CN113471364A - Preparation method of efficient and stable perovskite solar cell - Google Patents
Preparation method of efficient and stable perovskite solar cell Download PDFInfo
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- CN113471364A CN113471364A CN202110647655.8A CN202110647655A CN113471364A CN 113471364 A CN113471364 A CN 113471364A CN 202110647655 A CN202110647655 A CN 202110647655A CN 113471364 A CN113471364 A CN 113471364A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 68
- 230000005525 hole transport Effects 0.000 claims abstract description 44
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- 238000002161 passivation Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 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
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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 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 28
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
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- 239000012044 organic layer Substances 0.000 description 18
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- 229940125904 compound 1 Drugs 0.000 description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 16
- 229940125782 compound 2 Drugs 0.000 description 15
- 239000003480 eluent Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
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- 238000001035 drying Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 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 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XTAALASUYSUXDX-UHFFFAOYSA-N n-(4-methoxyphenyl)-9,9-dimethylfluoren-2-amine Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(C=2C(=CC=CC=2)C2(C)C)C2=C1 XTAALASUYSUXDX-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 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
- 241000282461 Canis lupus Species 0.000 description 1
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
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- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 206010041232 sneezing Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Abstract
The invention belongs to the technical field of solar cells, and discloses a preparation method of a high-efficiency stable perovskite solar cell. Introducing a functional material CZ-Py taking carbazole As a core structure on the surface of the perovskite As a passivation layer, and adopting an organic small molecular material CZ-As As a hole transport material, thereby assembling the perovskite solar cell device. Firstly, the introduction of the passivation layer can passivate the defects of the surface and the grain boundary of the perovskite, effectively improve the transmission performance of electric charges, isolate the contact of the perovskite with water vapor and oxygen, inhibit the degradation of the perovskite and further improve the stability of a device; secondly, the energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, the energy levels are reasonably matched, and the extraction and transmission of charges are facilitated; in addition, the passivation material and the hole transport material have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, and are suitable for being used in the perovskite solar cell preparation process on a large scale.
Description
Technical Field
The invention belongs to the technical field of solar cells, and relates to a preparation method of a high-efficiency stable perovskite solar cell.
Background
The Photoelectric Conversion Efficiency (PCE) of organic-inorganic lead perovskite halide solar cells (PSCs) has been greatly improved over the past decade from the first 3.8% to over 25%, gaining wide attention from numerous scholars (j.j.yoo, g.seo, m.r. Chua, t.g.park, y.lu, f.rotamund, y.k.kim, c.s.moon, n.j.jeon, j.p.corea-Baena, v.bulovic, s.s.shin, m.g.bawendi, j.seo, Nature 2021,590, 587-. The high efficiency of perovskite solar cells results from the excellent optoelectronic properties of perovskite materials such as higher light absorption coefficient, higher carrier mobility, lower exciton binding energy, and tunable direct band gap (s.de Wolf, j.holovsky, s.j.moon, p.loper, b.niesen, m.leinsky, f.j.haug, j.h.yum, c.ballif, j.phys.chem.lett.2014,5, 1035-. Nevertheless, further improvements in efficiency and long-term stability of the device still limit large-scale production and commercial application of perovskite solar cells. One of the main factors adversely affecting the efficiency and stability of the battery is due to the presence of defects in the bulk phase and at the surface interface of the perovskite material. Perovskite thin films prepared by a solution method are generally polycrystalline, and rapid crystal growth causes the structure of a perovskite layer to have disorder, and the disorder distribution can generate grain boundary defects and crystal defects. These defects not only cause a decrease in crystal quality and severely affect the transport of carriers, but also accelerate moisture/oxygen permeation and accelerate degradation of the perovskite, thereby adversely affecting the efficiency and long-term stability of the perovskite solar cell (h.li, j.shi, j.deng, z.chen, y.li, w.zhao, j.wu, h.wu, y.luo, d.li, q.meng, adv.mater.2020,32, e 1907396.). On the other hand, 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-omatad) and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) are mostly adopted as Hole Transport Materials (HTM) in current high-efficiency perovskite solar cells, but the complicated synthesis route and purification steps of Spiro-omatad and PTAA make them high-cost materials, limiting their large-scale application in future commercialization (e.h.jung, n.j.jeon, e.y.park, c.s.moon, t.j.shin, t.y.yang, j.h.noh, j.seo, Nature 2019,567, 511. jeon, n.j.jeon, h.g.lee, y.c.kim, j.78j.78j.seo, seo.788, soh.31, 2014.g.je, chej.g.. Therefore, in order to further improve the efficiency and stability of the battery, on one hand, an effective interface passivation strategy needs to be provided to reduce the defects of the perovskite surface interface; on the other hand, the development of a novel low-cost and efficient hole transport material is urgently needed, so that the preparation cost of the hole transport material is greatly reduced while the charge extraction and transmission efficiency is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to develop a preparation method of a high-efficiency stable perovskite solar cell, which comprises the steps of introducing a functional material CZ-Py taking carbazole As a core structure on the surface of a perovskite As a passivation layer, and adopting an organic small molecular material CZ-As As a hole transport material, thereby assembling a perovskite solar cell device. The passivation material and the hole transmission material both take carbazole as a core structure, diphenylamine derivatives or fluorene derivatives as end groups, and N-substituted groups are 4-methoxybenzene or pyridine groups. On one hand, the introduction of the passivation layer can passivate the defects of the surface and the grain boundary of the perovskite, effectively improve the transmission performance of charges, simultaneously isolate the contact of the perovskite with water vapor and oxygen, inhibit the degradation of the perovskite and further improve the stability of the device; on the other hand, the energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, the energy levels are reasonably matched, and the extraction and transmission of charges are facilitated; in addition, the passivation material and the hole transport material have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, are suitable for being applied to the perovskite solar cell preparation process on a large scale, and are beneficial to commercial application. Therefore, the invention can not only improve the photoelectric property of the perovskite solar cell, enhance the stability of the cell, but also reduce the manufacturing cost of the cell.
The technical scheme adopted by the invention is as follows: a preparation method of a high-efficiency stable perovskite solar cell is characterized by comprising the following steps: in the preparation process of the perovskite solar cell, introducing a carbazole functional material CZ-Py containing pyridine groups into an anti-solvent solution, dropwise adding the carbazole functional material CZ-Py to the surface of the perovskite, and passivating a perovskite layer; subsequently, a hole transport material CZ-As is spin-coated on the perovskite thin film.
The perovskite solar cell is composed of a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer, a surface passivation layer, a hole transmission layer and a metal electrode, and the perovskite solar cell is prepared by the following specific 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 an electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method;
(3) moving the conductive substrate coated with the electron transmission layer into a glove box, spin-coating perovskite precursor liquid on the electron transmission layer through a spin-coating method, and dropwise adding a chlorobenzene antisolvent containing 0.1-3 mg/mL of a passivation material CZ-Py in the process of spin-coating the perovskite precursor liquid, wherein the dropwise adding amount is 100-300 mu L, so as to form a perovskite light absorption layer with a passivated surface;
(4) covering a hole transport layer solution containing a hole transport material CZ-As on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method to form a hole transport layer; the dosage of the hole transport layer solution is 30-60 mu L, and the concentration is 30-60 mg/mL;
(5) 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 metal oxides such as titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the perovskite light absorption layer is FAXMA1-XPb(IXBr1-X)3、CH3NH3PbI3-xClxOr all-inorganic perovskite CsPbI3、CsPbBr3One of (1); wherein FA is CH2＝CHNH3MA is CH3NH3，0≤x≤1；
The structural characteristics of the passivation material CZ-Py are as follows: the carbazole group is taken as a core structure, two ends of the carbazole group are directly connected with electron donating groups of fluorene derivatives or diphenylamine derivatives, and an N-substituted group is a pyridine group and has the following chemical structural general formula (I):
in the formula (I), R is a fluorene derivative or diphenylamine derivative electron-donating group respectively, and is specifically one of the following structures:
the synthesis method of the passivation material CZ-Py comprises the following steps: reacting carbazole and 4-iodopyridine to generate Buchwald-Hartwig reaction to obtain an intermediate 1; carrying out bromination reaction on the intermediate 1 to obtain an intermediate 2; the intermediate 2 and RH are subjected to Buchwald carbon nitrogen coupling reaction to obtain a final product CZ-Py, and the method comprises the following specific steps:
(i) adding carbazole, 4-iodopyridine, palladium acetate, tri-tert-butylphosphine, sodium tert-butoxide and a solvent toluene into a dry reaction vessel, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃, reacting for 24-48h, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction solution, washing for several times by using water, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain a compound 1;
(ii) dissolving the compound 1 in a tetrahydrofuran solvent, cooling the reaction liquid to 0-5 ℃, adding N-bromosuccinimide (NBS) into the reaction liquid in batches, and reacting for 8-12h after the NBS is added. After the reaction is finished, adding 50mL of dichloromethane into the reaction solution, washing the reaction solution for three times by using 150mL of water, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the residue by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (1:4vol/vol) as an eluent, and drying the mixture in vacuum to obtain a compound 2;
(iii) adding a compound 2, RH, palladium acetate, tri-tert-butylphosphine, potassium tert-butoxide and a solvent toluene into a dried reaction vessel, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 18-24h, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction liquid, washing with water for several times, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the compound CZ-Py.
The synthetic route is as follows:
in step (i), carbazole: 4-iodopyridine: palladium acetate: tri-tert-butylphosphine: the molar ratio of sodium tert-butoxide is 1:1.1:0.05:0.1: 3; the reaction concentration of carbazole is 0.04-0.08 mol/L; the volume ratio of the used amount of the reaction liquid to the used amount of dichloromethane is 1: 1-2.
In step (ii), compound 1: the molar ratio of NBS is 1: 2; the reaction concentration of the compound 1 is 0.02-0.04 mol/L.
In step (iii), compound 2: RH: palladium acetate: tri-tert-butylphosphine: the molar ratio of sodium tert-butoxide is 1:2.3:0.1:0.2: 6; the reaction concentration of the compound 2 is 0.04-0.08 mol/L.
In the step (4), the hole transport layer solution further comprises an additive; the additive is one or more of LiTFSI, tert-butyl pyridine or FK 209; the adding concentration is respectively as follows: LiTFSI is 20-30mmol/L, tert-butylpyridine is 200-300mmol/L, and FK209 is 1.0-2.0 mmol/L.
The hole transport material CZ-As has the structural characteristics that: carbazole is taken as a core structure, two ends of carbazole are directly connected with fluorene derivative groups, and an N-substituted group is a 4-methoxyphenyl group, which has the following chemical structure general formula (II):
the method for synthesizing the hole transport material CZ-As comprises the following steps: reacting carbazole and 4-iodoanisole by Buchwald-Hartwig reaction to obtain an intermediate 1'; carrying out bromination reaction on the intermediate 1 'to obtain an intermediate 2'; the intermediate 2' and fluorene derivative are subjected to Buchwald carbon nitrogen coupling reaction to obtain a final product CZ-As, and the method comprises the following specific steps:
(i) adding carbazole, 4-iodoanisole, palladium acetate, tri-tert-butylphosphine, sodium tert-butoxide and a solvent toluene into a dry reaction vessel, stirring uniformly at room temperature under the protection of nitrogen, heating to 110 ℃ and 120 ℃ for reaction for 24-48h, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction liquid, washing for several times by using water, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain a compound 1';
(ii) dissolving the compound 1' in a tetrahydrofuran solvent, cooling the reaction liquid to 0-5 ℃, adding N-bromosuccinimide (NBS) into the reaction liquid in batches, and reacting for 8-12h after the NBS is added. After the reaction is finished, adding 50mL of dichloromethane into the reaction solution, washing the reaction solution for three times by using 150mL of water, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the residue by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (1:4vol/vol) as an eluent, drying the mixture in vacuum, separating and purifying the obtained solid, and drying the solid in vacuum to obtain a compound 2';
(iii) adding a compound 2', a fluorene derivative, palladium acetate, tri-tert-butylphosphine, potassium tert-butoxide and a solvent toluene into a dry reaction vessel, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 18-24h, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction liquid, washing for several times by using water, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the compound CZ-As.
The synthetic route is as follows:
in step (i), carbazole: 4-iodoanisole: palladium acetate: tri-tert-butylphosphine: the molar ratio of sodium tert-butoxide is 1:1.1:0.05:0.1: 3; the reaction concentration of carbazole is 0.04-0.08 mol/L; the volume ratio of the used amount of the reaction liquid to the used amount of dichloromethane is 1: 1-2.
In step (ii), compound 1: the molar ratio of NBS is 1: 2; the reaction concentration of the compound 1 is 0.02-0.04 mol/L.
In step (iii), compound 2: fluorene derivatives: palladium acetate: tri-tert-butylphosphine: the molar ratio of sodium tert-butoxide is 1:2.3:0.1:0.2: 6; the reaction concentration of the compound 2 is 0.04-0.08 mol/L.
In the step (5), the metal electrode is one of gold, silver or copper.
The invention has the following advantages:
(1) the preparation process of the perovskite solar cell provided by the invention can effectively passivate the defects of the surface and the grain boundary of the perovskite, improve the transmission performance of electric charges, simultaneously isolate the contact of the perovskite with water vapor and oxygen, inhibit the degradation of the perovskite and further improve the stability of a device.
(2) In the perovskite solar cell prepared by the method, the energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, the energy levels are reasonably matched, and the extraction and transmission of charges are facilitated.
(3) The passivation material and the hole transport material used in the process have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, are suitable for being applied to the perovskite solar cell preparation process on a large scale, and are beneficial to commercial application.
Therefore, the invention not only can effectively improve the photoelectric property of the perovskite solar cell, enhance the stability of the cell, but also can reduce the manufacturing cost of the cell.
Drawings
FIG. 1 is a schematic structural diagram of a perovskite solar cell;
FIG. 2 is a schematic view showing the molecular structures of the passivation materials CZ-Py-1, CZ-Py-2 and the hole transport material CZ-As used in examples 1 and 2 of the present invention.
FIG. 3(a) is a cross-sectional scanning electron microscope image of a perovskite solar cell in which CZ-Py-1 is a passivation material and CZ-As is a hole transport material in example 1 of the present invention; (b) (c), (d), (e) and (f) are respectively the appearance diagrams of a perovskite film, a CZ-Py-1 passivated perovskite film, a hole transport material CZ-As film coated on the surface of the CZ-Py-1 passivated perovskite, a CZ-Py-2 passivated perovskite film and a CZ-As film coated on the surface of the CZ-Py-2 passivated perovskite.
FIG. 4 is an XRD pattern of a perovskite thin film and a CZ-Py-1, CZ-Py-2 modified perovskite thin film.
FIG. 5 is a J-V diagram of a perovskite solar cell based on a non-modified perovskite thin film and a CZ-Py-1, CZ-Py-2 modified perovskite thin film using CZ-As As a hole transport material.
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:
the preparation method and the process of the perovskite solar cell which adopts CZ-Py-1 As a passivation material and CZ-As As a hole transport material comprise the following steps:
the perovskite solar cell has a cell structure of FTO/c-TiO2/m-TiO2The Perovskite solar cell is prepared by the following steps of:
(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) Using spray pyrolysis, a 0.2M solution of titanium tetraisopropoxide and 2M acetylacetone in isopropanol was sprayed onto an FTO glass substrate heated to 500 deg.C to form a very thin layer of TiO2A dense layer; 150mg/ml of nano TiO2Is spin-coated on TiO2On the dense layer, the rotation speed was controlled to 5000rpm, the spin coating time was 30s, and then it was dried on a heating plate at 100 ℃ for 15min, and it was sintered at 500 ℃ for 60 min.
(3) Mixing lead iodide (PbI)2) Formamidinium iodide (FAI), lead bromide (PbBr)2) Methyl ammonium bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) with stirring at room temperature. Spin-coating the prepared 31 μ L perovskite solution on TiO with a spin coater2On the film, the rotation speed was controlled to 1000rpm, the spin-coating time was controlled to 10s, and subsequently the rotation speed was controlled to 5000rpm, and the spin-coating time was controlled to 30s, during which 200. mu.L of CZ-Py-1 chlorobenzene containing 1mg/mL was dropped onto the film, and the perovskite thin film was annealed and calcined at 100 ℃ for 30 min. Then placed in a glove box for 1h and cooled.
(4) After 45. mu.L of a hole transport layer solution (40mg of CZ-As, 125. mu.L of t-butylpyridine, 17.5. mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the perovskite thin film by a spin coating method, the number of revolutions was controlled at 4500rpm, and the spin coating time was 30 s.
(5) Finally, 100nm Au was deposited on the device film by vacuum evaporation.
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
In the step (3), the synthesis route and the specific steps of the passivation material CZ-Py-1 are as follows:
(i) carbazole (0.335g, 2.0mmol), 4-iodopyridine (0.451g, 2.2mmol), palladium acetate (0.023g, 0.1mmol), tri-tert-butylphosphine (0.040g, 0.2mmol), sodium tert-butoxide (0.577g, 6.0mmol) and toluene (50ml) solvent are added into a dry reaction vessel, stirred uniformly under nitrogen protection at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 12-24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, 50mL of dichloromethane was added to the reaction mixture, and the mixture was washed with 150mL of water three times, and the organic layer was collectedThe solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel with petroleum ether/ethyl acetate (1:3vol/vol) as eluent and dried in vacuo to give compound 1 as a yellow oil (0.442g, 85% yield).1H NMR(400MHz,CDCl3): δ8.83(d,2H,J＝6.0Hz),8.13(d,2H,J＝7.6Hz),7.54-7.58(m,4H),7.43(t,2H,J＝7.6Hz), 7.33(t,2H,J＝7.2Hz).
(ii) Compound 1(0.520g, 2.0mmol) was dissolved in 50mL tetrahydrofuran solvent, the reaction solution was cooled to 0-5 ℃ and N-bromosuccinimide (NBS,0.712g, 4.0mmol) was added to the reaction solution in several portions and reacted for 8-12 h. After the reaction was completed, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (1:4vol/vol) as an eluent and dried in vacuo to give Compound 2(0.772g, 96% yield) as a yellow powder.1H NMR(400MHz,DMSO)δ8.62(d,J＝1.9Hz, 2H),7.77(dd,J＝4.7,1.4Hz,2H),7.64(dd,J＝8.8,2.0Hz,2H),7.56(d,J＝8.8Hz,2H).
(iii) Compound 2(0.480g, 1.2mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882g, 2.8mmol), palladium acetate (0.028g, 0.12mmol), tri-tert-butylphosphine (0.049g, 0.24mmol), sodium tert-butoxide (0.692g, 7.2mmol) and the solvent toluene (50ml) were added to a dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 18-24H. After the reaction was completed, it was cooled to room temperature, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography using petroleum ether/ethyl acetate (6:1vol/vol) as an eluent and dried in vacuo to obtain CZ-Py-1 (0.731g, yield 70%) as a yellow powder.1H NMR (400MHz, DMSO) δ 8.81(dd, J ═ 13.9,6.1Hz,2H),7.90(d, J ═ 2.0Hz,2H),7.73(ddd, J ═ 11.2,4.7,1.5Hz,2H),7.59(ddd, J ═ 16.9,14.6,7.8Hz,6H),7.47-7.38 (m,2H),7.29-7.14(m,6H),7.12-6.99(m,6H),6.89(dd, J ═ 25.1,9.0Hz,4H),6.73(dd, J ═ 8.3,2.1Hz,2H), 3.72(d, J ═ 20.6Hz,6H), 1.33-1.20 (m,12H), calculated values of C: C, 1: 1H, 1.7.7.7.7, 6H, and 1.7.7.9 (calculated values of d, 6H)61H50N4O2870.3943, found in factValue 870.3928.
In the step (4), the synthesis route and the specific steps of the hole transport material CZ-As are As follows:
(i) carbazole (0.335g, 2mmol), 4-iodoanisole (0.515g, 2.2mmol), palladium acetate (0.023g, 0.1mmol), tri-tert-butylphosphine (0.040g, 0.2mmol), sodium tert-butoxide (0.577g, 6.0mmol) and toluene (50ml) solvent are added into a dry reaction vessel, stirred uniformly under nitrogen protection at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 12-24 h. After completion of the reaction, it was cooled to room temperature, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (1:10vol/vol) as an eluent and dried in vacuo to give Compound 1' (0.442g, 81% yield) as a white powder.1H NMR(400MHz,CDCl3)δ, 8.15(d,J＝8.0Hz,2H),7.46(d,J＝8.8Hz,2H),7.40(td,J＝8.4,0.8Hz,2H),7.32(d,J＝8.4Hz, 2H),7.28(td,J＝8.0,0.8Hz,2H),7.12(d,J＝8.8Hz,2H),3.93(s,3H).
(ii) Compound 1(0.546g, 2mmol) was dissolved in 50mL tetrahydrofuran solvent, the reaction solution was cooled to 0-5 deg.C, and then N-bromosuccinimide (NBS,0.712g, 4mmol) was added to the reaction solution in several portions, and reacted for 8-12 h. After the reaction was completed, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel chromatography using petroleum ether/dichloromethane (1:10vol/vol) as an eluent and dried in vacuo to give Compound 2' (0.802g, 93% yield) as a white powder.1H NMR(400MHz,CDCl3)δ,8.19(dd,J＝2.0,0.8 Hz,2H),7.48(dd,J＝8.4,2.0Hz,2H),7.38(d,J＝8.8Hz,2H),7.17(dd,J＝8.4,0.8Hz,2H), 7.10(d,J＝8.8Hz,2H),3.92(s,3H).
(iii) Adding a compound of 2' (0.515g, 1.2mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882g, 2.8mmol) into a dry reaction vessel,Palladium acetate (0.028g, 0.12mmol), tri-tert-butylphosphine (0.049g, 0.24mmol), sodium tert-butoxide (0.692g, 7.2mmol) and toluene (50ml) as solvent are stirred uniformly under nitrogen at room temperature and then heated to 110 ℃ and 120 ℃ for reaction for 18-24 h. After completion of the reaction, it was cooled to room temperature, 50mL of methylene chloride was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography using petroleum ether/ethyl acetate (6:1vol/vol) As an eluent and dried in vacuo to give Compound CZ-As (0.961g, 89% yield) As a yellow powder.1H NMR (400MHz, DMSO) δ 7.94(d, J ═ 2.0Hz,2H),7.62(d, J ═ 7.5Hz, 2H),7.56(dd, J ═ 8.6,2.8Hz,4H),7.43(d, J ═ 7.3Hz,2H),7.30-7.16(m,10H),7.06(t, J ═ 6.2Hz, 4H),6.99(d, J ═ 2.1Hz,2H),6.89(d, J ═ 9.0Hz,4H),6.73(dd, J ═ 8.3,2.1Hz,2H),3.88(d, J ═ 10.2Hz,3H),3.72(s,6H),1.30-1.25(m,12H), calculated values of C: C-C63H53N3O3899.4081, found 899.4071.
Example 2:
the preparation method and the process of the perovskite solar cell which adopts CZ-Py-2 As a passivation material and CZ-As As a hole transmission material comprise the following steps:
the perovskite solar cell has a cell structure of FTO/c-TiO2/m-TiO2The Perovskite solar cell is prepared by the following steps of:
(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 respectively, and then treating the glass substrate in an ultraviolet ozone machine for 30 min.
(2) Using spray pyrolysis, a 0.2M solution of titanium tetraisopropoxide and 2M acetylacetone in isopropanol was sprayed onto an FTO glass substrate heated to 500 deg.C to form a very thin layer of TiO2A dense layer; 150mg/ml of nano TiO2Is spin-coated on TiO2On the dense layer, the rotation speed was controlled to 5000rpm, the spin coating time was 30s, and then it was dried on a heating plate at 100 ℃ for 15min, and it was sintered at 500 ℃ for 60 min.
(3) Mixing lead iodide (PbI)2) Formamidinium iodide (FAI), lead bromide (PbBr)2) Methyl ammonium bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) with stirring at room temperature. Spin-coating the prepared 31 μ L perovskite solution on TiO with a spin coater2On the film, the rotation speed was controlled to 1000rpm, the spin-coating time was controlled to 10s, and subsequently the rotation speed was controlled to 5000rpm, and the spin-coating time was controlled to 30s, during which 150. mu.L of CZ-Py-2 chlorobenzene containing 2mg/mL was dropped onto the film, and the perovskite thin film was annealed and calcined at 100 ℃ for 30 min. Then placed in a glove box for 1h and cooled.
(4) After 60. mu.L of a hole transport layer solution (60mg of CZ-As, 125. mu.L of t-butylpyridine, 17.5. mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the perovskite thin film by a spin coating method, the number of revolutions was controlled at 4500rpm, and the spin coating time was 30 s.
(5) Finally, 100nm Au was deposited on the device film by vacuum evaporation.
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
In the step (3), the synthesis route and the specific steps of the passivation material CZ-Py-2 are as follows:
(i) carbazole (0.335g, 2.0mmol), 4-iodopyridine (0.451g, 2.2mmol), palladium acetate (0.023g, 0.1mmol), tri-tert-butylphosphine (0.040g, 0.2mmol), sodium tert-butoxide (0.577g, 6.0mmol) and toluene (50ml) solvent are added into a dry reaction vessel, stirred uniformly under nitrogen protection at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 12-24 h. After completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of dichloromethane was added to the reaction mixture, and the mixture was washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography using petroleum ether/ethyl acetate (1:3vol/vol) as an eluent and dried in vacuo to give Compound 1(0.442g, 85% yield) as a yellow oil.1H NMR(400MHz,CDCl3): δ8.83(d,2H,J＝6.0Hz),8.13(d,2H,J＝7.6Hz),7.54-7.58(m,4H),7.43(t,2H,J＝7.6Hz), 7.33(t,2H,J＝7.2Hz).
(ii) Compound 1(0.520g, 2.0mmol) was dissolved in 50mL tetrahydrofuran solvent, the reaction solution was cooled to 0-5 ℃ and N-bromosuccinimide (NBS,0.712g, 4.0mmol) was added to the reaction solution in several portions and reacted for 8-12 h. After the reaction was completed, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (1:4vol/vol) as an eluent and dried in vacuo to give Compound 2(0.772g, 96% yield) as a yellow powder.1H NMR(400MHz,DMSO)δ8.62(d,J＝1.9Hz,2H), 7.77(dd,J＝4.7,1.4Hz,2H),7.64(dd,J＝8.8,2.0Hz,2H),7.56(d,J＝8.8Hz,2H).
(iii) In a dry reaction vessel, compound 2(0.480g, 1.2mmol), 4' -dimethoxydiphenylamine (0.642 g, 2.8mmol), palladium acetate (0.028g, 0.12mmol), tri-tert-butylphosphine (0.049g, 0.24mmol), sodium tert-butoxide (0.692g, 7.2mmol) and solvent toluene (50ml) are added, stirred uniformly under nitrogen protection at room temperature, and then heated to 110-. After the reaction was completed, it was cooled to room temperature, 50mL of methylene chloride was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography using petroleum ether/ethyl acetate (6:1vol/vol) as an eluent and dried in vacuo to obtain CZ-Py-2(0.578g, 69% yield) as a yellow powder.1H NMR (400MHz, DMSO) δ 8.81(ddd, J ═ 12.4,4.7,1.5Hz,2H),7.72-7.66(m,4H),7.52(d, J ═ 8.9Hz,2H), 7.14-7.03(m,2H),6.99-6.90(m,1H),6.90-6.79(m,15H),3.71(d, J ═ 12.6Hz,12H), HR-MS calculated C: calculated45H38N4O4698.2888, found 698.2871
In the step (4), the synthesis route and the specific steps of the hole transport material CZ-As are As follows:
(i) carbazole (0.335g, 2mmol), 4-iodoanisole (0.515g, 2.2mmol), palladium acetate (0.023g, 0.1mmol), tri-tert-butylphosphine (0.040g, 0.2mmol), sodium tert-butoxide (0.577g, 6.0mmol) and toluene (50ml) solvent are added into a dry reaction vessel, stirred uniformly under nitrogen protection at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 12-24 h. After completion of the reaction, it was cooled to room temperature, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (1:10vol/vol) as an eluent and dried in vacuo to give Compound 1' (0.442g, 81% yield) as a white powder.1H NMR(400MHz,CDCl3) δ,8.15(d,J＝8.0Hz,2H),7.46(d,J＝8.8Hz,2H),7.40(td,J＝8.4,0.8Hz,2H),7.32(d,J＝8.4 Hz,2H),7.28(td,J＝8.0,0.8Hz,2H),7.12(d,J＝8.8Hz,2H),3.93(s,3H).
(ii) Compound 1(0.546g, 2mmol) was dissolved in 50mL tetrahydrofuran solvent, the reaction solution was cooled to 0-5 deg.C, and then N-bromosuccinimide (NBS,0.712g, 4mmol) was added to the reaction solution in several portions, and reacted for 8-12 h. After the reaction was completed, 50mL of dichloromethane was added to the reaction solution and washed with 150mL of water three times, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel chromatography using petroleum ether/dichloromethane (1:10vol/vol) as an eluent and dried in vacuo to give Compound 2' (0.802g, 93% yield) as a white powder.1H NMR(400MHz,CDCl3)δ,8.19(dd,J＝2.0, 0.8Hz,2H),7.48(dd,J＝8.4,2.0Hz,2H),7.38(d,J＝8.8Hz,2H),7.17(dd,J＝8.4,0.8Hz,2H), 7.10(d,J＝8.8Hz,2H),3.92(s,3H).
(iii) The compound 2' (0.515g, 1.2mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882g, 2.8mmol), palladium acetate (0.028g, 0.12mmol), tri-tert-butylphosphine (0.049g, 0.24mmol), sodium tert-butoxide (0.692g, 7.2mmol) and the solvent toluene (50ml) were added to a dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110 ℃ and 120 ℃ for reaction for 18-24H. After the reaction was completed, the reaction mixture was cooled to room temperature, 50mL of methylene chloride was added to the reaction mixture, and the mixture was washed with 150mL of water three times, the organic layer was collected, and the solvent was removed under reduced pressureThe reagent and the residue were separated and purified by silica gel column chromatography using petroleum ether/ethyl acetate (6:1vol/vol) As an eluent, and dried in vacuo to give CZ-As (0.961g, 89% yield) As a yellow powder.1H NMR (400MHz, DMSO) δ 7.94(d, J ═ 2.0Hz,2H),7.62(d, J ═ 7.5Hz, 2H),7.56(dd, J ═ 8.6,2.8Hz,4H),7.43(d, J ═ 7.3Hz,2H),7.30-7.16(m,10H),7.06(t, J ═ 6.2Hz, 4H),6.99(d, J ═ 2.1Hz,2H),6.89(d, J ═ 9.0Hz,4H),6.73(dd, J ═ 8.3,2.1Hz,2H),3.88(d, J ═ 10.2Hz,3H),3.72(s,6H),1.30-1.25(m,12H), calculated values of C: C-C63H53N3O3899.4081, found 899.4071.
FIG. 2 is a schematic view showing the molecular structures of the passivation materials CZ-Py-1, CZ-Py-2 and the hole transport material CZ-As used in examples 1 and 2 of the present invention.
FIG. 3(a) is a scanning electron microscope image of the cross section of a perovskite solar cell in which CZ-Py-1 is used As a passivation material and CZ-As is used As a hole transport material in example 1 of the present invention; (b) (c), (d), (e) and (f) are respectively the appearance diagrams of a perovskite film, a CZ-Py-1 passivated perovskite film, a hole transport material CZ-As film coated on the surface of the CZ-Py-1 passivated perovskite, a CZ-Py-2 passivated perovskite film and a CZ-As film coated on the surface of the CZ-Py-2 passivated perovskite. As can be seen, the surface of the perovskite after the CZ-Py-1, CZ-Py-2 passivation treatment is smoother, PbI, than that of the unmodified perovskite film2Less crystallization; meanwhile, the CZ-As-based hole transport layer can completely cover the surface of the perovskite light absorption layer, and a layer of compact and uniform thin film is formed on the surface of the perovskite light absorption layer.
FIG. 4 is an XRD pattern of a perovskite thin film and a CZ-Py-1, CZ-Py-2 modified perovskite thin film. As is clear from the graph, the peak intensity of the crystal of the perovskite thin film after the CZ-Py-1, CZ-Py-2 passivation treatment was increased as compared with that of the unmodified perovskite thin film, and the peak intensity was attributed to PbI2The XRD peak of the complex is obviously weakened, which shows that CZ-Py-1, CZ-Py-2 can be combined with Pb in perovskite2+The coordination effect is generated, the perovskite surface is effectively passivated, and PbI is inhibited2Is generated.
FIG. 5 shows CZ-As As hole transport material based on non-modified perovskite thin film and CZ-Py-1, CZ-PAnd y-2 is a J-V diagram of the perovskite solar cell of the modified perovskite thin film. As can be seen from FIG. 5(a), 23.5% (V) was obtained for a device using CZ-As As hole transport material by the CZ-Py-1 passivation processoc＝1.15V,Jsc＝25.2mA·cm-2and FF 81.2%); as can be seen from FIG. 5(b), 18.24% (V) was obtained for the device using CZ-As As hole transport material by the CZ-Py-2 passivation processoc＝1.07V,Jsc＝22.9mA·cm-2FF — 74.4%) of the photoelectric conversion efficiency; and the battery has no obvious hysteresis phenomenon under the working condition.
Claims (10)
1. A preparation method of a high-efficiency stable perovskite solar cell is characterized in that the perovskite solar cell is composed of a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer, a surface passivation layer, a hole transmission layer and a metal electrode, and the preparation method specifically 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 an electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method;
(3) moving the conductive substrate coated with the electron transmission layer into a glove box, spin-coating perovskite precursor liquid on the electron transmission layer by a spin-coating method, and dropwise adding a chlorobenzene antisolvent containing a passivation material CZ-Py in the process of spin-coating the perovskite precursor liquid to form a perovskite light absorption layer with a passivated surface; wherein the structural formula of the passivation material CZ-Py is as follows:
wherein, R is a fluorene derivative or a diphenylamine derivative electron-donating group respectively;
(4) covering a hole transport layer solution containing a hole transport material CZ-As on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method to form a hole transport layer; wherein, the chemical structure general formula of the hole transport material CZ-As is:
(5) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
2. The method according to claim 1, wherein in the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence.
3. The method according to claim 1, wherein in the step (2), the electron transport layer is one of metal oxides such as titanium dioxide, tin dioxide, zinc oxide, and niobium pentoxide.
4. The production method according to claim 1, wherein in the step (3), the perovskite light absorption layer is FAXMA1-XPb(IXBr1-X)3、CH3NH3PbI3-xClxOr all-inorganic perovskite CsPbI3、CsPbBr3One of (1); wherein FA is CH2＝CHNH3MA is CH3NH3，0≤x≤1。
5. The method according to claim 1, wherein in the step (3), the chlorobenzene antisolvent containing the passivation material CZ-Py is added dropwise in an amount of 100 to 300. mu.L, wherein the concentration of the passivation material is 0.1 to 3 mg/mL.
6. The method according to claim 1, wherein the synthesis method of the passivation material CZ-Py comprises: reacting carbazole and 4-iodopyridine to generate Buchwald-Hartwig reaction to obtain an intermediate 1; carrying out bromination reaction on the intermediate 1 to obtain an intermediate 2; and carrying out Buchwald carbon nitrogen coupling reaction on the intermediate 2 and RH to obtain a final product CZ-Py.
7. The method according to claim 1, wherein in the step (4), the hole transport layer solution is used in an amount of 30 to 60 μ L and has a concentration of 30 to 60 mg/mL.
8. The method according to claim 1, wherein in the step (4), the hole transport layer solution further contains an additive; the additive is one or more of LiTFSI, tert-butyl pyridine or FK 209; the adding concentration is respectively as follows: LiTFSI is 20-30mmol/L, tert-butylpyridine is 200-300mmol/L, and FK209 is 1.0-2.0 mmol/L.
9. The method of claim 1, wherein the hole transport material CZ-As is synthesized by: reacting carbazole and 4-iodoanisole by Buchwald-Hartwig reaction to obtain an intermediate 1'; carrying out bromination reaction on the intermediate 1 'to obtain an intermediate 2'; and carrying out Buchwald carbon nitrogen coupling reaction on the intermediate 2' and a fluorene derivative to obtain a final product CZ-As.
10. The method according to claim 1, wherein in the step (5), the metal electrode is one of gold, silver, or copper.
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