:
;
其制备方法如下:
/> ;
S1:将化合物2-a(79mg,790.02g/mol,0.1mmo1)和化合物2-b(330.57mg,734.61g/mol,0.45mmo1)加入20mL的四氢呋喃中并搅拌溶解,再加入溶于5mL水中的碳酸钾(34.55mg,138.2g/mol,0.25mmo1)和四(三苯基膦)钯(1.16mg,1155.56g/mol,0.001mmo1),搅拌升温至70℃,反应4h后加入20mL水,搅拌分液,有机相以饱和氯化钠溶液洗涤后干燥,过滤,减压蒸馏除去溶剂得到粗产物,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚:二氯甲烷=1:3),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到化合物2-c,产率为55.6%。
S2:将化合物2-c(161.48mg,3229.54g/mol,0.05mmo1)和醋酸锌(45.87mg,183.48g/mol,0.25mmo1)加入到20mL DMF中,并在氮气保护条件下140℃搅拌反应10h,反应结束后减压去除溶剂后,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚/乙酸乙酯=4/1),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到目标产物TM,产率为60.8%,ESI-MS(m/z)(M+H+):理论值3292.91,实测值3293.50,元素分析结果(分子式C208H136N24O16Zn):理论值C, 75.87; H, 4.16; N,10.21; O, 7.77; Zn, 1.99;实测值C, 75.44; H, 4.20; N, 10.35; O, 7.26; Zn,1.83。
使用空间电荷限制电流法测得目标产物TM的空穴迁移率为1.99×10–4 cm2/(V·s)。
实施例3
一种空穴传输材料,其结构式如下所示:
;/>
其制备方法如下:
/>;
S1:将化合物1-a(79mg,790.02g/mol,0.1mmo1)和化合物1-b(325.3mg,722.89g/mol,0.45mmo1)加入20mL的四氢呋喃中并搅拌溶解,再加入溶于5mL水中的碳酸钾(34.55mg,138.2g/mol,0.25mmo1)和四(三苯基膦)钯(1.16mg,1155.56g/mol,0.001mmo1),搅拌升温至70℃,反应4h后加入20mL水,搅拌分液,有机相以饱和氯化钠溶液洗涤后干燥,过滤,减压蒸馏除去溶剂得到粗产物,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚:二氯甲烷=1:3),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到化合物3-c,产率为53.5%。
S2:将化合物1-c(171.91mg,3438.20g/mol,0.05mmo1)和醋酸锌(45.87mg,183.48g/mol,0.25mmo1)加入到20mL DMF中,并在氮气保护条件下130℃搅拌反应10h,反应结束后减压去除溶剂后,用硅胶柱层析法对粗产物进行纯化(洗脱液:石油醚/乙酸乙酯=4/1),再用适量二氯甲烷将柱层析产物加热溶解后滴加正己烷至出现浑浊,搅拌下自然降温析晶12h后过滤,即可得到目标产物TM,产率为58.3%,ESI-MS(m/z)(M+H+):理论值3501.56,实测值3502.88,元素分析结果(分子式C232H184N24O8Zn):理论值C, 79.58; H, 5.30; N,9.60; O, 3.66; Zn, 1.87;实测值C, 79.50; H, 5.15; N, 9.64; O, 3.57; Zn, 1.83。
使用空间电荷限制电流法测得目标产物TM的空穴迁移率为2.04×10–4 cm2/(V·s)。
性能测试:
将实施例1-3中所制备的空穴传输材料制备成太阳能电池进行性能测试,制备方法如下:
(1)FTO基底经过异丙醇超声清洗后,用氮气吹干;
(2)将SnO2溶液后以4000r/s旋涂在紫外处理过的FTO基底上,持续30s,然后再150℃退火30min形成电子传输层;
(3)将MAI、PbI2溶解在DMSO和DMF的混合溶液(DMSO:DMF=3:7)中,以配制浓度为1.4M的MAPbI3钙钛矿前驱体溶液,溶解好的溶液放在摇床上摇12h,将钙钛矿前驱体溶液以1000rpm和5000rpm的转速旋涂10s和30s,旋涂结束前15s内滴入110uL氯苯,120℃退火30min,得到钙钛矿层;
(4)分别取实施例1-3中所制备的空穴传输材料及市售spiro-OMeTAD 30mg溶于1mL氯苯中配制成30mg/mL的前驱体溶液,取前驱体溶液滴加至钙钛矿层表面,以5000rpm的转速旋涂30s后于加热板上140℃退火30min得到空穴传输层;
(5)最后通过真空蒸镀法在器件顶部沉积约70nm的金作为电极。
对比例1太阳能电池的制备方法与上述方法相似,区别在于将空穴传输材料替换为市售spiro-OMeTAD;
对比例2太阳能电池的制备方法与上述方法相似,区别在于步骤(4)中将空穴传输材料替换为市售spiro-OMeTAD,并且加入LiTFSI和t-BP,步骤(4)操作具体如下:
将30mg市售spiro-OMeTAD溶于1mL氯苯配制成30mg/mL的溶液,加入35μL Li-TFSI(0.91M,乙腈为溶剂)和30μL TBP,以3000r/s将其旋涂30s,得到空穴传输层。
在AM1.5,100mW/cm2光照下,用太阳能模拟器来测试上述太阳能电池的各项性能,测试结果如表1所示;
表1:
;
由上表1可知,本发明所公开的空穴传输材料作为空穴传输层所制备的太阳能电池具有良好的光电性能。
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (7)
1.一种空穴传输材料,其特征在于,其结构式如下式Ⅰ所示:
;
式Ⅰ中R1为锌;
R2为式Ⅱ基团;
;
Ar1、Ar2、Ar3、Ar4各自独立的为以下基团:
。
2.如权利要求1所述的空穴传输材料,其特征在于,具体为以下化合物中的任意一种或多种:
;
;
。
3.如权利要求1所述的空穴传输材料,其特征在于,其制备方法如下:
将化合物A与化合物B溶于THF中,再依次加入碳酸钾、四(三苯基膦)钯,加热至回流反应,得到化合物C,在保护性气体氛围下,将化合物C与金属有机盐在DMF中加热至120-140℃反应,即得到所述空穴传输材料;
;
所述金属有机盐为醋酸锌。
4.一种太阳能电池,其特征在于,包括FTO层、电子传输层、钙钛矿层、空穴传输层和金属电极层,所述空穴传输层包括权利要求1-3中任一项所述的空穴传输材料。
5.如权利要求4所述的太阳能电池,其特征在于,所述电子传输层为SnO2、TiO2、ZnO中的任意一种或多种组合。
6.如权利要求5所述的太阳能电池,其特征在于,所述钙钛矿层包括CH3NH3PbI3、CH(NH2)2PbI3、CH3CH2NH3PbI3中的任意一种或多种组合。
7.如权利要求6所述的太阳能电池,其特征在于,所述太阳能电池的制备方法如下:
S1:利用旋涂法在所述FTO层上生成所述电子传输层;
S2:利用旋涂法在所述电子传输层上生成钙钛矿层;
S3:将所述空穴传输材料溶解于氯苯中得到前驱体溶液,取前驱体溶液滴加至钙钛矿层表面,以3000-5000rpm的转速旋涂30-50s后于加热板上120-150℃退火10-30min得到空穴传输层;
S4:最后再于所述空穴传输层上生成金属电极层,即可获得所述太阳能电池。
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