CN-115942849-B - Organic hole transport layer capable of being doped by solution pre-oxidation, preparation method and application thereof

Abstract

The invention belongs to the technical field of organic semiconductors, and discloses a solution pre-oxidation doped organic hole transport layer, and a preparation method and application thereof, wherein the preparation method comprises the steps of forming a solution A from an organic hole transport material and an organic solvent A; the preparation method comprises the steps of forming a solution B by metal salt and an organic solvent B, dispersing the solution B and tert-butylpyridine into the solution A to form a solution C, blowing oxidizing gas into the solution C to obtain a P-type doped solution D, and spin-coating the solution D on a light absorber or a substrate to obtain the organic hole transport layer capable of being doped by solution pre-oxidation. The preparation method is simple, the prepared organic hole transport layer has excellent hole mobility and conductivity without being oxidized in air for a long time, and after the organic hole transport layer is prepared into a perovskite solar cell, the photoelectric conversion efficiency is high and can reach more than 24%, the performance and the stability are obviously improved, and the organic hole transport layer has good application prospect in the perovskite solar cell device.

Inventors

• WANG HONGQIANG
• YE LINFENG
• GUO PENGFEI
• YE QIAN
• YANG PENGHUI
• ZHANG KAIYUAN
• ZHAO PENGZHEN

Assignees

• 西北工业大学

Dates

Publication Date

20260508

Application Date

20221129

Claims (9)

1. 1. The preparation method of the organic hole transport layer capable of being doped by solution pre-oxidation is characterized by comprising the following steps: Step 1, uniformly dispersing an organic hole transport material in an organic solvent A to form a solution A; Step 2, uniformly dispersing metal salt in an organic solvent B to form a solution B, and dispersing the solution B and tert-butylpyridine into the solution A to form a solution C; Step 3, blowing oxidizing gas into the solution C to obtain a P-type doped solution D, and spin-coating the P-type doped solution D on a light absorber or a substrate to obtain the organic hole transport layer capable of being subjected to solution pre-oxidation doping; The structural formula of the metal salt is AB 2 ; Wherein A is a metal cation selected from any one of Fe 2+ 、Sn 2+ 、Pb 2+ 、Sm 2+ 、Eu 2+ ; b is an anion selected from one or more of bis-pentafluoroethane sulfonyl imide and bis-trifluoromethyl sulfonyl imide.
2. 2. The production method according to claim 1, wherein the organic hole transporting material is any one of poly 3-hexylthiophene, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] and poly [ bis (4-phenyl) (4-butylphenyl) amine ].
3. 3. The preparation method according to claim 1, wherein the organic solvent a is selected from one or more of chlorobenzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, petroleum ether, diethyl ether and ethylene glycol ether; the organic solvent B is one or more selected from acetonitrile, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
4. 4. The preparation method according to claim 1, wherein the concentration of the organic hole transport material in the solution a is 5-70 mg/mL; In the solution B, the molar concentration of the metal salt is 0.1-1 mol/L.
5. 5. The preparation method according to claim 1, wherein in the solution C, the molar ratio of the metal salt to the organic hole transport material is 0.1 to 1:1; the molar ratio of the tert-butylpyridine to the metal salt is 1-10:1.
6. 6. The method of claim 1, wherein the oxidizing gas is one or more of dry air, oxygen, ozone, and nitrogen dioxide.
7. 7. The method according to claim 1, wherein in step 3, the bubbling time of the oxidizing gas is 0.1 to 30 minutes.
8. 8. A solution preoxidatively dopable organic hole transporting layer made by the method of any one of claims 1-7.
9. 9. Use of the organic hole transport layer of claim 8 for the preparation of perovskite solar cells.

Description

Organic hole transport layer capable of being doped by solution pre-oxidation, preparation method and application thereof Technical Field The invention relates to the technical field of organic semiconductors, in particular to a solution pre-oxidation doped organic hole transport layer, a preparation method thereof and application thereof in perovskite solar cells. Background The organic hole transport material used in the perovskite solar cell has very low hole mobility per se, so that a large amount of doped lithium bistrifluoromethylsulfonyl imide (LiTFSI) is required, and the organic hole transport material is required to be placed in air for at least 12 hours, and the P-type doping of the organic hole transport layer can be realized by utilizing the combined action of oxygen and LiTFSI to obtain higher hole mobility. However, the hole transport layer doped with LiTFSI has strong hygroscopicity, and can absorb water vapor in the air to degrade the perovskite layer when placed in the air, and in addition, lithium ions added in the hole transport layer can permeate into the perovskite layer along the grain boundary of the perovskite film due to the existence of a built-in electric field when the lithium salt is used, so that serious carrier recombination is caused, and the performance of the perovskite solar cell is reduced. The organic hole transport layer needs to be doped with LiTFSI and placed in air, which results in poor stability of the perovskite solar cell, severely hampering the commercialization process of the perovskite solar cell. Therefore, efficient P-type doping treatment of the organic hole transport layer to improve the stability of the perovskite cell is a critical issue to be solved urgently, and how to prepare a hole transport layer having high mobility without lithium salt doping is a difficulty in obtaining a high-performance solar cell excellent in long-term stability. Therefore, the invention provides a solution pre-oxidation doped organic hole transport layer, and a preparation method and application thereof. Disclosure of Invention In order to solve the defects in the prior art, the invention provides a solution pre-oxidation doped organic hole transport layer, and a preparation method and application thereof. The organic hole transport layer prepared by the method can be directly put into use without a subsequent long-time standing process, and the perovskite solar cell prepared by using the perovskite solar cell has excellent long-term stability and high photoelectric conversion efficiency. The organic hole transport layer capable of being doped by solution pre-oxidation and the preparation method and application thereof are realized by the following technical scheme: the first object of the present invention is to provide a method for preparing a solution preoxidation doped organic hole transport layer, comprising the steps of: Step 1, uniformly dispersing an organic hole transport material in an organic solvent A to form a solution A; Step 2, uniformly dispersing metal salt in an organic solvent B to form a solution B, and dispersing the solution B and tert-butylpyridine (TBP) in the solution A to form a solution C; and step 3, blowing oxidizing gas into the solution C to obtain a P-type doped solution D, and spin-coating the P-type doped solution D on a light absorber or a substrate to obtain the organic hole transport layer capable of being subjected to solution pre-oxidation doping. Further, the organic hole transport material is any one of P 3 HT (poly 3-hexylthiophene), spira-ome tad (2, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene), PTAA (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]) and TPD (poly [ bis (4-phenyl) (4-butylphenyl) amine ]). Further, the structural formula of the metal salt is AB 2; Wherein A is a metal cation selected from any one of Fe 2+、Sn2+、Pb2+、Sm2+、Eu2+; B is an anion selected from one or more of bis (pentafluoroethanesulfonyl) imide, bis (trifluoromethylsulfonyl) imide and bis (trifluoromethylsulfonyl) imide. Further, the organic solvent A is selected from one or more of chlorobenzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, petroleum ether, diethyl ether and ethylene diether; The organic solvent B is selected from one or more of acetonitrile, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide) and NMP (N-methylpyrrolidone). Further, in the solution A, the concentration of the organic hole transport material is 5-70 mg/mL; In the solution B, the molar concentration of the metal salt is 0.1-1 mol/L. Further, in the solution C, the molar ratio of the metal salt to the organic hole transport material is 0.1-1:1; The molar ratio of TBP to the metal salt is 1-10:1. Further, the oxidizing gas is one or more of dry air, oxygen, ozone and nitrogen dioxide. In step 3, the bubbling time of the oxidizing gas is 0.1-30 min, the gas flow rate of the bubbling gas is suitably 0.1-1 m 3/min, an