CN109053735B - Organic semiconductor material based on pyrrole-nucleus aromatic amines and application thereof - Google Patents
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Abstract
The invention discloses a polypyrrole core aromatic amine based organic semiconductor material and application thereof, and belongs to the technical field of memories in the semiconductor industry. The pyrrole-core aromatic amine organic semiconductor material has a tetraaryl substituted pyrrole-core and an aromatic amine substituent group, has high stability, proper energy level, high hole mobility, good solubility and film forming property, and can be used as a hole transport layer material to be applied to perovskite solar cell devices. The invention has simple synthesis process, low cost and easy purification of products, can obtain better performance of the perovskite battery device, and is beneficial to popularization and application.
Description
Technical Field
The invention relates to an organic semiconductor material based on a polypyrrole core aromatic amine and application thereof in a perovskite cell device, and can be used in the technical field of solar cells in the semiconductor industry.
Background
With the aggravation of the energy crisis, people are actively seeking cheap and clean new energy to replace the currently widely used non-renewable energy sources such as petroleum, coal, natural gas and the like. Solar energy is a renewable energy source and is the basis of clean energy based on photovoltaic technology. How to benefit mankind from solar energy is the subject of research of numerous scholars, and among them, solar cells are an effective means for converting solar energy into electric energy.
In recent years, perovskite solar cells have attracted much attention due to their excellent characteristics, such as high photoelectric conversion efficiency and simple process. Intensive research on perovskite solar cells has improved the photoelectric conversion efficiency to more than 23%, possibly reaching or exceeding 25.6% of that of monocrystalline silicon solar cells. The significant achievement and the success of Science in 2013 are evaluated as one of ten scientific breakthroughs.
However, the hole transport materials used in the perovskite solar cells which are widely researched at present are mainly based on Spiro-OMeTAD, and the synthesis cost of other hole transport materials is higher. Spiro-OMeTAD needs to be pre-doped as the hole transport layer material. The doping operation can have an impact on device performance, particularly device operational stability. Therefore, in recent years, undoped hole transport materials have been designed and synthesized. However, these hole transport materials have large differences in characteristics such as chemical stability, synthesis cost, separation and purification techniques, and hole mobility.
Research shows that pyrrole and pyrrole structures have very high carrier affinity, but pyrrole itself is rarely used for constructing a hole transport material usable in a perovskite solar cell device.
Disclosure of Invention
Aiming at the technical problems of the existing perovskite solar cell hole transport material, the invention provides the aromatic amine organic semiconductor material based on the polypyrrole core and the application thereof.
The purpose of the invention is realized by the following technical scheme: the structural general formula of the organic semiconductor material based on the pyrrole-core aromatic amine is shown as the general formula A:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene.
Preferably, the formula a may be represented by:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and R is one of H, methoxy, methylthio, diarylamine or carbazole.
Preferably, the formula a may be represented by:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and R is one of H, methoxy, methylthio, diarylamine or carbazole.
Preferably, the formula a may be represented by:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and Ar3 is benzene ring or naphthalene ring; r is one of H, methoxy, methylthio, diarylamine or carbazole.
The invention also discloses an application of the organic semiconductor material based on the polypyrrole nuclear aromatic amine, wherein the polypyrrole nuclear aromatic amine organic semiconductor material is applied to a perovskite battery device, the perovskite battery device comprises an FTO substrate, a metal oxide layer is arranged on the upper surface of the substrate, a perovskite layer is arranged on the metal oxide layer, a hole transport layer is arranged on the upper surface of the perovskite layer, and a gold electrode or a silver electrode is arranged on the upper surface of the hole transport layer.
Preferably, the pyrrole-based aromatic amine organic semiconductor material is used as a hole transport layer applied to a perovskite solar cell device, and one of the pyrrole-based aromatic amine organic semiconductor materials shown in the general formula (I) is used, and the thickness of the semiconductor material is 30-500 nanometers.
Preferably, the material of the hole transport layer is based on a polypyrrole core aromatic amine organic semiconductor material, and the material of the metal oxide semiconductor layer is one of titanium oxide and zinc oxide.
The technical scheme of the invention has the advantages that: the invention takes the tetraarylpyrrole as the mother nucleus designed by the hole transport material, and the tetraarylpyrrole and common arylamine or substituted arylamine react through C-N coupling chain, so that the hole transport material without doping can be obtained with high yield and high flux. The hole transport material has high stability and high mobility, and can be prepared into a high-quality thin film by a solution method, so that the high performance of the perovskite solar cell device is ensured. In addition, the high distortion and steric hindrance between a plurality of aromatic ring structures and the polypyrrole units in the molecule of the polypyrrole core aromatic amine organic semiconductor material can effectively maintain the stability of a thin film phase structure, so that the stability and the tolerance capability of the prepared perovskite solar cell are improved.
The invention introduces a tetraaryl substituted pyrrole structure into the design of the hole transport material, and provides a feasible idea for developing other hole transport materials and the commercial popularization of related materials; the polypyrrole core aromatic amine organic semiconductor material provided by the invention is simple in preparation method, convenient to purify, wide in source of synthetic raw materials, and capable of remarkably reducing the labor cost and the material preparation cost; the polypyrrole core aromatic amine organic semiconductor material can be used as a hole transport layer in a perovskite solar cell device on the premise of not increasing the process complexity and being suitable for simple equipment preparation through a simple spin coating process.
In conclusion, compared with the prior art, the organic semiconductor material based on the polypyrrole core aromatic amine provided by the invention is used in a perovskite solar cell device, and a high-efficiency and stable solar cell can be obtained.
Drawings
FIG. 1 is a structural schematic diagram of a perovskite solar cell based on a hole transport layer of a polypyrrole core aromatic amine organic semiconductor material.
FIG. 2 is a synthesis scheme of BPTBOMe, a pyrrole core aromatic amine organic semiconductor material, in example 1 of the present invention.
FIG. 3 is a synthesis scheme of BPTTOMe, an organic semiconductor material of pyrrole core aromatic amine in example 2.
FIG. 4 is a synthesis scheme of BPTBOMeNa as the organic semiconductor material of pyrrole-core aromatic amines in example 3.
Fig. 5 is a synthesis route diagram of the polypyrrole core aromatic amine organic semiconductor material bptbcbome in embodiment 4 of the present invention.
FIG. 6 is a current-voltage curve of BPTBOMeNa, which is the organic semiconductor material of pyrrole core aromatic amine in example 5.
Fig. 7 is a current-voltage curve of the polypyrrole core aromatic amine organic semiconductor material bptbcbome according to the embodiment 6 of the present invention.
Detailed Description
Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.
The starting materials used in the present invention are known compounds, commercially available, or can be synthesized by methods known in the art.
Example 1
This example provides a benzopyrrole-based aromatic amine organic semiconductor material, wherein the structure formula of the conjugated BPTBOMe is as follows:
the synthetic route of the organic semiconductor material BPTBOMe based on the pyrrole nucleus aromatic amine is shown in figure 2. 0.73g (1.0mmol) of tetrabromo-tetraphenylpyrrole and 1.13g (5.0mmol) of 4, 4' -dimethoxyaniline were put into a 50mL reaction tube, and then the mixture was put into the reaction tube in this order0.1g of the catalyst PdppfCl was added20.04g (0.12mmol) of ligand tri-o-methylphenyl phosphorus, 6 times of equivalent of potassium tert-butoxide, 30mL of anhydrous toluene and 0.5mL of anhydrous N, N-dimethylformamide are stirred for reaction at 110 ℃ under the protection of argon for 12 h. And (2) cooling the reaction system to room temperature, pouring the reaction solution into a mixed solvent of water and methanol (the volume ratio is 1: 1), filtering the obtained solid, filtering inorganic matters by using diatomite, and re-precipitating in an ethyl acetate/n-hexane or dichloromethane/n-hexane mixed solvent to obtain pure BPTBOMe with the yield of about 87%.1H NMR(400MHz， CDCl3)δ：7.6-6.9(m，48H)，6.4(s，2H)，3.8(s，24H)。
The structural formula of tetrabromo-tetraphenyl pyrrole and 4, 4' -dimethoxy aniline is shown in figure 2.
Example 2
This example provides a benzopyrrole core aromatic amine organic semiconductor material, wherein the structural formula of BPTTOMe is as follows:
the synthetic route of the organic semiconductor material BPTTOMe of the pyrrole nucleus aromatic amine is shown in figure 3. 0.73g (1.0mmol) of 1, 4-bis (4-bromophenyl) -2, 5- (5-bromo-2-thienyl) -pyrrolopyrrole and 1.13g (5.0mmol) of 4, 4' -dimethoxyaniline were taken and added to a 50mL reaction tube, and then 0.1g of the catalyst PddppfCl was added to the reaction tube in this order20.04g (0.12mmol) of ligand tri-o-methylphenyl phosphorus, 6 times of equivalent of potassium tert-butoxide, 30mL of anhydrous toluene and 0.5mL of anhydrous N, N-dimethylformamide are stirred and reacted for 8h at 110 ℃ under the protection of argon. And (2) cooling the reaction system to room temperature, pouring the reaction liquid into a mixed solvent of water and methanol (the volume ratio is 1: 1), filtering the obtained solid, filtering inorganic matters by using diatomite, and then re-precipitating in an ethyl acetate/n-hexane or dichloromethane/n-hexane mixed solvent (or performing column chromatography: dichloromethane/n-hexane, the volume ratio is 2: 1 as an eluent), so that pure BPTTOMe can be obtained, wherein the yield is about 65%.1H NMR(400MHz，CDCl3)：7.5-6.6(m，40H)，6.5(d， 4)，6.3(s，2H)，3.8(s，24H)。
The structural formula of the 1, 4-bis (4-bromophenyl) -2, 5- (5-bromo-2-thienyl) -pyrrole and 4, 4' -dimethoxyaniline is shown in figure 3.
Example 3
This example provides a pyrrole nucleus aromatic amine organic semiconductor material, BPTBOMeNa, the structural formula of compound BPTBOMeNa is as follows:
the synthetic route of the organic semiconductor material BPTBOMeNa with the pyrrole nucleus and the aromatic amine is shown in figure 4. 0.73g (1.0mmol) of 1, 4-bis (4-bromophenyl) -2, 5- (5-bromo-2-thienyl) -pyrrole and 1.25g (5.0mmol) of N- (4-methoxyphenyl) -1-naphthylamine were added to a 50mL reaction tube, and then 0.1g of the catalyst PddppfCl was sequentially added to the reaction tube20.04g (0.12mmol) of ligand tri-o-methylphenyl phosphorus, 6 times of equivalent of potassium tert-butoxide, 30mL of anhydrous dimethyl sulfoxide and 0.5mL of anhydrous N, N-dimethylformamide are stirred and reacted for 8h at 110 ℃ under the protection of argon. Cooling the reaction system to room temperature, pouring the reaction liquid into a mixed solvent of water and methanol (volume ratio is 1: 1), filtering the obtained solid, filtering inorganic matters by diatomite, and re-precipitating in an ethyl acetate/n-hexane or dichloromethane/n-hexane mixed solvent (or performing column chromatography: dichloromethane/n-hexane, volume ratio is 2: 1 as eluent) to obtain pure BPTBOMeNa, wherein the yield is about 68%.1H NMR(400MHz，CDCl3)： 7.8-6.4(m，52H)，6.3(d，4)，6.2(s，2H)，3.7(s，12H)。
The structural formula of 1, 4-bis (4-bromophenyl) -2, 5- (5-bromo-2-thienyl) -pyrrole and N- (4-methoxyphenyl) -1-naphthylamine is shown in figure 4.
Example 4
The embodiment provides a polypyrrole core aromatic amine organic semiconductor material BPTBBzBOMe, and the structural formula of the compound BPTBBzBOMe is as follows:
the synthetic route of the polypyrrole core aromatic amine organic semiconductor material BPTBCZBOMe is shown in figure 5. Taking 1.5g (2.1mmol) of tetrabromo-tetraphenylpyrrole and 1.9 g (11.0mmol) of carbazole to a 150mL reaction tube, and then sequentially adding 0.1g of catalyst PdppfCl to the reaction tube20.06g (0.12mmol) of ligand tri-o-methylphenyl phosphorus, 6 times equivalent of potassium tert-butoxide, 70mL of anhydrous toluene and 1.0mL of anhydrous N, N-dimethylformamide are stirred and reacted for 12h at 110 ℃ under the protection of argon. And (2) cooling the reaction system to room temperature, pouring the reaction solution into a mixed solvent of water and methanol (the volume ratio is 1: 1), filtering the obtained solid, filtering inorganic matters by using diatomite, and re-precipitating in an ethyl acetate/n-hexane or dichloromethane/n-hexane mixed solvent to obtain pure BPTBTCz, wherein the yield is about 90%. 1.07g (1.0mol) of BPTBTCz was dissolved in tetrahydrofuran, and 1.5g (8.2mmol) of NBS was added thereto in four portions and stirred at room temperature for 8 hours. Adding a mixed solvent of water and methanol (volume ratio is 1: 1), filtering precipitated light yellow solid, and recrystallizing with toluene to obtain 8 Br-BPTBTCz. 1.1g of 8Br-BPTBTCz and 2.5g of 4, 4' -dimethoxyaniline were added into a 150mL reaction tube, and then 0.2g of catalyst PddppfCl was sequentially added into the reaction tube20.08g (0.12mmol) of ligand tri-o-methylphenyl phosphorus, 12 times of equivalent of potassium tert-butoxide, 70mL of anhydrous toluene and 10mL of dimethyl sulfoxide are stirred and reacted for 16h at 110 ℃ under the protection of argon. And (2) cooling the reaction system to room temperature, pouring the reaction liquid into a mixed solvent of water and methanol (the volume ratio is 1: 1), filtering the obtained solid, filtering inorganic matters by using diatomite, and then re-precipitating in an ethyl acetate/n-hexane or dichloromethane/n-hexane mixed solvent (or performing column chromatography: dichloromethane/n-hexane, the volume ratio is 1: 2 to 2: 1 is an eluent), so that pure BPTBCzBOMe can be obtained, wherein the yield is about 60%.1H NMR(400MHz，CDCl3)：8.0-6.3(m，104H)，6.2(s，2H)，3.7(s，48H)。
The structural formula of the intermediates such as tetrabromo-tetraphenylpyrrole, 4' -dimethoxyaniline and the like is shown in figure 5.
Example 5
The embodiment provides a perovskite solar cell device based on a polypyrrole core aromatic amine organic semiconductor material BPTBOMeNa hole transport material, the structure of which is shown in fig. 1, and the perovskite solar cell device comprises: the FTO substrate, the upper surface of substrate sets up the metal oxide layer on set up the perovskite layer upper surface sets up the hole transport layer the upper surface on hole transport layer sets up the gold electrode.
The perovskite of this example may be prepared in the general procedure as follows:
1. the FTO glass substrate is firstly etched by zinc powder and hydrochloric acid, the etched FTO substrate is firstly cleaned by a surfactant, then washed by acetone, ethanol and deionized water in sequence, and finally treated for 30 minutes under oxygen plasma to remove organic matter residues on the surface.
2. An isopropanol solution of tetradiisopropyl titanate was spin coated on the FTO substrate at 2000r.p.m for 60s followed by 500 degree sintering for 30 minutes to form a dense layer of titanium dioxide of about 50 nm.
3. An absolute ethanol solution of titanium dioxide slurry was spin-coated on a substrate at 2000rpm for 60 seconds and then sintered at 500 degrees for 30 minutes, followed by immersion in a 70-degree titanium tetrachloride aqueous solution for 30 minutes, natural drying and then sintered at 500 degrees for 30 minutes.
4. After methylamine and hydroiodic acid were mixed and stirred at 0 ℃ for 2 hours, the product was obtained after evaporation at 50 ℃ for 1 hour, and after washing the product three times with diethyl ether, it was dried under vacuum at 60 ℃ for 24 hours to obtain the desired product, ammonium methyliodide, as a white crystalline powder.
5. A DMF solution of lead iodide is spin-coated on the mesoporous titanium dioxide film at 2500rpm for 30s, then the film is sintered for 15 minutes at 100 ℃, the composite film is immersed in an isopropanol solution of methyl ammonium iodide for 60 minutes after being cooled to room temperature, and then the perovskite film is washed by dry isopropanol and nitrogen and then dried for 30 minutes at 100 ℃.
6. A solution of BPTBOMeNa in chloroform was spin coated and deposited on the substrate by vacuum evaporation.
7. The vacuum evaporation process will evaporate a gold electrode over the BPTBOMeNa described above.
All test results show that the perovskite solar cell device based on the organic semiconductor material BPTBOMeNa hole transport material of the pyrrole-core aromatic amine can realize the photoelectric conversion efficiency of more than 17%, the main process is finished in solution, the energy is saved, and the large-scale production can be realized. The current-voltage curve obtained from the test is shown in fig. 6.
Example 6
The embodiment provides a perovskite solar cell device based on a polypyrrole core aromatic amine organic semiconductor material BPTBCZBOMe hole transport material, the structure of which is shown in FIG. 1, and the perovskite solar cell device comprises: the FTO substrate, the upper surface of substrate sets up the metal oxide layer on set up the perovskite layer upper surface sets up the hole transport layer the upper surface on hole transport layer sets up the gold electrode.
The perovskite of this example may be prepared in the general procedure as follows:
1. the FTO glass substrate is firstly etched by zinc powder and hydrochloric acid, the etched FTO substrate is firstly cleaned by a surfactant, then washed by acetone, ethanol and deionized water in sequence, and finally treated for 30 minutes under oxygen plasma to remove organic matter residues on the surface.
2. An isopropanol solution of tetradiisopropyl titanate was spin coated on the FTO substrate at 2000r.p.m for 60s followed by 500 degree sintering for 30 minutes to form a dense layer of titanium dioxide of about 50 nm.
3. An absolute ethanol solution of titanium dioxide slurry was spin-coated on a substrate at 2000rpm for 60 seconds and then sintered at 500 degrees for 30 minutes, followed by immersion in a 70-degree titanium tetrachloride aqueous solution for 30 minutes, natural drying and then sintered at 500 degrees for 30 minutes.
4. After methylamine and hydroiodic acid were mixed and stirred at 0 ℃ for 2 hours, the product was obtained after evaporation at 50 ℃ for 1 hour, and after washing the product three times with diethyl ether, it was dried under vacuum at 60 ℃ for 24 hours to obtain the desired product, ammonium methyliodide, as a white crystalline powder.
5. A DMF solution of lead iodide is spin-coated on the mesoporous titanium dioxide film at 2500rpm for 30s, then the film is sintered for 15 minutes at 100 ℃, the composite film is immersed in an isopropanol solution of methyl ammonium iodide for 60 minutes after being cooled to room temperature, and then the perovskite film is washed by dry isopropanol and nitrogen and then dried for 30 minutes at 100 ℃.
6. The polypyrrole nuclear aromatic amine organic semiconductor material BPTBCZBOMe is deposited on the substrate by vacuum evaporation through spin coating in chloroform.
7. The vacuum evaporation process will evaporate a gold electrode on top of the above described bptbcbome hole transport layer.
All test results show that the perovskite solar cell device based on the polypyrrole core aromatic amine organic semiconductor material BPTBCZBOMe hole transport material can realize the photoelectric conversion efficiency of more than 20.3%, the main process is completed in solution, the energy is saved, and the large-scale production can be realized. The current-voltage curve obtained from the test is shown in fig. 7.
The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.
Claims (6)
1. An organic semiconductor material based on a pyrrole-nucleus aromatic amine is characterized in that: the structure is shown as a general formula I, wherein the general formula I is as follows:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and R is one of H, methoxy, methylthio, diarylamine or carbazole.
2. An organic semiconductor material based on a pyrrole-nucleus aromatic amine is characterized in that: the structure is general formula II, wherein the general formula II is as follows:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and R is one of H, methoxy, methylthio, diarylamine or carbazole.
3. An organic semiconductor material based on a pyrrole-nucleus aromatic amine is characterized in that: the structure is general formula III, and the general formula III is as follows:
wherein Ar1 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, Ar2 is one of benzene ring, naphthalene ring, thiophene, bithiophene, fluorene and benzothiophene, and Ar3 is benzene ring or naphthalene ring; r is one of H, methoxy, methylthio, diarylamine or carbazole.
4. Use of a polypyrrole core aromatic amine based organic semiconductor material according to any of the claims 1 to 3 in perovskite solar cell, characterized in that: the organic semiconductor material based on the polypyrrole core aromatic amine is used as a hole transport layer material and applied to a perovskite battery device; the perovskite battery device includes the FTO substrate the upper surface of FTO substrate sets up the metal oxide layer set up the perovskite layer on the metal oxide layer set up the hole transport layer on the perovskite layer upper surface set up gold electrode or silver electrode on the hole transport layer.
5. The application of the organic semiconductor material based on the polypyrrole core aromatic amine in the perovskite solar cell according to the claim 4 is characterized in that: the thickness of the hole transport layer is 30-500 nanometers.
6. The application of the organic semiconductor material based on the polypyrrole core aromatic amine in the perovskite solar cell according to the claim 4 is characterized in that: the metal oxide layer is made of one of titanium oxide or zinc oxide.
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| CN105753769A (en) * | 2016-02-14 | 2016-07-13 | 天津理工大学 | Small-molecular hole transporting material containing carbazolyl and further being low in dosage of 4-tert-butyl pyridine and application thereof to perovskite cell |
| CN106188067A (en) * | 2016-07-19 | 2016-12-07 | 南京信息工程大学 | Diketopyrrolopyrrolederivative derivative and perovskite battery thereof |
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| CN107915744A (en) * | 2017-08-21 | 2018-04-17 | 淮阴工学院 | It is a kind of using dithieno pyrroles as the organic hole transport material of core and its preparation and application |
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| CN106188067A (en) * | 2016-07-19 | 2016-12-07 | 南京信息工程大学 | Diketopyrrolopyrrolederivative derivative and perovskite battery thereof |
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