CN114805324A - Carbazole hole transport material and synthesis method and application thereof - Google Patents
Carbazole hole transport material and synthesis method and application thereof Download PDFInfo
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- CN114805324A CN114805324A CN202210332534.9A CN202210332534A CN114805324A CN 114805324 A CN114805324 A CN 114805324A CN 202210332534 A CN202210332534 A CN 202210332534A CN 114805324 A CN114805324 A CN 114805324A
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- 230000005525 hole transport Effects 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 50
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims abstract description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940125904 compound 1 Drugs 0.000 claims abstract description 9
- 229930192474 thiophene Natural products 0.000 claims abstract description 5
- 150000001716 carbazoles Chemical class 0.000 claims abstract description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims abstract description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 3
- 238000005893 bromination reaction Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 62
- 238000004528 spin coating Methods 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
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- 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 12
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
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- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 claims description 5
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- 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 claims description 5
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- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 4
- VUWBMXNMKRWSEI-UHFFFAOYSA-N C1(CCCCC1)P(C1=C(C=CC=C1)C1=C(C=C(C=C1C(C)C)C(C)C)C(C)C)C1CCCCC1.[Cl] Chemical group C1(CCCCC1)P(C1=C(C=CC=C1)C1=C(C=C(C=C1C(C)C)C(C)C)C(C)C)C1CCCCC1.[Cl] VUWBMXNMKRWSEI-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- UJQAHAANAPEYLR-UHFFFAOYSA-N [2-chloro-6-[2,4,6-tri(propan-2-yl)phenyl]phenyl]-dicyclohexylphosphane Chemical group CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC(Cl)=C1P(C1CCCCC1)C1CCCCC1 UJQAHAANAPEYLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012296 anti-solvent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
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- 238000005118 spray pyrolysis Methods 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- -1 6,6' - (3- ((9, 9-dimethyl-9H-fluoren-3-yl) (4-methoxyphenyl) amino) thiophene-2, 5-diyl) bis (N- (9, 9-dimethyl-9H-fluoren-2-yl) -N, 9-bis (4-methoxyphenyl) -9H-carbazole-3-amine) Chemical compound 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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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
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- H—ELECTRICITY
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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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
- H10K85/60—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
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Abstract
The invention belongs to the technical field of solar cells, and discloses a carbazole hole transport material, a synthetic method thereof, and application thereof in Cs 2 AgBiBr 6 Use in a double perovskite solar cell. The carbazole hole transport material takes thiophene as a core structure, a carbazole derivative as a bridging group and N- (9, 9-dimethyl-9H-3-fluorene) -4-methoxyaniline as an end group. Firstly, carrying out Suzuki coupling reaction on 2, 5-dibromothiophene and a compound 1 to obtain an intermediate 2; carrying out bromination reaction on the intermediate 2 to obtain an intermediate 3; then the intermediate 3 and a reactant 4 are subjected to Buchwald-Hartwig coupling reaction to obtain a final product PTDCZ-TFNP. PTDCZ-TFNP and Spiro-OMeTADThe hole transport layer constructs a double-hole transport layer and is applied to Cs 2 AgBiBr 6 In the double perovskite solar cell, the energy level arrangement inside the device is optimized, the charge extraction and transmission performance is improved, the loss of internal energy is avoided, and the efficiency and the stability of the cell are greatly improved.
Description
Technical Field
The invention belongs to the technical field of solar cells, and relates to a carbazole hole transport material, a synthesis method thereof, and application thereof in Cs 2 AgBiBr 6 Use in a double perovskite solar cell.
Background
In recent years, organic-inorganic hybrid lead-halogen Perovskite Solar Cells (PSCs) have been breaking through and have received wide attention all over the world. To date, the highest certified Photoelectric Conversion Efficiency (PCE) of single-junction PSCs has reached 25.7% (Min, H.; Lee, D.Y.; Kim, J.; Kim, G.; Lee, K.S.; Kim, J.; Paik, M.J.; Kim, Y.K.; Kim, K.S.; Kim, M.G.; Shin, T.J.; Il Seok, S.Nature 2021,598,444.). However, stability and lead toxicity are two major critical factors that limit their commercialization. In response to this problem, efforts have been made in recent years to develop stable non-lead-based perovskite materials, where Cs is present as a substitute for conventional lead-based perovskite materials 2 AgBiBr 6 The double perovskite has the advantages of stable chemical structure, excellent photoelectric property, environmental friendliness and the like, and is a potential candidate for a non-lead-based perovskite material, which is one of research hotspots in the field of perovskite solar cells (Slavey, A.H.; Hu, T.; Lindenberg, A.M.; Karunadasa, H.I.J.Am.Chem.Soc.2016,138, 2138; Londo, G.; Mahesh, S.; Buizza, L.R.V.; Wright, A.D.; Ramadan, A.J.; Abdi-Jaleby, M.; Nayak, P.K.; Herz, L.M.; Snaith, H.J.ACS. Energy Lett.2020,5,2200.). At present, Cs 2 AgBiBr 6 The maximum photoelectric conversion efficiency of the double perovskite solar cell is only 3.11 percent (based on photosensitive dye and Cs) 2 AgBiBr 6 The maximum cell efficiency of the light-absorbing layer was 4.23%), which is far from the theoretical limit efficiency of 8% (Wang, b.; li, N.; yang, L.; dall' Agnese, c.; jena, a.k.; sasaki, s.i.; miyasaka, t.; tamiaki, h.; wang, x.f.j.am.chem.soc.2021,143, 2207; sirtl, m.t.; hooijer, r.; amer, m.; ebadi, f.g.; mohammadi, m.; maheu, c.; weis, a.; van Gorkom, b.t.;
S.；Janssen,R.A.J.；Mayer,T.；Dyakonov,V.；Tress,W.；Bein,T.Adv.Energy Mater.2022,12,2103215.). At present, limit Cs 2 AgBiBr 6 One of the main factors for improving the efficiency of the double perovskite battery is Cs 2 AgBiBr 6 Double perovskite material and traditional hole transport material 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-the problem of energy level mismatch of 9,9' -spirobifluorene (Spiro-OMeTAD); meanwhile, studies have shown that lithium salt, an additive in a Spiro-OMeTAD hole transport layer, has strong hydrophilicity and is one of the main causes of perovskite decomposition (Yang, X.; Chen, Y.; Liu, P.; Xiang, H.; Wang, W.; Ran, R.; Zhou, W.; Shao, Z.Adv.Funct.Mater.2020,30,2001557; Liu, C.; Igci, C.; Yang, Y.; Syzganteva, O.A.; Syzganteva, M.A.; Rakstys, K.; Kanda, H.; Shibayama, N.; Ding, B.; Zhang, X.; Jankauskaska, V.; Ding, Y.; Das.; Dyson, P.udJ.; M.Andin, M.England, E.1.Egld. 60,20489).
Therefore, to further increase Cs 2 AgBiBr 6 The photoelectric conversion efficiency and stability of the double perovskite solar cell, on one hand, a hole transport material with a deeper energy level needs to be developed to reasonably allocate the energy level arrangement in the cell, so that the charge extraction and transmission performance is improved, and excessive internal energy loss is avoided; on the other hand, the hole transport material is required to have better hydrophobicity, and a hydrophilic additive is not required to be introduced, so that the stability of the battery is enhanced.
Disclosure of Invention
Aiming at the defects of the traditional hole transport material, the invention aims to develop a non-doped hole transport material with deeper energy level, good hydrophobicity and excellent charge transport performance, and apply the non-doped hole transport material to Cs 2 AgBiBr 6 In a double perovskite solar cell. The hole transport material PTDCZ-TFNP is constructed by taking thiophene as a core structure, taking a carbazole derivative as a bridging group and taking N- (9, 9-dimethyl-9H-3-fluorene) -4-methoxyaniline as an end group. The material has a deeper energy level, and a double-hole transmission layer is constructed by the material and a traditional hole transmission material Spiro-OMeTAD and is applied to Cs 2 AgBiBr 6 In the double perovskite solar cell, the energy level arrangement inside the device is optimized, the charge extraction and transmission performance is improved, and the internal energy loss is avoidedThereby improving the efficiency of the battery; meanwhile, the PTDCZ-TFNP is a non-doped hole transport material, does not need an additive when in use, has stronger hydrophobicity, and can effectively isolate Cs 2 AgBiBr 6 The degradation of two perovskite and the contact of steam prevents the perovskite, and then promotes the stability of battery. At present, a double-hole-transport-layer-based Cs is constructed by using a non-doped hole-transport material PTDCZ-TFNP 2 AgBiBr 6 The preparation method of the double perovskite solar cell is not reported.
The technical scheme adopted by the invention is as follows:
a carbazole hole transport material is chemically known as 6,6' - (3- ((9, 9-dimethyl-9H-fluoren-3-yl) (4-methoxyphenyl) amino) thiophene-2, 5-diyl) bis (N- (9, 9-dimethyl-9H-fluoren-2-yl) -N, 9-bis (4-methoxyphenyl) -9H-carbazole-3-amine), is PTDCZ-TFNP for short, and is characterized in that: thiophene is used as a core structure, a carbazole derivative is used as a bridging group, N- (9, 9-dimethyl-9H-3-fluorene) -4-methoxyaniline is used as an end group, and the thiophene has the following chemical structural formula:
the synthetic method of the undoped hole transport material PTDCZ-TFNP comprises the following steps: carrying out Suzuki coupling reaction on the 2, 5-dibromothiophene and the compound 1 to obtain an intermediate 2; obtaining an intermediate 3 by bromination reaction of the intermediate 2; the intermediate 3 and the reactant 4 are subjected to Buchwald-Hartwig coupling reaction to obtain a final product PTDCZ-TFNP, and the specific steps are as follows:
(i) adding 2, 5-dibromothiophene, a compound 1, chlorine (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II) (Xphos Pd G2), potassium phosphate aqueous solution and a solvent tetrahydrofuran into a dry reaction vessel, stirring uniformly under the protection of nitrogen, heating to 40-60 ℃ for reaction for 15-24h, cooling the reaction liquid to room temperature after the reaction is finished, extracting and separating the reaction liquid for three times by using dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a yellow-green solid compound 2;
(ii) adding a compound 2 and a solvent tetrahydrofuran into a dry reaction container, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding an N, N-dimethylformamide solution of N-bromosuccinimide, heating to room temperature, reacting for 12-24h, adding ice water, stirring for 30-60min after the reaction is finished, extracting and separating a reaction solution for three times by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a yellow solid compound 3;
(iii) adding a compound 3, a compound 4, palladium acetate, potassium tert-butoxide, tri-tert-butylphosphine and a solvent toluene into a dry reaction vessel, stirring uniformly under the protection of nitrogen, heating to 100 ℃ and 120 ℃ for reaction for 12-24h, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution for three times by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain the yellow solid hole transport material PTDCZ-TFNP.
The synthetic route is as follows:
in step (i), 2, 5-dibromothiophene: compound 1: chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II): the molar ratio of potassium phosphate is 1:2.1:0.03: 10; the concentration of the 2, 5-dibromothiophene is 0.1-0.2 mol/L; the molar concentration of the potassium phosphate aqueous solution is 0.5 mol/L; the volume ratio of the tetrahydrofuran to the potassium phosphate aqueous solution is 1: 2-3.
In step (ii), compound 2: the molar ratio of NBS is 1: 2; the concentration of the compound 2 is 0.02-0.04 mol/L.
In step (iii), compound 3: compound 4: potassium tert-butoxide: palladium acetate: the molar ratio of tri-tert-butylphosphine is 1:2.5:5:0.1: 0.2; the concentration of the compound 3 is 0.02-0.05 mol/L.
Cs (volatile organic Compounds) 2 AgBiBr 6 Double perovskiteA solar cell comprising a dual hole transport layer comprising a PTDCZ-TFNP hole transport layer and a Spiro-OMeTAD hole transport layer prepared according to the present invention.
The Cs 2 AgBiBr 6 The double perovskite solar cell structurally comprises a transparent conductive substrate, an electron transport layer and Cs 2 AgBiBr 6 The double perovskite photoactive layer, the PTDCZ-TFNP hole transport layer, the Spiro-OMeTAD hole transport layer and the metal electrode, and the preparation method comprises the following steps:
(1) cutting a transparent conductive substrate into a fixed size, etching, sequentially ultrasonically cleaning the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone sterilization treatment on the substrate;
(2) preparing a metal oxide electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method, and transferring the metal oxide electron transport layer into a glove box for later use;
(3) transferring the conductive substrate coated with the electron transport layer into a glove box, and spin-coating Cs 2 AgBiBr 6 Spin-coating the double perovskite precursor solution on the electron transport layer, and dripping isopropanol anti-solvent in the spin-coating process of the perovskite precursor solution to form Cs 2 AgBiBr 6 A double perovskite light absorbing layer;
(4) covering a chlorobenzene solution containing a hole transport material PTDCZ-TFNP on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method, and sintering at the temperature of 100-120 ℃ for 10-20 minutes to form a PTDCZ-TFNP hole transport layer;
(5) covering a hole transport layer solution containing Spiro-OMeTAD on the PTDCZ-TFNP hole transport layer prepared in the step (4) by a spin coating method to form a Spiro-OMeTAD hole transport layer;
(6) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
In the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence;
in the step (2), the electron transport layer is one of titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the Cs 2 AgBiBr 6 The preparation method of the double perovskite precursor liquid comprises the following steps: adding bismuth tribromide, silver bromide and cesium bromide into an N, N-Dimethylformamide (DMSO) solution in a glove box, sealing and keeping out of the sun, placing the mixture on a hot table at 100 ℃ for magnetic stirring for 2 hours, and storing the solution for later use after the solution is cooled to room temperature;
in the step (4), the concentration of the hole transport layer solution is 5-20 mg/mL;
in the step (5), the solution of the hole transport layer containing the Spiro-OMeTAD comprises a hole transport material Spiro-OMeTAD and additives LiTFSI and TBP;
in the step (6), the metal electrode is one of gold, silver or copper.
(3) The operation steps of (4) and (5) are all finished in a glove box filled with nitrogen.
The invention has the following advantages:
(1) the undoped hole transport material PTDCZ-TFNP provided by the invention and the Spiro-OMeTAD hole transport layer construct a double-hole transport layer, and the double-hole transport layer is applied to Cs 2 AgBiBr 6 In the double perovskite solar cell, the energy level arrangement inside the device is successfully optimized, the charge extraction and transmission performance is effectively improved, the loss of internal energy is avoided, and the efficiency of the cell is greatly improved;
(2) the undoped hole transport material PTDCZ-TFNP provided by the invention has stronger hydrophobicity, does not need to use additives, and can effectively isolate Cs 2 AgBiBr 6 The degradation of two perovskite and the contact of steam prevents the perovskite, and then promotes the stability of battery.
Drawings
FIG. 1 shows Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 Structural schematic diagram of double perovskite solar cell (1 is FTO conductive substrate, 2 is TiO) 2 Dense layer, 3 is TiO 2 Mesoporous layer, 4 is Cs 2 AgBiBr 6 A double perovskite photoactive layer, 5 is a PTDCZ-TFNP hole transport layer, and 6 is a Spiro-OMeTAD hole transport layerA transmission layer, 7 is a gold electrode);
FIG. 2 shows Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 A schematic energy level diagram of a double perovskite solar cell;
FIG. 3 shows Cs of examples 1 and 2 of the present invention and comparative example 2 AgBiBr 6 Double perovskite solar cell and traditional Cs 2 AgBiBr 6 J-V curve diagram (illumination intensity of 100 mW/cm) of double perovskite solar cell 2 )；
FIG. 4 shows Cs of example 1 of the present invention and comparative example 2 AgBiBr 6 Double perovskite solar cell and traditional Cs 2 AgBiBr 6 Stability test chart of double perovskite solar cell.
Detailed Description
The present invention is further described in the following examples in order to enable those skilled in the art to better understand the present invention, but the scope of the present invention is not limited to the following examples, and the scope of the present invention is defined by the claims.
Example 1:
synthesis of carbazole hole transport material PTDCZ-TFNP and application thereof in Cs 2 AgBiBr 6 Application in double perovskite solar cells:
(i) 2, 5-Dibromothiophene (1.5G,3.76mmol), Compound 1(0.43G,1.79mmol), Xphos Pd G2(0.04G,0.05mmol), 0.5M K were added to a dry reaction vessel 3 PO 4 Stirring the aqueous solution (24mL) and tetrahydrofuran (12mL) serving as a solvent uniformly under the protection of nitrogen, heating to 40 ℃ for reaction for 20 hours, cooling the reaction liquid to room temperature after the reaction is finished, extracting and separating the reaction liquid for three times by using dichloromethane solution (150mL), collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, using petroleum ether/dichloromethane (3:1vol/vol) as an eluent, and drying in vacuum to obtain a yellow-green solid compound 2(2.02g, yield: 86%). 1 H NMR(400MHz,DMSO-d 6 )δ8.62(dd,J＝1.9,0.7Hz,2H),8.39–8.33(m,2H),7.80(2H,dd,J＝8.5,1.9Hz,2H),7.62–7.54(m,6H),7.47(ddd,J＝8.4,7.1,1.3Hz,2H),7.38–7.29(m,6H),7.28–7.22(m,4H),3.90(s,6H).
(ii) Adding compound 2(1g,1.60mmol) and tetrahydrofuran (50mL) as a solvent into a dry reaction vessel, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding 5mL of N, N-dimethylformamide solution (0.64mol/L) of N-bromosuccinimide, then heating to room temperature for reaction for 15h, adding ice water after the reaction is finished, stirring for 30min, extracting and separating the reaction solution for three times by using dichloromethane solution (150mL), collecting an organic layer, removing the solvent under reduced pressure, separating and extracting a collection by using a silica gel chromatographic column, using petroleum ether/dichloromethane (2:1vol/vol) as an eluent, and drying in vacuum to obtain yellow solid compound 3(1.15g, yield: 92%). 1 H NMR(400MHz,Chloroform-d)δ8.52–8.42(m,1H),8.32(t,J＝1.9Hz,2H),7.78(ddt,J＝15.1,6.9,2.1Hz,1H),7.72–7.65(m,1H),7.56–7.30(m,11H),7.27–7.09(m,6H),3.98–3.92(m,6H).
(iii) Adding compound 3(1g,1.28mmol), compound 4(0.89g,2.81mmol), palladium acetate (0.06g,0.26mmol), potassium tert-butoxide (0.36g,3.2mmol), tri-tert-butylphosphine (1.03g,5.12mmol) and solvent toluene (50mL) into a dry reaction vessel, stirring uniformly under nitrogen protection, heating to 120 ℃ for reaction for 24h, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution with dichloromethane solution (150mL) for three times, collecting an organic layer, removing the solvent under reduced pressure, separating and extracting the collection by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (1:1vol/vol) as an eluent, and drying in vacuum to obtain a yellow solid hole transport material PTDCZ-TFNP (1.07g, yield: 53.4%). 1 H NMR(400MHz,DMSO-d6)δ7.70–7.65(m,1H),7.66–7.59(m,3H),7.58–7.49(m,5H),7.45–7.40(m,4H),7.39–7.35(m,2H),7.33(d,J＝7.4Hz,1H),7.30–7.16(m,12H),7.14(d,J＝1.6Hz,1H),7.11(d,J＝8.8Hz,3H),7.09–7.03(m,4H),7.01(td,J＝6.4,3.2Hz,4H),6.96(d,J＝2.1Hz,1H),6.87(ddd,J＝9.1,6.4,2.9Hz,4H),6.75(dq,J＝8.3,3.1,2.1Hz,5H),3.84(d,J＝14.1Hz,6H),3.71(d,J＝5.8Hz,6H),3.60(s,3H),1.27(d,J＝5.0Hz,9H),1.22(s,9H).HR-MSThe calculated value is C 108 H 87 N 5 O 5 S,1565.6428, found 1566.6414.
Cs using undoped hole transport materials PTDCZ-TFNP and Spiro-OMeTAD hole transport layers as double hole transport materials 2 AgBiBr 6 The preparation method and the process of the double perovskite solar cell are as follows:
the perovskite solar cell has a cell structure of FTO/c-TiO 2 /m-TiO 2 Perovskite/PTDCZ-TFNP/Spiro-OMeTAD/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of 15mm x 15mm size and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30 min.
(2) Spin-coating ethanol solution of 960mg/ml tetraisopropyl titanate on a glass conductive substrate by spin-coating method, controlling the rotation speed at 4000rpm and the spin-coating time at 30s, heating to 200 deg.C, and sintering for 30min to form a layer of TiO 2 The compact layer is subjected to ultraviolet ozone treatment; subsequently, 390mg/ml of nano TiO 2 Is spin-coated on TiO 2 And (3) controlling the revolution number to be 3000rpm and the spin coating time to be 30s on the compact layer, heating the compact layer to 500 ℃, sintering the compact layer for 30min, carrying out ultraviolet ozone treatment on the compact layer, and then transferring the prepared electronic transmission layer film into a glove box for standby.
(3) In a glove box, bismuth tribromide (228.8mg,0.51mmol), silver bromide (129.6mg,0.69mmol) and cesium bromide (255.4mg,1.2mmol) were added to 1mL of DMSO solution, sealed and protected from light, placed on a 100 ℃ hot bench and magnetically stirred for 2 hours, and the solution was stored until it cooled to room temperature. Using a spin coater, the prepared 30 μ L of Cs 2 AgBiBr 6 Spin coating of double perovskite solution on TiO 2 Controlling the revolution number of the film to be 4000rpm, controlling the spin coating time to be 60s, dropwise adding 200 mu L of isopropanol-containing solution 25 s before the end of the spin coating, and annealing and calcining the perovskite film at 250 ℃ for 10min after the end of the spin coating to obtain compact and uniform Cs 2 AgBiBr 6 A double perovskite thin film.
(4) PTDCZ-TFNP hole transport layer solution (15mg PTDCZ-TFNP dissolved in 1mL chlorobenzene) 30 μ L was spin-coated onto the surface of the perovskite thin film by spin coating, the number of revolutions was controlled to 4000rpm, the spin-coating time was 30s, and it was annealed and calcined at 100 ℃ for 10min to obtain PTDCZ-TFNP hole transport layer thin film.
(5) After a solution of Spiro-OMeTAD hole transport layer (72.3mg of Spiro-OMeTAD, 28.8. mu.L of t-butylpyridine, 17.5. mu.L of LiTFSI dissolved in 845. mu.L of chlorobenzene) was spin-coated onto the surface of the PTDCZ-TFNP hole transport layer thin film by a spin coating method, the number of revolutions was controlled at 4000rpm, and the spin coating time was 30 s.
(6) Finally, 100nm Au is deposited on the device film by a vacuum evaporation method, and the evaporation area of the Au is 20mm by a special die 2 。
(3) The operation steps of (4) and (5) are all finished in a glove box filled with nitrogen.
Example 2:
synthesis of carbazole hole transport material PTDCZ-TFNP and application thereof in Cs 2 AgBiBr 6 Application in double perovskite solar cells:
(i) 2, 5-Dibromothiophene (1.5G,3.76mmol), Compound 1(0.43G,1.79mmol), Xphos Pd G2(0.04G,0.05mmol), 0.5M K were added to a dry reaction vessel 3 PO 4 Stirring the aqueous solution (24mL) and solvent tetrahydrofuran (10mL) uniformly under the protection of nitrogen, heating to 50 ℃ for reaction for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, extracting and separating the reaction liquid for three times by using dichloromethane solution (150mL), collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, using petroleum ether/dichloromethane (3:1vol/vol) as an eluent, and drying in vacuum to obtain a yellow-green solid compound 2(2.02g, yield: 86%). 1 H NMR(400MHz,DMSO-d 6 )δ8.62(dd,J＝1.9,0.7Hz,2H),8.39–8.33(m,2H),7.80(2H,dd,J＝8.5,1.9Hz,2H),7.62–7.54(m,6H),7.47(ddd,J＝8.4,7.1,1.3Hz,2H),7.38–7.29(m,6H),7.28–7.22(m,4H),3.90(s,6H).
(ii) Adding compound 2(1g,1.60mmol) and tetrahydrofuran (60mL) as a solvent into a dry reaction vessel, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding 5mL of N, N-dimethylformamide solution (0.64mol/L) of N-bromosuccinimide, then heating to room temperature for reaction for 20h, adding ice water after the reaction is finished, stirring for 50min, extracting and separating the reaction solution for three times by using dichloromethane solution (150mL), collecting an organic layer, removing the solvent under reduced pressure, separating and extracting a collection by using a silica gel chromatographic column, using petroleum ether/dichloromethane (2:1vol/vol) as an eluent, and drying in vacuum to obtain yellow solid compound 3(1.15g, yield: 92%). 1 H NMR(400MHz,Chloroform-d)δ8.52–8.42(m,1H),8.32(t,J＝1.9Hz,2H),7.78(ddt,J＝15.1,6.9,2.1Hz,1H),7.72–7.65(m,1H),7.56–7.30(m,11H),7.27–7.09(m,6H),3.98–3.92(m,6H).
(iii) Adding compound 3(1g,1.28mmol), compound 4(0.89g,2.81mmol), palladium acetate (0.06g,0.26mmol), potassium tert-butoxide (0.36g,3.2mmol), tri-tert-butylphosphine (1.03g,5.12mmol) and solvent toluene (40mL) into a dry reaction vessel, stirring uniformly under nitrogen protection, heating to 110 ℃ for reaction for 20h, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution with dichloromethane solution (150mL) for three times, collecting an organic layer, removing the solvent under reduced pressure, separating and extracting the collection by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (1:1vol/vol) as an eluent, and drying in vacuum to obtain a yellow solid hole transport material PTDCZ-TFNP (1.07g, yield: 53.4%). 1 H NMR (400MHz, DMSO-d6) δ 7.70-7.65 (m,1H), 7.66-7.59 (m,3H), 7.58-7.49 (m,5H), 7.45-7.40 (m,4H), 7.39-7.35 (m,2H),7.33(d, J ═ 7.4Hz,1H), 7.30-7.16 (m,12H),7.14(d, J ═ 1.6Hz,1H),7.11(d, J ═ 8.8Hz,3H), 7.09-7.03 (m,4H),7.01(td, J ═ 6.4,3.2Hz,4H),6.96(d, J ═ 2.1Hz,1H),6.87(ddd, J ═ 9.1,6.4,2.9, 2.4, 3.6H, 3.2Hz,4H), 6.7.7.7H, 5(d, J ═ 2, 3.1H), 3.8H, 3.1H, 5H, 3.1H, 5H, 3.8H, 3.1H, 5H, 3.8H, 5H, 3.1H, 5H, 1H, 7.8H, 7.1H, 1H, 7.8, 7.1H, 7H, 1, 7H, 1H, 7H, 1H, 7H, 1H, 7H, 1H 108 H 87 N 5 O 5 S,1565.6428, found 1566.6414.
Cs using undoped hole transport materials PTDCZ-TFNP and Spiro-OMeTAD hole transport layers as double hole transport materials 2 AgBiBr 6 The preparation method and the process of the double perovskite solar cell are as follows:
the perovskite solar cell has a cell structure of FTO/c-TiO 2 /m-TiO 2 Perovskite/PTDCZ-TFNP/Spiro-OMeTAD/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of 15mm x 15mm size and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30 min.
(2) Spin-coating ethanol solution of 960mg/ml tetraisopropyl titanate on a glass conductive substrate by spin-coating method, controlling the rotation speed at 4000rpm and the spin-coating time at 30s, heating to 200 deg.C, and sintering for 30min to form a layer of TiO 2 The compact layer is subjected to ultraviolet ozone treatment; subsequently, 150mg/ml of nano TiO 2 Is spin-coated on TiO 2 And (3) controlling the revolution number to be 3000rpm and the spin coating time to be 30s on the compact layer, heating the compact layer to 500 ℃, sintering the compact layer for 30min, carrying out ultraviolet ozone treatment on the compact layer, and then transferring the prepared electronic transmission layer film into a glove box for standby.
(3) In a glove box, bismuth tribromide (228.8mg,0.51mmol), silver bromide (129.6mg,0.69mmol) and cesium bromide (255.4mg,1.2mmol) were added to 1mL of DMSO solution, sealed and protected from light, placed on a 100 ℃ hot bench and magnetically stirred for 2 hours, and the solution was stored until it cooled to room temperature. Using a spin coater, the prepared 30 μ L of Cs 2 AgBiBr 6 Spin coating of double perovskite solution on TiO 2 Controlling the revolution number of the film to be 4000rpm, controlling the spin coating time to be 60s, dropwise adding 200 mu L of isopropanol-containing solution 25 s before the end of the spin coating, and annealing and calcining the perovskite film at 250 ℃ for 10min after the end of the spin coating to obtain compact and uniform Cs 2 AgBiBr 6 A double perovskite thin film.
(4) PTDCZ-TFNP hole transport layer solution (20mg of PTDCZ-TFNP dissolved in 1mL of chlorobenzene) 30 μ L was spin-coated onto the surface of the perovskite thin film by a spin coating method, the number of revolutions was controlled to 4000rpm, the spin-coating time was 30s, and it was annealed and calcined at 100 ℃ for 10min to obtain PTDCZ-TFNP hole transport layer thin film.
(5) A solution of Spiro-OMeTAD hole transport layer (72.3mg of Spiro-OMeTAD, 28.8. mu.L of t-butylpyridine, 17.5. mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the thin film of PTDCZ-TFNP hole transport layer by a spin coating method with the number of revolutions controlled at 4000rpm for 30 seconds.
(6) Finally, 100nm Au is deposited on the device film by a vacuum evaporation method, and the evaporation area of the Au is 20mm by a special die 2 。
(3) The operation steps of (4) and (5) are all finished in a glove box filled with nitrogen.
Comparative example:
the traditional hole transport material Spiro-OMeTAD is only selected as a hole transport layer to be applied to Cs 2 AgBiBr 6 In the double perovskite solar cell, the preparation method and the process are as follows:
the perovskite solar cell has a cell structure of FTO/c-TiO 2 /m-TiO 2 Perovskite/cyclone-OMeTAD/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of 15mm x 15mm size and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30 min.
(2) Spin-coating ethanol solution of 960mg/ml tetraisopropyl titanate on a glass conductive substrate by spin-coating method, controlling the rotation speed at 4000rpm and the spin-coating time at 30s, heating to 200 deg.C, and sintering for 30min to form a layer of TiO 2 The compact layer is subjected to ultraviolet ozone treatment; subsequently, 150mg/ml of nano TiO 2 Is spin-coated on TiO 2 Controlling the revolution number to be 3000rpm and the spin coating time to be 30s on the compact layer, heating the compact layer to 500 ℃, sintering the compact layer for 30min, carrying out ultraviolet ozone treatment on the compact layer, and then carrying out ultraviolet ozone treatment on the compact layerThe transfer layer film was transferred to a glove box for use.
(3) In a glove box, bismuth tribromide (228.8mg,0.51mmol), silver bromide (129.6mg,0.69mmol) and cesium bromide (255.4mg,1.2mmol) were added to 1mL of DMSO solution, sealed and protected from light, placed on a 100 ℃ hot bench and magnetically stirred for 2 hours, and the solution was stored until it cooled to room temperature. Using a spin coater, the prepared 30 μ L of Cs 2 AgBiBr 6 Spin coating of double perovskite solution on TiO 2 Controlling the revolution number of the film to be 4000rpm, controlling the spin coating time to be 60s, dropwise adding 200 mu L of isopropanol-containing solution 25 s before the end of the spin coating, and annealing and calcining the perovskite film at 250 ℃ for 10min after the end of the spin coating to obtain compact and uniform Cs 2 AgBiBr 6 A double perovskite thin film.
(4) A solution of Spiro-OMeTAD hole transport layer (72.3mg of Spiro-OMeTAD, 28.8. mu.L of t-butylpyridine, 17.5. mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the thin film of PTDCZ-TFNP hole transport layer by a spin coating method with the number of revolutions controlled at 4000rpm for 30 seconds.
(5) Finally, 100nm Au is deposited on the device film by a vacuum evaporation method, and the evaporation area of the Au is 20mm by a special die 2 。
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
FIG. 1 shows Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 Structural schematic diagram of double perovskite solar cell (1 is FTO conductive substrate, 2 is TiO) 2 Dense layer, 3 is TiO 2 Mesoporous layer, 4 is Cs 2 AgBiBr 6 A double perovskite photoactive layer, 5 a PTDCZ-TFNP hole transport layer, 6 a Spiro-OMeTAD hole transport layer, and 7 a gold electrode).
FIG. 2 shows Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 Energy level schematic of a double perovskite solar cell. As can be seen, Cs 2 AgBiBr 6 The energy levels of the double perovskite material, the hole transport material PTDCZ-TFNP and the Spiro-OMeTAD hole transport material are arranged in a step mode, the energy level matching is reasonable, and the extraction and the transmission of charges are facilitated.
FIG. 3 is the present inventionCs of inventive examples 1 and 2 and comparative example 2 AgBiBr 6 Double perovskite solar cell and traditional Cs 2 AgBiBr 6 J-V curve diagram (illumination intensity of 100 mW/cm) of double perovskite solar cell 2 ). As can be seen from the figures, examples 1 and 2 and conventional Cs 2 AgBiBr 6 The double perovskite solar cell respectively obtains the photoelectric conversion efficiency of 2.05%, 1.85% and 1.61%.
FIG. 4 shows Cs of example 1 of the present invention and comparative example 2 AgBiBr 6 Double perovskite solar cell and traditional Cs 2 AgBiBr 6 Stability test chart of double perovskite solar cell. As can be seen from the figure, the working of example 1 is continued after 1500h aging while the conventional Cs maintains the original efficiency of more than 90 percent 2 AgBiBr 6 The double perovskite solar cell maintained only 36.58% of the original efficiency after being subjected to a 1500h aging experiment.
Claims (10)
1. The carbazole hole transport material is characterized in that thiophene is used as a core structure, a carbazole derivative is used as a bridging group, N- (9, 9-dimethyl-9H-3-fluorene) -4-methoxyaniline is used as an end group, PTDCZ-TFNP is short, and the chemical structural formula is as follows:
2. the method for synthesizing the carbazole-based hole transport material according to claim 1, comprising the steps of:
carrying out Suzuki coupling reaction on the 2, 5-dibromothiophene and the compound 1 to obtain an intermediate 2;
carrying out bromination reaction on the intermediate 2 to obtain an intermediate 3;
the intermediate 3 and the reactant 4 are subjected to Buchwald-Hartwig coupling reaction to obtain a final product PTDCZ-TFNP; the reaction flow is as follows:
3. the synthesis method of the carbazole hole transport material according to claim 2, comprising the following specific steps:
(i) adding 2, 5-dibromothiophene, a compound 1, chlorine (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II), potassium phosphate aqueous solution and a solvent tetrahydrofuran into a dry reaction vessel, stirring uniformly under the protection of nitrogen, heating to 40-60 ℃ for reaction for 15-24h, cooling the reaction solution to room temperature after the reaction is finished, separating and purifying, and drying in vacuum to obtain a yellow-green solid compound 2;
(ii) adding a compound 2 and a solvent tetrahydrofuran into a dry reaction container, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding an N, N-dimethylformamide solution of N-bromosuccinimide, heating to room temperature, reacting for 12-24h, adding ice water after the reaction is finished, stirring for 30-60min, separating, purifying, and drying in vacuum to obtain a yellow solid compound 3;
(iii) adding a compound 3, a compound 4, palladium acetate, potassium tert-butoxide, tri-tert-butylphosphine and a solvent toluene into a dry reaction vessel, stirring uniformly under the protection of nitrogen, heating to 100 ℃ and 120 ℃ for reaction for 12-24h, cooling the reaction solution to room temperature after the reaction is finished, separating and purifying, and drying in vacuum to obtain the yellow solid hole transport material PTDCZ-TFNP.
4. The method for synthesizing a carbazole-based hole transport material according to claim 3, wherein in step (i), 2, 5-dibromothiophene: compound 1: chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II): the molar ratio of potassium phosphate is 1:2.1:0.03: 10; the concentration of the 2, 5-dibromothiophene is 0.1-0.2 mol/L; the molar concentration of the potassium phosphate aqueous solution is 0.5 mol/L; the volume ratio of the tetrahydrofuran to the potassium phosphate aqueous solution is 1: 2-3.
5. The method for synthesizing a carbazole-based hole transport material according to claim 3, wherein in step (ii), the ratio of compound 2: the molar ratio of NBS is 1: 2; the concentration of the compound 2 is 0.02-0.04 mol/L.
6. The method for synthesizing a carbazole-based hole transport material according to claim 3, wherein in step (iii), the ratio of compound 3: compound 4: potassium tert-butoxide: palladium acetate: the molar ratio of tri-tert-butylphosphine is 1:2.5:5:0.1: 0.2; the concentration of the compound 3 is 0.02-0.05 mol/L.
7. Use of a carbazole-based hole transport material according to claim 1 for preparing Cs 2 AgBiBr 6 Use of a double perovskite solar cell.
8. The use according to claim 7, wherein said Cs 2 AgBiBr 6 A double perovskite solar cell comprises a double hole transport layer, wherein the double hole transport layer comprises a PTDCZ-TFNP hole transport layer and a Spiro-OMeTAD hole transport layer.
9. The use of claim 8, wherein said Cs is 2 AgBiBr 6 The preparation steps of the double perovskite solar cell are as follows:
(1) cutting a transparent conductive substrate into a fixed size, etching, sequentially ultrasonically cleaning the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone sterilization treatment on the substrate;
(2) preparing a metal oxide electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method, and transferring the metal oxide electron transport layer into a glove box for later use;
(3) transferring the conductive substrate coated with the electron transport layer into a glove box, and spin-coating Cs 2 AgBiBr 6 Spin-coating the double perovskite precursor solution on the electron transport layer, and dripping isopropanol anti-solvent in the spin-coating process of the perovskite precursor solution to form Cs 2 AgBiBr 6 Double perovskiteA light absorbing layer;
(4) covering a chlorobenzene solution containing a hole transport material PTDCZ-TFNP on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method, and sintering at the temperature of 100-120 ℃ for 10-20 minutes to form a PTDCZ-TFNP hole transport layer;
(5) covering a hole transport layer solution containing Spiro-OMeTAD on the PTDCZ-TFNP hole transport layer prepared in the step (4) by a spin coating method to form a Spiro-OMeTAD hole transport layer;
(6) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
10. The use according to claim 9,
in the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence;
in the step (2), the electron transport layer is one of titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the Cs 2 AgBiBr 6 The preparation method of the double perovskite precursor liquid comprises the following steps: adding bismuth tribromide, silver bromide and cesium bromide into an N, N-dimethylformamide DMSO solution in a glove box, sealing and keeping out of the sun, placing on a hot table at 100 ℃ for magnetic stirring for 2 hours, and storing the solution after the solution is cooled to room temperature for later use;
in the step (4), the concentration of the hole transport layer solution is 5-20 mg/mL;
in the step (5), the hole transport layer solution containing Spiro-OMeTAD comprises a hole transport material Spiro-OMeTAD and additives LiTFSI and TBP;
in the step (6), the metal electrode is one of gold, silver or copper;
and (5) finishing the operations of the steps (3), (4) and (5) in a glove box filled with nitrogen.
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