CN111187280A - Doping-free hole transport material based on indeno [1,2-b ] carbazole and synthetic method and application thereof - Google Patents
Doping-free hole transport material based on indeno [1,2-b ] carbazole and synthetic method and application thereof Download PDFInfo
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- CN111187280A CN111187280A CN202010062261.1A CN202010062261A CN111187280A CN 111187280 A CN111187280 A CN 111187280A CN 202010062261 A CN202010062261 A CN 202010062261A CN 111187280 A CN111187280 A CN 111187280A
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- hole transport
- carbazole
- indeno
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 230000005525 hole transport Effects 0.000 title claims abstract description 55
- 238000010189 synthetic method Methods 0.000 title description 2
- JVVVNZPYZOACCH-UHFFFAOYSA-N indeno[1,2-b]carbazole Chemical compound C1=CC=CC2=C3C=C4C(C=C3C=C12)=C1C=CC=CC1=N4 JVVVNZPYZOACCH-UHFFFAOYSA-N 0.000 title 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 74
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 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 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- HTJWUNNIRKDDIV-UHFFFAOYSA-N bis(1-adamantyl)-butylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCC)C1(C2)CC(C3)CC2CC3C1 HTJWUNNIRKDDIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 claims description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
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- 238000000605 extraction Methods 0.000 abstract description 6
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 3
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- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
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- 229910052786 argon Inorganic materials 0.000 description 7
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 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 3
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- WYURNTSHIVDZCO-SVYQBANQSA-N deuterated tetrahydrofuran Substances [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
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- 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 1
- ISADKOKKVZYYMM-UHFFFAOYSA-N 9h-carbazole;thiophene Chemical compound C=1C=CSC=1.C1=CC=C2C3=CC=CC=C3NC2=C1 ISADKOKKVZYYMM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
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- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000001318 differential pulse voltammogram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms 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
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of organic photoelectric materials, and discloses an organic photoelectric material based on indeno [1,2-b]The doping-free hole transmission material of carbazole, its preparation method and application, said material is indeno [1,2-b]Carbazole-thiophene is a peripheral electron donor unit, and tetrathienopyrrole is a molecular core; the invention has simple synthetic route and low preparation cost, and can realize large-scale synthesis of materials; the material disclosed by the invention has good dissolving and film-forming properties and excellent thermal stability; steady-state fluorescence spectrum tests show that the material has high hole extraction efficiency. The invention based on indeno [1,2-b]The doping-free hole transport material of carbazole is applied to perovskite solar cells, and the short-circuit photocurrent density of the cell device reaches 22.31 mA cm‑2Open circuit voltage of 1.089V, fillThe fill factor 0.7784, photoelectric conversion efficiency is as high as 18.91%, shows wide commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a solar cell based on indeno [1,2-b]A doping-free hole transport material of carbazole, and preparation and application thereof.
Background
As a new generation of photovoltaic technology, Perovskite Solar Cells (PSCs for short) have the advantages of simple preparation process, easily adjustable materials, low cost, and the like, and the latest certification efficiency has reached 25.2% (National Renewable Energy Laboratory, NREL, 2019). The hole transport layer is used as an important component of PSCs, plays a role in collecting photogenerated holes of the perovskite absorption layer and transporting the photogenerated holes to the counter electrode, effectively inhibits the recombination of device interface electrons, and plays a crucial role in influencing the efficiency and stability of the battery. At present, a hole transport material applied to a perovskite solar cell mostly needs to use dopants such as 4-tert-butylpyridine, LiTFSI and cobalt salt to obtain high-efficiency photoelectric conversion efficiency. On one hand, doping causes the preparation process of the battery to be complicated, and the preparation cost is increased; on the other hand, the use of the dopant also leads to the significant improvement of the hygroscopicity of the battery, thereby reducing the service life of the battery and accelerating the aging speed of the battery. Therefore, the doping-free hole transport material is developed, and the method has important practical significance for future industrial application of the perovskite solar cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst based on indeno [1,2-b]The doping-free hole transport material of carbazole is used as a hole transport layer to prepare a perovskite solar cell device, and dopants such as 4-tert-butylpyridine, LiTFSI, cobalt salt and the like are not needed, so that the perovskite solar cell device is simpleThe preparation process of the device is simplified, the preparation cost is reduced, meanwhile, the aging of the perovskite light absorption layer is effectively prevented, and the stability of the device is greatly improved; the invention also aims to provide a preparation method of the hole transport material and application of the hole transport material in a perovskite solar cell.
The invention is realized by the following technical scheme:
based on indeno [1,2-b]A doping-free hole transport material of carbazole having the chemical structural formula of formula (V):
the invention further improves the scheme as follows:
the above-mentioned materials based on indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole comprises the following steps:
s1: subjecting the compound of the formula (I) and 2-tributylstannyl thiophene to Still coupling reaction to generate a compound of a formula (II);
s2: brominating the compound of formula (II) to produce a compound of formula (III);
s3: the compound of formula (III) and the compound of formula (IV) are subjected to a coupling reaction to produce the compound of formula (V), i.e. based on indeno [1,2-b]Doping-free hole transport materials of carbazole.
Further, in said S1, the compound of formula (I) is subjected to a Still coupling reaction with 2-tributylstannyl thiophene in toluene solvent under the catalysis of tetratriphenylphosphine palladium to generate a compound of formula (II), wherein the amount of each substance is calculated by the amount of substance, the compound of formula (I): 2-tributylstannyl thiophene: palladium catalyst = 1: 1-2: 0.01 to 0.2; the reaction time is 6-12 h.
Further, in the step S2, brominating the compound of formula (II) with N-bromosuccinimide (NBS) in tetrahydrofuran as a solvent to generate a compound of formula (III), wherein the amount of each substance is calculated by the amount of substance, the compound of formula (II): NBS = 1: 1 to 1: 2; the reaction time is 2-8 h.
Further, in the S3, the compound of formula (III) is reacted with the compound of formula (IV) in the solvent N, N-Dimethylformamide (DMF) under the action of a palladium catalyst, an organophosphorus ligand, an organic acid and a base to obtain the compound of formula (V), wherein the amount of each substance is calculated by the amount of substance, and the compound of formula (IV): a compound of formula (III): palladium catalyst: organophosphorus ligands: organic acid: alkali = 1: 2-5: 0.01-0.2: 0.02-0.5: 0.2-1: 2-4.
Further, in S3, the palladium catalyst is one or more of tetrakistriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, and palladium acetate;
the organophosphorus ligand is one or more than two of triphenylphosphine, tri (o-methylphenyl) phosphorus, tri (m-methylphenyl) phosphorus, tri (p-methylphenyl) phosphorus, tricyclohexylphosphine, n-butyl di (1-adamantyl) phosphine, tri-tert-butylphosphine, 1' -bis (diphenylphosphine) ferrocene or 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl;
the organic acid is one or a mixture of more than two of pivalic acid, acetic acid and trifluoroacetic acid;
the alkali is one or more of sodium carbonate, potassium carbonate, sodium tert-butoxide or potassium tert-butoxide.
Further, each step of the method also comprises a separation and purification step.
The invention further improves the scheme as follows:
the above is based onIndeno [1,2-b]The application of the doping-free hole transport material of carbazole in perovskite solar cells.
The invention has the beneficial effects that: the material is indeno [1,2-b]Carbazole-thiophene is taken as a peripheral electron donor unit, tetrathienopyrrole is taken as a molecular core, and when the carbazole-thiophene is taken as a hole transport layer to prepare the perovskite solar cell device, dopants such as 4-tert-butylpyridine, LiTFSI, cobalt salt and the like are not needed, so that the preparation process of the device is simplified, the preparation cost is reduced, meanwhile, the perovskite light absorption layer is effectively prevented from aging, and the stability of the device is greatly improved; the battery test results show that: the short-circuit photocurrent density of the device reaches 22.31 mA cm-2The open circuit voltage is 1.089V, the filling factor is 0.7784, and the photoelectric conversion efficiency is as high as 18.91%. The invention has simple synthetic route and low preparation cost, and can realize large-scale synthesis of materials; the material disclosed by the invention has good dissolving and film-forming properties and excellent thermal stability; steady-state fluorescence spectrum tests show that the material has high hole extraction efficiency.
Drawings
FIG. 1 shows a hole transport material (V)1H NMR;
FIG. 2 shows a hole transport material (V)13C NMR;
FIG. 3 is a UV-VIS absorption and fluorescence emission spectrum of the hole transport material (V);
FIG. 4 is a differential pulse voltammogram of a hole transport material (V);
FIG. 5 shows the stable fluorescence test of the hole transport material (V);
FIG. 6 is a schematic diagram of a perovskite solar cell structure prepared based on a hole transport material (4); in the figure: 1. the solar cell comprises a metal electrode, 2, a hole transport layer, 3, a perovskite photosensitive layer, 4, an electron transport layer, 5 and conductive glass;
FIG. 7 is an I-V plot of a perovskite solar cell prepared based on the hole transport material (4);
fig. 8 is an I-V plot of a perovskite solar cell prepared based on the hole transport material Spiro-OMeTAD.
Detailed Description
The embodiment provides a method based on indeno [1,2-b]Doping-free hole transport materials of carbazole of the formula
。
The above-mentioned hole transport material (compound of formula (V)) is prepared by the following method:
the compounds of the formula (I) used in the present examples were prepared and synthesized according to the literature Wang, J.; Zhang, H.; Wu, B.; Wang, Z.; Sun, Z.; Xue, S.; Wu, Y.; Hagfeldt, A.; Liang, M. Angew. chem. 2019, 58 (44), 15724-; the compound of formula (IV) was prepared and synthesized according to patent CN 201811021012.7; other reagents are commercially available.
S1: subjecting the compound of the formula (I) and 2-tributylstannyl thiophene to Still coupling reaction to generate a compound of a formula (II);
the method specifically comprises the following steps: under the protection of argon, a compound (5 mmol, 2.02 g) of the formula (I), 2-tributylstannyl thiophene (6 mmol, 2.24 g), tetrakistriphenylphosphine palladium (0.1 mmol, 116 mg) and 20mL of toluene are sequentially added into a 100 mL three-neck round-bottom flask; stirring the mixed solution, heating to 110 ℃, reacting for 8 hours, cooling to room temperature, adding water and ethyl acetate for extraction, washing an organic phase for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 25/1-3/1) to yield 1.55 g of the compound of formula (II) as a pale yellow viscous liquid with a yield of 76%.
The structural characterization data for the compound of formula (II) is:1H NMR (400 MHz, CDCl3): δ 8.32 (s, 1H),8.13 (s, 1H), 7.83 (d,J= 7.2 Hz, 1H), 7.67-7.64 (m, 2H), 7.46 (d,J= 7.2Hz, 1H), 7.38-7.30 (m, 4H), 7.22 (d,J= 4.4 Hz, 1H), 7.08 (dd,J= 4.8 Hz,J= 3.6 Hz, 1H), 4.26 (t,J= 7.2Hz, 2H), 1.98-1.88 (m, 2H), 1.6 (s, 6h), 0.99(t,J= 7.2 Hz, 3H).13C NMR (100 MHz, CDCl3): δ 154.8, 146.2, 145.7, 141.2,140.9, 139.8, 138.4, 128.2, 127.5, 127.2, 125.8, 124.2, 123.7, 123.6, 123.0,122.1, 120.1, 117.7, 114.4, 109.2, 100.2, 46.5, 15.0, 28.3, 22.6, 12.1. HRMS(ESI) calcd for C28H26NS (M+H+): 408.1768, found: 408.1747.
s2: brominating the compound of formula (II) to produce a compound of formula (III);
the method specifically comprises the following steps: to a 100 mL single neck round bottom flask, under ice bath conditions, was added the compound of formula (II) (3 mmol, 1.22 g) and 15 mL tetrahydrofuran, followed by the addition of N-bromosuccinimide (3.3 mmol, 588 mg) to the system in portions; removing the ice bath, heating the mixed solution to 25 ℃ and reacting for 3 hours in a dark place; extracting with water and ethyl acetate, washing the organic phase with water for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-3/1) to yield 1.4 g of the compound of formula (III) as a pale yellow solid with a yield of 96%.
The structural characterization data for the compound of formula (III) is:1H NMR (400 MHz, CDCl3): δ 8.23 (sd,J=1.0 Hz, 1H), 8.12 (s, 1H), 7.85 (d,J= 7.2 Hz, 1H), 7.69 (s, 1H), 7.59 (dd,J= 8.4 Hz, J = 1.0 Hz, 1H), 7.48 (d,J= 8.4 hz, 1H), 7.39-7.32 (m, 3H),7.08 (d,J= 4.0 Hz, 1H), 7.05 (d,J= 4.0 Hz, 1H), 4.33 (t,J= 7.2 Hz, 2H),2.02-1.93 (M, 2H), 1.61 (s, 6H), 1.03 (t,J= 7.2 Hz, 3H).13C NMR (100 MHz,CDCl3): 154.7, 147.6, 145.8, 141.1, 141.0, 139.6, 138.4, 130.9, 127.4, 127.1,124.9, 123.7, 123.5, 122.9, 122.7, 122.1, 120.0, 117.5, 114.3, 109.8, 109.1,100.2, 46.4, 45.0, 28.2, 22.5, 12.0. HRMS (ESI) calcd for C28H25BrNS (M+H+):486.0891, found: 486.0881.
s3: the compound of formula (III) and the compound of formula (IV) are subjected to a coupling reaction to produce the compound of formula (V), i.e. based on indeno [1,2-b]Doping-free hole transport materials of carbazole.
The method specifically comprises the following steps: under the protection of argon, sequentially adding a compound IV (467 mg, 1 mmol), a compound III (1.21 g, 2.5 mmol), potassium carbonate (345 mg, 2.5 mmol), palladium acetate (34 mg, 0.15 mmol), tri (o-methylphenyl) phosphorus (91 mg, 0.3 mmol), acetic acid (36 mg, 0.6 mmol) and anhydrous N, N-dimethylformamide (5 mL) into a dried Schlenk tube, and heating the reaction solution to 150 ℃ for continuous stirring reaction for 30 h; adding water for quenching, extracting by dichloromethane, washing an organic phase for three times by water, drying by anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; purifying the crude product by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-1/1) to obtain 549 mg of the compound shown as the formula V, wherein the yield is 43 percent of orange solid
The structural characterization data for the compound of formula (V) is:1H NMR (400 MHz,d8-THF): δ 8.42 (s, 2H),8.27 (s, 2H), 7.89-7.87 (m, 4H), 7.73-7.69 (m, 4H), 7.55-7.48 (m, 6H), 7.37-7.24 (m, 10H), 4.43 (t,J= 6.8 Hz, 4H), 4.19 (t,J= 6.4 Hz, 2H), 2.0-1.89(m, 8H), 1.60 (s, 12H), 1.46-1.40 (m, 4H), 1.04-0.99 (m, 9H).13C NMR (100MHz,d8-THF): δ 157.4, 155.7, 152.6, 148.5, 145.6, 144.4, 143.7, 141.7,139.4, 138.0, 136.5, 134.0,130.7, 128.9, 128.5, 127.8, 127.4, 126.8, 125.2,124.9, 123.7, 121.8, 121.0, 120.7, 117.9, 114.9, 113.8, 112.4, 107.3, 107.1,102.5, 98.4, 66.4, 44.2, 42.6, 30.0, 27.9, 27.7, 25.7, 24.1, 20.9, 11.7, 9.2.HRMS (ESI) calcd for C80H67N3OS6(M+H+): 1278.3687, found: 1278.3627.
example 2:
this example is substantially the same as example 1, with the main differences:
synthesis of a compound of formula (II):
a100 mL three-necked round-bottomed flask was charged with the compound of formula (I) (5 mmol, 2.02 g), 2-tributylstannyl thiophene (7.5 mmol, 2.79 g), tetrakistriphenylphosphine palladium (0.1 mmol, 116 mg), and 20mL toluene in this order under argon protection; stirring the mixed solution, heating to 110 ℃, reacting for 8 hours, cooling to room temperature, adding water and ethyl acetate for extraction, washing an organic phase for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 25/1-3/1) to yield 1.55 g of the compound of formula (II) as a pale yellow viscous liquid with a yield of 78%.
Synthesis of a compound of formula (III):
to a 100 mL single neck round bottom flask, under ice bath conditions, was added the compound of formula (II) (3 mmol, 1.22 g) and 15 mL tetrahydrofuran, followed by the addition of N-bromosuccinimide (3.3 mmol, 588 mg) to the system in portions; removing the ice bath, heating the mixed solution to 25 ℃ and reacting for 6 hours in a dark place; extracting with water and ethyl acetate, washing the organic phase with water for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-3/1) to yield 1.3g of the compound of formula (III) as a pale yellow solid with a yield of 89%.
Based on indeno [1,2-b]Synthesis of a doping-free hole transport material of carbazole, a compound of formula (V).
Under the protection of argon, sequentially adding a compound IV (467 mg, 1 mmol), a compound III (1.21 g, 2.5 mmol), potassium carbonate (345 mg, 2.5 mmol), palladium acetate (34 mg, 0.15 mmol), tri (o-methylphenyl) phosphorus (91 mg, 0.3 mmol), pivalic acid (61 mg, 0.6 mmol) and anhydrous N, N-dimethylformamide (5 mL) into a dried Schlenk tube, and heating the reaction solution to 150 ℃ for continuous stirring reaction for 30 h; adding water for quenching, extracting by dichloromethane, washing an organic phase for three times by water, drying by anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; and (3) purifying the crude product by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-1/1) to obtain 613 mg of the compound shown in the formula V, wherein the compound is an orange solid and the yield is 48%.
Example 3:
this example is substantially the same as example 1, with the main differences:
synthesis of a compound of formula (II):
under the protection of argon, a compound (5 mmol, 2.02 g) of the formula (I), 2-tributylstannyl thiophene (6 mmol, 2.24 g), tetrakistriphenylphosphine palladium (0.25 mmol, 290 mg) and 20mL of toluene are sequentially added into a 100 mL three-neck round-bottom flask; stirring the mixed solution, heating to 110 ℃, reacting for 12 h, cooling to room temperature, adding water and ethyl acetate for extraction, washing an organic phase for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 25/1-3/1) to give 1.57 g of the compound of formula (II) as a pale yellow viscous liquid with a yield of 79%.
Synthesis of a compound of formula (III):
to a 100 mL single neck round bottom flask, under ice bath conditions, was added the compound of formula (II) (3 mmol, 1.22 g) and 15 mL tetrahydrofuran, followed by the addition of N-bromosuccinimide (3.6 mmol, 641 mg) to the system in portions; removing the ice bath, heating the mixed solution to 25 ℃ and reacting for 8 hours in a dark place; extracting with water and ethyl acetate, washing the organic phase with water for 3 times, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to remove solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-3/1) to yield 1.1g of the compound of formula (III) as a pale yellow solid with a yield of 75%.
Based on indeno [1,2-b]Synthesis of a doping-free hole transport material of carbazole, a compound of formula (V).
Under the protection of argon, sequentially adding a compound IV (467 mg, 1 mmol), a compound III (1.21 g, 2.5 mmol), potassium carbonate (345 mg, 2.5 mmol), palladium acetate (34 mg, 0.15 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (123 mg, 0.3 mmol), acetic acid (36 mg, 0.6 mmol) and anhydrous N, N-dimethylformamide (5 mL) into a dried Schlenk tube, and heating the reaction solution to 150 ℃ for continuous stirring reaction for 30 hours; adding water for quenching, extracting by dichloromethane, washing an organic phase for three times by water, drying by anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; and (3) purifying the crude product by column chromatography (eluent: petroleum ether/dichloromethane = 15/1-1/1) to obtain 103 mg of the compound shown as the formula V, wherein the compound is an orange solid and the yield is 8.1%.
Example 4:
this example is substantially the same as example 1, with the main differences:
based on indeno [1,2-b]Synthesis of a doping-free hole transport material of carbazole, a compound of formula (V).
Under the protection of argon, sequentially adding a compound IV (467 mg, 1 mmol), a compound III (1.21 g, 2.5 mmol), potassium carbonate (345 mg, 2.5 mmol), tris (dibenzylideneacetone) dipalladium (138 mg, 0.15 mmol), tris (o-methylphenyl) phosphorus (91 mg, 0.3 mmol), acetic acid (36 mg, 0.6 mmol) and anhydrous N, N-dimethylformamide (5 mL) into a dried Schlenk tube, and heating the reaction solution to 150 ℃ for continuous stirring reaction for 30 hours; the reaction solution is detected by a TLC spot plate and a liquid chromatograph-mass spectrometer, no target product is produced, and the yield is 0%.
Test example: characterization of hole-transporting material (V):
1. photophysical and electrochemical testing of hole transport materials (V)
The results, as measured by uv-vis absorption and fluorescence emission spectroscopy (fig. 3) and cyclic voltammograms (fig. 4), show: the energy levels of the HOMO (-5.11 eV) and the LUMO (-2.68 eV) of the hole transport material (V) are obviously higher than the energy levels of the halogen-mixed perovskite (HOMO = -5.6 eV and LUMO = -3.9 eV), so that the efficient separation and transmission of holes can be effectively ensured, the transition of electrons from the perovskite layer to the hole transport layer can be effectively blocked, and the occurrence of the interface electron recombination phenomenon can be inhibited.
2. Thermal stability of the hole-transporting Material (V)
The thermal stability of the cavity has a great influence on the stability of the perovskite cell as a whole, for which the thermal stability of (V) was tested by measuring the glass transition temperature by differential temperature scanning: (T g). The results of measurement are shown in FIG. 5, and it can be seen from the results of measurement that the hole transport material (V)T gIs 187.2oC, the hole transport material is more stableThe amorphous state of the porous structure is beneficial to improving the thermal stability of the cavity when the porous structure is applied to the perovskite solar cell.
3. Steady-state fluorescence test of hole transport materials (V)
In order to better understand the interaction of hole transport between the interface of the hole layer and the Perovskite layer, a sample of ITO/Perovskite/HTM was prepared to study the interface behavior, and the steady-state photoluminescence spectrum of the holes was measured (6). The graph obtained by the test shows that after the perovskite material shows that a layer of hole transport material (V) is coated in a spinning mode, the fluorescence quenching efficiency reaches 93.4%, and the hole transport material is shown to have excellent hole extraction efficiency, so that the battery performance is improved.
4. I-V Curve test of hole transport Material (V)
The structural schematic diagram of the perovskite solar cell device designed by the invention is shown in FIG. 7, and the preparation steps are as follows:
(1) the method comprises the following steps of (1) ultrasonically cleaning ITO (indium tin oxide) conductive glass for 30 minutes by using glass cleaning liquid, deionized water and ethanol in sequence, soaking the cleaned ITO conductive glass in the ethanol for later use, blow-drying before use, placing in an ozone environment, and irradiating for 30 minutes by using ultraviolet light;
(2) controlling the conditions, namely, mixing tin oxide (SnO) at the rotating speed of 3500rmp for 30s2) The aqueous solution is coated on ITO conductive glass in a spinning way, and then the ITO conductive glass is annealed for 1 hour on a hot plate at the temperature of 170 ℃;
(3) formamidine iodide (FAI, concentration of 1M), methylamine bromide (MABr, 0.2M) and lead bromide (PbBr) were sequentially added to a mixed solvent of absolute anhydrous N, N-dimethylformamide and dimethyl sulfoxide20.22M), lead iodide (PbI)21.1M) and CsI (concentration of 1.5M), prepared as a cesium-containing triple cation perovskite precursor solution and stirred for 30 minutes with heating at 50 ℃ before use;
(4) depositing the perovskite film on SnO by adopting a two-step method2On a substrate: dropping the perovskite precursor solution on a substrate at 200 rpm s-1The acceleration of (2) was such that the substrate was held at 1000 rpm for 10 seconds and then at 2000 rpm s-1Acceleration ofThe substrate was held at 6000 rpm for 20 seconds. Dripping 110 μ L of anhydrous chlorobenzene at the center of the substrate 6 seconds before the end of the program, immediately transferring the substrate to a heating plate after the end of the spin coating, and heating at 100 ℃ for 45 minutes;
(5) a solution of the hole transporting material was prepared by dissolving 15 mg of the compound of formula (V) in 1 mL of chlorobenzene. Controlling the rotation speed to be 4000 rpm for 30s, spin-coating the hole transport material on the perovskite layer, immediately transferring the substrate onto a heating plate outside a glove box after the spin-coating is finished, and heating for 10 minutes at 100 ℃;
(6) and depositing gold with the thickness of about 80 nm on the hole transport layer as a counter electrode by a vacuum evaporation method.
Based on indeno [1,2-b]The I-V curve of perovskite solar cell device with carbazole doping-free hole transport material as hole transport layer is shown in figure 8, and the short circuit photocurrent density of the cell device reaches 22.31 mA cm-2The open-circuit voltage is 1.089V, the filling factor is 0.7784, the photoelectric conversion efficiency is as high as 18.91 percent, and a smaller hysteresis effect is shown, which indicates that the doping-free hole transport material has a higher application prospect.
Claims (8)
1. Based on indeno [1,2-b]A doping-free hole transport material of carbazole characterized by having the chemical structural formula of formula (V):
2. indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized by comprising the following steps:
s1: subjecting the compound of the formula (I) and 2-tributylstannyl thiophene to Still coupling reaction to generate a compound of a formula (II);
s2: brominating the compound of formula (II) to produce a compound of formula (III);
s3: the compound of formula (III) and the compound of formula (IV) are subjected to a coupling reaction to produce the compound of formula (V), i.e. based on indeno [1,2-b]Doping-free hole transport materials of carbazole;
3. indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized in that:
in said S1, the compound of formula (I) is subjected to Still coupling reaction with 2-tributylstannyl thiophene in solvent toluene under the catalysis of palladium tetratriphenylphosphine to generate a compound of formula (II), wherein the amount of each substance is calculated by the amount of the substance, the compound of formula (I): 2-tributylstannyl thiophene: palladium catalyst = 1: 1-2: 0.01 to 0.2; the reaction time is 6-12 h.
4. Indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized in that:
in said S2, brominating the compound of formula (II) with N-bromosuccinimide (NBS) in tetrahydrofuran as a solvent to produce a compound of formula (III), wherein the amounts of each material are based on the amount of material, the compound of formula (II): NBS = 1: 1 to 1: 2; the reaction time is 2-8 h.
5. Indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized in that:
in the S3, the compound of the formula (III) reacts with the compound of the formula (IV) in a solvent of N, N-Dimethylformamide (DMF) under the action of a palladium catalyst, an organophosphorus ligand, an organic acid and a base to obtain the compound of the formula (V), wherein the amount of each substance is calculated by the amount of the substance, and the compound of the formula (IV): a compound of formula (III): palladium catalyst: organophosphorus ligands: organic acid: alkali = 1: 2-5: 0.01-0.2: 0.02-0.5: 0.2-1: 2-4.
6. Indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized in that:
in the step S3, the palladium catalyst is one or a mixture of two or more of tetrakistriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium and palladium acetate;
the organophosphorus ligand is one or more than two of triphenylphosphine, tri (o-methylphenyl) phosphorus, tri (m-methylphenyl) phosphorus, tri (p-methylphenyl) phosphorus, tricyclohexylphosphine, n-butyl di (1-adamantyl) phosphine, tri-tert-butylphosphine, 1' -bis (diphenylphosphine) ferrocene or 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl;
the organic acid is one or a mixture of more than two of pivalic acid, acetic acid and trifluoroacetic acid;
the alkali is one or more of sodium carbonate, potassium carbonate, sodium tert-butoxide or potassium tert-butoxide.
7. Indeno [1,2-b]The preparation method of the doping-free hole transport material of carbazole is characterized in that: the method also comprises a separation and purification step in each step.
8. Indeno [1,2-b]The application of the doping-free hole transport material of carbazole in perovskite solar cells.
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| CN112778354A (en) * | 2021-01-27 | 2021-05-11 | 淮阴工学院 | Silicon-containing thick pentacyclic hole transport material and preparation method and application thereof |
| CN112778354B (en) * | 2021-01-27 | 2022-05-27 | 淮阴工学院 | Hole transport material containing silicon fused pentacyclic ring, and preparation method and application thereof |
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Application publication date: 20200522 Assignee: Suzhou Liwei New Materials Technology Co.,Ltd. Assignor: HUAIYIN INSTITUTE OF TECHNOLOGY Contract record no.: X2023980047090 Denomination of invention: Doping free hole transport materials based on indeno [1,2-b] carbazole and their synthesis methods and applications Granted publication date: 20220823 License type: Common License Record date: 20231115 |