CN113461483A - Perovskite material, solar cell device and preparation method - Google Patents

Perovskite material, solar cell device and preparation method Download PDF

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CN113461483A
CN113461483A CN202110599221.5A CN202110599221A CN113461483A CN 113461483 A CN113461483 A CN 113461483A CN 202110599221 A CN202110599221 A CN 202110599221A CN 113461483 A CN113461483 A CN 113461483A
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perovskite
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linking agent
hydrophobic
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CN113461483B (en
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詹义强
刘凯
李崇源
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Zhongshan Fudan Joint Innovation Center
Zhongshan Fuyuan New Material Technology Co ltd
Fudan University
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Zhongshan Fuyuan New Material Technology Co ltd
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Abstract

The invention relates to a perovskite material, a solar cell device and a preparation method, wherein the perovskite material is prepared by crosslinking a main material and a hydrophobic micromolecule crosslinking agent; the main material is organic-inorganic perovskite; the hydrophobic small molecule cross-linking agent is trifluoropropyl bisaziridine compound. The perovskite material disclosed by the invention is uniform and compact in film formation, has excellent water vapor stability, the solar cell device disclosed by the invention is high in operation stability, and the preparation methods of the perovskite material and the solar cell device disclosed by the invention are simple and feasible.

Description

Perovskite material, solar cell device and preparation method
Technical Field
The invention relates to the field of materials, in particular to a perovskite material, a solar cell device and a preparation method.
Background
Organic-inorganic hybrid perovskite materials and devices thereof are easily degraded in water vapor, illumination or high temperature environments. The existing method for improving the stability of the perovskite material mainly comprises the following steps: (1) by introducing additive molecules to form hydrogen bonds with organic components (methylamine and formamidine) of the perovskite material, the organic components are solidified through the weak interaction of the hydrogen bonds, and the movement or degradation of the organic components in the perovskite is inhibited; (2) a cross-linker polymer is introduced. The cross-linking agent polymer can exist at the crystal boundary of the perovskite thin film, and the migration/diffusion channel of ions inside the perovskite along the crystal boundary is blocked, so that the stability of the perovskite material is improved.
The existing method for improving the stability of the perovskite material has limited improvement on the stability, so that the perovskite material is difficult to adapt to severe environment. For example, the method of forming hydrogen bonds with perovskites is easy to break under a severe environment and has limited improvement in stability because the hydrogen bonds are weak interactions; the method for introducing the self-crosslinking cross-linking agent polymer mainly improves the stability of the perovskite material by inhibiting the movement of ions in the grain boundary, but the self-crosslinking cross-linking agent polymer does not essentially interact with perovskite components, only has the function of blocking the movement of ions in the grain boundary, and cannot effectively solidify the movable components, so that the self-crosslinking cross-linking polymer is difficult to inhibit the movement of the ions in other defects, such as vacancies and Frenkel defects, and the improvement of the stability is limited. In addition, most of the existing stability improvement methods are used for researching the storage stability of devices, and the method is also very important for researching the operation stability of commercial solar cells.
Disclosure of Invention
In view of the deficiencies of the prior art, a first object of the present invention is to provide a perovskite material, a second object of the present invention is to provide a method for preparing the perovskite material, a third object of the present invention is to provide a solar cell device having the perovskite material, and a fourth object of the present invention is to provide a method for preparing the solar cell device. The perovskite material disclosed by the invention is uniform and compact in film formation, has excellent water vapor stability, the solar cell device disclosed by the invention is high in operation stability, and the preparation methods of the perovskite material and the solar cell device disclosed by the invention are simple and feasible.
In order to achieve the first object of the invention, the invention provides a perovskite material which is prepared by crosslinking a main material and a hydrophobic small molecule crosslinking agent; the main material is organic-inorganic perovskite; the hydrophobic micromolecule cross-linking agent is trifluoropropyl bisaziridine compound, and the structural formula of the trifluoropropyl bisaziridine compound is as follows:
Figure BDA0003092184340000021
wherein R is an organic group, preferably a hydrophobic organic group.
Preferably, the trifluoropropylbisaziridine-based compound is selected from at least one of the following compounds:
Figure BDA0003092184340000022
the trifluoropropyl bisaziridine compound has the advantages of relatively easily obtained raw materials, good micromolecule hydrophobicity of the cross-linking agent, high chemical stability and the like.
Preferably, the hydrophobic small molecule cross-linking agent is dispersed throughout the host material; or the hydrophobic small molecules are dispersed in a first portion of the host material and contacted with a second portion of the remaining host material to be re-crosslinked.
Preferably, the mole percentage of the hydrophobic small molecule cross-linking agent in the perovskite material is 0.2-0.5%.
Preferably, the host material comprises monovalent cations, divalent cations and anions; the univalent cation is at least one of methylamine ion, formamidine ion and cesium ion; the divalent cation is at least one of lead ions and tin ions; the anion is a halide anion.
In order to achieve the second object of the present invention, the present invention provides a method for preparing a perovskite material according to any one of the above aspects, wherein the perovskite material comprising a host material and a hydrophobic small molecule cross-linking agent is made into a thin film and is cross-linked by means of ultraviolet irradiation and/or heating.
Preferably, the following steps are included prior to crosslinking: step A: preparing a perovskite precursor solution, and adding a solution of a hydrophobic micromolecule cross-linking agent into the perovskite precursor solution for dispersion; and B: and C, coating and annealing the perovskite precursor solution treated in the step A to prepare the perovskite thin film.
More preferably, in step a, the perovskite precursor solution is prepared by adding a DMSO solution of CsI to a mixed solution of iodoformamidine, bromomethylamine, lead bromide and lead iodide in a solvent of a volume ratio of dimethylformamide to dimethyl sulfoxide of 4: 1; the solution of the hydrophobic micromolecule cross-linking agent is DMF solution of the hydrophobic micromolecule cross-linking agent, and the concentration of the hydrophobic micromolecule cross-linking agent in the DMF solution is 100-200 mg/mL; the solution of the hydrophobic micromolecule cross-linking agent is added into the perovskite precursor solution for dispersion under the condition of keeping out of the light.
More preferably, in step B, the method of coating is spin coating; the annealing temperature is 100 ℃, and the annealing time is 60 min.
More preferably, after the step B, the hydrophobic small molecule cross-linking agent and the main material are cross-linked by ultraviolet irradiation, or the hydrophobic small molecule cross-linking agent and the main material are cross-linked by heating, wherein the heating temperature is 140-150 ℃, and the heating time is 10-20 min.
As an alternative, the following steps are included prior to crosslinking: step a: respectively preparing a lead iodide precursor solution and an organic salt solution, and adding a solution of a hydrophobic micromolecule cross-linking agent into the lead iodide precursor solution for dispersion; step b: coating and annealing the lead iodide precursor solution treated in the step a to prepare a lead iodide layer; step c: coating the organic salt solution on the lead iodide layer to further prepare the perovskite thin film.
More preferably, in step a, the lead iodide precursor solution is a solution of lead iodide in a solvent with a volume ratio of N, N-dimethylformamide to dimethyl sulfoxide of 9: 1; the solution of the hydrophobic micromolecule cross-linking agent is DMF solution of the hydrophobic micromolecule cross-linking agent, and the concentration of the hydrophobic micromolecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic micromolecule cross-linking agent into the lead iodide precursor solution for dispersion under the condition of keeping out of the sun; the organic salt solution is isopropanol solution of iodoformamidine, bromomethylamine and chloromethylamine.
More preferably, the method of coating is spin coating; the annealing temperature is 70 ℃ and the annealing time is 1 min.
More preferably, the method of coating is spin coating.
More preferably, annealing is carried out by heating, and the hydrophobic micromolecule cross-linking agent is cross-linked with the main material, wherein the heating temperature is 140-150 ℃, and the heating time is 10-20 min; or heating and annealing, and then irradiating by ultraviolet light to enable the hydrophobic small molecule cross-linking agent to be cross-linked with the main body material.
The conditions adopted in each step can well control the grain condition and the film performance, so that the material is fully crosslinked.
In order to achieve the third object of the present invention, the present invention provides a solar cell device comprising a transparent substrate, a first electrode layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second electrode layer, which are sequentially stacked, wherein the perovskite light absorption layer is the perovskite material according to any one of the above aspects or the perovskite material obtained by the method according to any one of the above aspects.
To achieve the fourth object of the present invention, the present invention provides a method for manufacturing a solar cell device, comprising the steps of: step 1: cleaning the conductive glass; the conductive glass comprises a transparent substrate and a first conductive layer deposited on the transparent substrate; step 2: spin coating an electron transport layer on the first conductive layer; and step 3: forming a film-like cross-linked perovskite material on the electron transport layer by any one of the methods described above to prepare a perovskite light absorbing layer; and 4, step 4: spin-coating a hole transport layer on the perovskite light absorption layer; and 5: and evaporating a second electrode on the hole transport layer.
Compared with the prior art, the invention can obtain the following beneficial effects:
the invention provides a new material, a new device and a new method for improving the stability of organic and inorganic hybrid perovskite materials and devices. Specifically, the trifluoromethyl bisaziridine compound is introduced to be crosslinked with the perovskite material under ultraviolet irradiation or high temperature to form a covalent bond, so that the degradation of the perovskite material is effectively prevented. Because the trifluoromethyl bisaziridine compound is crossed and linked with the perovskite at the crystal boundary, the perovskite crystallization is promoted, and therefore, the perovskite thin film is uniform and compact and has no obvious holes. Simultaneously, contain the hydrophobicity cross-linking agent micromolecule in the perovskite film, this cross-linking micromolecule has excellent steam stability, and this cross-linking agent can act on the organic component of grain boundary department, and the cladding plays the effect of protective layer on perovskite grain boundary surface, blocks the invasion that external steam passes through the grain boundary, avoids causing the decomposition of perovskite because steam, improves the stability of perovskite in the air. In addition, under the action of photo-thermal, ion migration/diffusion inside the perovskite is an important factor influencing the photo-thermal stability of the perovskite, and the cross-linked small molecules can be cross-linked with organic components (methylamine and formamidine) at perovskite grain boundaries to solidify the organic components and inhibit the decomposition and migration of the organic components. Meanwhile, due to the fact that cross-linking agent micromolecules are attached to the grain boundary, other ions in the perovskite are prevented from moving/diffusing along the grain boundary, and the photo-thermal stability of the perovskite is further improved. Therefore, the durability of the perovskite thin film to air, high temperature and light can be improved by virtue of the cross-linking agent micromolecules, and the water vapor stability, the thermal stability and the light stability of the perovskite thin film are further improved.
Drawings
FIG. 1 shows a chemical reaction structure of an example of the crosslinking reaction of the crosslinking agent of the present invention.
Fig. 2 is a schematic structural view of an example of a solar cell device in the present invention.
Fig. 3 is a graph comparing the stability of the perovskite solar cells of example 1 of the present invention and comparative example 1 in actual operation.
Fig. 4 is a graph comparing the stability of the perovskite solar cells of example 2 of the present invention and comparative example 2 in actual operation.
Fig. 5 is a graph showing the results of water stability tests of the perovskite thin films prepared in example 1 of the present invention and comparative example 1.
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Detailed Description
The invention introduces a hydrophobic small molecule cross-linking agent of trifluoromethyl bisaziridine compound into the traditional organic/inorganic perovskite material, the chemical structural formula of the hydrophobic small molecule cross-linking agent can be, for example, the compound shown in figure 1, but is not limited to the compound, and R in figure 1 can adopt other organic groups, preferably hydrophobic groups. The hydrophobic small molecule cross-linking agent can perform cross-linking reaction with perovskite organic components such as methylamine, formamidine and the like. The micromolecule cross-linking agent can be cross-linked with an organic matter under the condition of ultraviolet illumination or heating to form a covalent bond with strong interaction, and as shown in figure 1, the hydrophobic micromolecule cross-linking agent can capture hydrogen atoms in the organic matter to be cross-linked with the organic matter. Different from the self-crosslinking mode of the conventionally used crosslinking agent molecules, the trifluoromethyl bisaziridine compound crosslinking agent molecules are introduced into the perovskite material, so that the perovskite material can be cross-linked with the organic components of the perovskite material at the grain boundary to form covalent bonds with stronger interaction, thereby solidifying the organic components in the perovskite and inhibiting the organic components from moving in the grain boundary, vacancy, Frenkel defect and other defects. And simultaneously, organic components near the grain boundary are prevented from volatilizing and escaping in the photo-thermal environment. Due to the fact that the introduced trifluoromethyl bis-aziridine compound cross-linking agent small molecules have hydrophobicity, such as hydrophobicity brought by trifluoromethyl groups, the cross-linking agent small molecules are adsorbed in perovskite grain boundaries, external water vapor invasion can be effectively prevented, and water vapor stability of the perovskite material is improved.
The structure of the solar cell device prepared by using the organic-inorganic hybrid perovskite material of the invention is shown in fig. 2, and the structure of the solar cell device comprises a transparent substrate 101, a first electrode layer 102, an electron transport layer 103, a perovskite light absorption layer 104, a hole transport layer 105 and a second electrode layer 106 which are sequentially stacked. Wherein 101 is a transparent substrate, which may be, for example, quartz glass; 102 is a first electrode layer; 103 is an electron transport layer; 104 is a perovskite light absorbing layer; 105 is a hole transport layer; 106 is the second electrode layer.
Example 1
This example prepares an organic-inorganic hybrid perovskite material and prepares a perovskite solar cell using the material. The transparent substrate of the perovskite solar cell is quartz glass; the first transparent electrode layer is ITO and has the thickness of 180 nm; the hole transport layer is Spiro-OMeTAD and has the thickness of 40 nm; the modification layer is formed by interaction after acetic acid is spin-coated; the main component of the perovskite layer is Cs0.05(MA0.13FA0.87)0.95Pb(I0.87Br0.13)3The thickness is 580 nm; the electron transport layer is SnO2The thickness is 30 nm; the second electrode layer was gold and was 80nm thick. The perovskite solar cell is prepared by the following steps:
(1) and cleaning the ITO conductive glass by using a glass cleaning solution, acetone and ethanol in sequence, drying, and removing residual organic matters by using an ultraviolet ozone cleaning machine.
(2) Mixing 360 μ L SnO2Mixing with 2.4mL of deionized water, and preparing SnO by using spin coating method2And (3) after the spin coating of the electron transport layer is finished, placing the sample in an oven at 80 ℃, and carrying out vacuum annealing for 1 h.
(3) Preparation of perovskite material, namely perovskite layer: iodoformamidine, bromomethylamine, lead bromide and lead iodide are added into a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, wherein the mass of the lead iodide, the mass of the lead bromide, the mass of the bromomethylamine and the mass of the iodoformamidine are 117.97mg, 22.39mg, 80.74mg and 507.1mg respectively. Another 45. mu.L of CsI in DMSO at a concentration of 194.86mg/0.5mL was added. Stirring the mixture for 2 hours in a glove box at the constant temperature of 60 ℃ to form a yellow uniform perovskite precursor solution. 22mg of the crosslinker small molecule shown in FIG. 1 was dissolved in 100. mu.L of DMF and stirred in a glove box at room temperature for 2 h. And (3) taking 15 mu L of cross-linking agent solution to the perovskite precursor solution, and stirring for 1h in a dark place. And spin-coating the obtained perovskite precursor solution on the modified electron transport layer by using an inverse solution method to form a perovskite-homogenizing thin film, annealing at 100 ℃ for 60min, and assisting UV illumination to enable the cross-linking agent to be cross-linked with the perovskite, so as to obtain a compact and stable perovskite light absorption layer. By changing the dosage of the small molecules of the cross-linking agent, perovskite layers with different dosage of the cross-linking agent can be obtained.
(4) To 1mL of chlorobenzene was added 72.3mg of Spiro-OMeTAD, 17.5. mu.L of lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI), 25. mu.L of FK209 (520 mg/mL) and 29. mu.L of 4-t-butylpyridine (300 mg/mL), and the mixture was stirred at room temperature for 3 hours to form a hole transporting layer solution. The obtained hole transport layer solution was spin-coated on the perovskite light absorbing layer to form a hole transport layer.
(5) And finally, evaporating a gold electrode on the hole transport layer through thermal evaporation, wherein the thickness of the gold electrode is 85nm, and the preparation of the perovskite solar cell is completed.
Example 2
This example prepares an organic-inorganic hybrid perovskite material and prepares a perovskite solar cell using the material. The transparent substrate of the perovskite solar cell is quartz glass; the first transparent electrode layer is ITO and has the thickness of 180 nm; the electron transport layer is SnO2The thickness is 30 nm; the perovskite layer is (FAPBI)3)1-x-y(MAPbBr3)x)(MAPbCl3)y) Wherein x, y and 1-x-y are respectively greater than or equal to 0 and less than or equal to 1, and the thickness is 700 nm; the hole transport layer is Spiro-OMeTAD and has the thickness of 100 nm; the second electrode layer was gold and was 80nm thick. The perovskite solar cell of the embodiment is prepared by the following steps:
(1) and cleaning the ITO conductive glass by using a glass cleaning solution, acetone and ethanol in sequence, drying, and removing residual organic matters by using an ultraviolet ozone cleaning machine.
(2) Mixing 360uL of SnO2Mixing with 2.4mL of deionized water, and preparing SnO by using spin coating method2And (4) placing the sample in an 80-degree oven after the spin coating of the electron transport layer is finished, and carrying out vacuum annealing for 1 h.
(3) Preparation of perovskite material, namely perovskite layer: adding 600mg of lead iodide into a mixed solution of dimethylformamide and dimethyl sulfoxide in a volume ratio of 9:1, stirring at a constant temperature of 60 ℃ for 12 hours in a glove box to form a yellow uniform lead iodide precursor solution, cooling the solution to room temperature, and adding 11 mu L of a cross-linking agent molecular solution containing bis (trifluoromethyl) bisaziridine groups with a concentration of 155mg/mL, wherein the solvent is DMF. Further, 2mL of IPA (isopropyl alcohol) was added iodoformamidine, bromomethylamine and chloromethylamine in an amount of 120mg, 12mg and 12mg, respectively, to obtain an organic salt solution. The perovskite solar cell is prepared by a two-step spin coating method, a layer of lead iodide is spin-coated on an electron transmission layer, annealing is carried out on a hot table at 70 ℃ for 1min, then an organic salt solution is spin-coated on the lead iodide layer to form a uniform perovskite thin film, the perovskite thin film is kept at 150 ℃ for 15min, the perovskite organic component and a cross-linking agent are subjected to cross-linking, and a compact and stable perovskite light absorption layer is obtained.
(4) To 1mL of chlorobenzene was added 72.3mg of Spiro-OMeTAD, 17.5. mu.L of lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI), 25. mu.L of FK209 at 520mg/mL, 29. mu.L of 4-t-butylpyridine at 300mg/mL, and the mixture was stirred at room temperature for 3 hours to form a hole transporting layer solution; the obtained hole transport layer solution was spin-coated on the perovskite light absorbing layer to form a hole transport layer.
(5) And finally, evaporating a gold electrode on the hole transport layer through thermal evaporation, wherein the thickness of the gold electrode is 85nm, and the preparation of the perovskite solar cell is completed.
Comparative example 1
Comparative example 1 is the same as example 1 except that the perovskite precursor solution of comparative example 1 does not contain a trifluoromethyl bis-aziridine compound, and the resulting perovskite thin film does not contain the cross-linking agent small molecules.
Comparative example 2
Comparative example 2 is identical to example 2 except that the perovskite precursor solution of comparative example 2 does not contain a trifluoromethyl bis-aziridine compound, and the resulting perovskite thin film does not contain the crosslinker small molecules.
The perovskite thin films and solar cell devices obtained in examples 1 to 2 and comparative examples 1 to 2 were tested:
(1) the stability of the perovskite solar cells of example 1 and comparative example 1 in actual operation is compared.
The working conditions are as follows: AM1.5G Sun illumination (100 mW/cm)2) The operating stability, at a temperature of 45 ℃, actually includes light stability and thermal stability. Results are shown in fig. 3, where 0.5 mol% or 0.25 mol% crosslinker (uv) in fig. 3 corresponds to two examples of uv-crosslinked solar cell devices obtained by adjusting the concentration of the crosslinking agent in the perovskite precursor solution in example 1; 0.5 mol% or 0.25 mol% crosslinker corresponds to two solar cell devices without ultraviolet crosslinking obtained by adjusting the concentration of the crosslinking agent in the perovskite precursor solution in example 1, as a comparison; control devices and control devices (UV) correspond to the two comparative solar cell device examples of comparative example 1 without added cross-linking agent and without UV irradiation and with UV irradiation, respectively. Mol% in the figure refers to the mole percentage of the cross-linking agent in the perovskite layer.
As can be seen from fig. 3, after the perovskite solar cell device added with the small molecules of the cross-linking agent is subjected to ultraviolet irradiation, the operation stability of the device is greatly improved, which indicates that the interaction between the molecules of the cross-linking agent and the perovskite component inhibits the decomposition and movement of the organic component of the perovskite, thereby improving the working stability of the perovskite solar cell. And the perovskite solar cell device which is not subjected to ultraviolet irradiation and is added with the cross-linking agent micromolecules has reduced operation stability because the cross-linking agent molecules are not cross-linked.
(2) The stability of the perovskite solar cells of example 2 and comparative example 2 was compared in actual operation.
The working conditions are as follows: AM1.5G Sun illumination (100 mW/cm)2) At a temperature of 45 ℃. Results as shown in fig. 4, 0.5% in fig. 4 corresponds to the thermally crosslinked solar cell device example obtained by adjusting the concentration of the crosslinking agent in the perovskite precursor solution in example 2, with 0.5% of the molar percentage of the crosslinking agent in the perovskite layer; control corresponds to the comparative solar cell device example of comparative example 3 without the addition of a crosslinking agent.
As can be seen from fig. 4, the stability of the perovskite solar cell using the perovskite thin film improved by the small molecules of the cross-linking agent in the actual operating state is significantly improved.
(3) Water stability testing of the perovskite thin films prepared in example 1 and comparative example 1.
The working conditions are as follows: the humidity is 51-78%, the temperature is 19-24 ℃, and the testing time is 130 hours. As shown in FIG. 5, (a) is the perovskite thin film of comparative example 1 which is not irradiated with ultraviolet light, (b) is the perovskite thin film of comparative example 1 which is irradiated with ultraviolet light, (c) is the perovskite thin film of example 1 which is not irradiated with ultraviolet light, and (d) is the perovskite thin film of example 1 which is irradiated with ultraviolet light.
As can be seen from FIG. 5, the perovskite thin film added with the small molecules of the cross-linking agent has no obvious change no matter whether the perovskite thin film is irradiated by ultraviolet light or not after the water stability test. While the film of comparative example 1 turned yellow in color due to degradation of the organic component, resulting in lead iodide. Since the cross-linking agent has hydrophobicity, the hydrophobic group of the cross-linking agent is the main reason for improving the stability of the film, and whether the cross-linking agent and the perovskite are subjected to cross-linking reaction has little influence on the water stability.
Finally, it should be emphasized that the above-described embodiments are merely preferred examples of the invention, which is not intended to limit the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A perovskite material is characterized in that the perovskite material is prepared by crosslinking a main material and a hydrophobic micromolecule crosslinking agent; the main material is organic-inorganic hybrid perovskite; the hydrophobic small molecule cross-linking agent is a trifluoropropyl bis-aziridine compound, and the structural formula of the trifluoropropyl bis-aziridine compound is as follows:
Figure FDA0003092184330000011
wherein R is an organic group.
2. A perovskite material according to claim 1, characterized in that said trifluoropropylbisaziridine-based compound is selected from at least one of the following compounds:
Figure FDA0003092184330000012
3. a perovskite material according to claim 1 or 2, characterized in that the hydrophobic small molecule cross-linker is dispersed throughout the host material; or the hydrophobic small molecules are dispersed in a first part of the main material and contacted with a second part of the main material to be crosslinked again.
4. A perovskite material according to claim 1 or 2, characterized in that the molar percentage of the hydrophobic small molecule cross-linker in the perovskite material is between 0.2% and 0.5%.
5. A perovskite material according to claim 1 or 2, characterized in that said host material comprises monovalent cations, divalent cations and anions; the univalent cation is at least one of methylamine ion, formamidine ion and cesium ion; the divalent cation is at least one of lead ions and tin ions; the anion is a halide anion.
6. A process for preparing a perovskite material as claimed in any one of claims 1 to 5, wherein the perovskite material comprising the host material and the hydrophobic small molecule cross-linking agent is cross-linked as a thin film by means of UV irradiation and/or heating.
7. The method according to claim 6, characterized in that it comprises, before crosslinking, the steps of: step A: preparing a perovskite precursor solution, and adding the solution of the hydrophobic micromolecule cross-linking agent into the perovskite precursor solution for dispersion; and B: coating and annealing the perovskite precursor solution treated in the step A to prepare a perovskite thin film;
or comprising the following steps before crosslinking: step a: respectively preparing a lead iodide precursor solution and an organic salt solution, and adding the solution of the hydrophobic micromolecule cross-linking agent into the lead iodide precursor solution for dispersion; step b: coating and annealing the lead iodide precursor solution treated in the step a to prepare a lead iodide layer; step c: coating the organic salt solution on the lead iodide layer to further prepare the perovskite thin film.
8. The method of claim 7, wherein:
in the step A, the perovskite precursor solution is prepared by adding CsI DMSO solution into a mixed solution of iodoformamidine, bromomethylamine, lead bromide and lead iodide in a solvent with the volume ratio of N, N-Dimethylformamide (DMF) to dimethyl sulfoxide (DMSO) being 4: 1; the solution of the hydrophobic micromolecule cross-linking agent is DMF solution of the hydrophobic micromolecule cross-linking agent, and the concentration of the hydrophobic micromolecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic micromolecule cross-linking agent into the perovskite precursor solution for dispersion under the condition of keeping out of the sun;
in the step B, the coating method is spin coating; the annealing temperature is 100 ℃, and the annealing time is 60 min;
after the step B, crosslinking the hydrophobic small molecule crosslinking agent and the main body material through ultraviolet irradiation, or crosslinking the hydrophobic small molecule crosslinking agent and the main body material through heating, wherein the heating temperature is 140-150 ℃, and the heating time is 10-20 min;
or:
in the step a, the lead iodide precursor solution is a solution formed by lead iodide in a solvent with the volume ratio of N, N-dimethylformamide to dimethyl sulfoxide being 9: 1; the solution of the hydrophobic micromolecule cross-linking agent is DMF solution of the hydrophobic micromolecule cross-linking agent, and the concentration of the hydrophobic micromolecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic micromolecule cross-linking agent into the lead iodide precursor solution for dispersion under the condition of keeping out of the sun; the organic salt solution is an isopropanol solution of iodoformamidine, bromomethylamine and chloromethane;
in step b, the coating method is spin coating; the annealing temperature is 70 ℃, and the annealing time is 1 min;
in step c, the coating method is spin coating;
after the step c, annealing by heating and crosslinking the hydrophobic micromolecule crosslinking agent and the main material, wherein the heating temperature is 140-150 ℃, and the heating time is 10-20 min; or heating and annealing, and then irradiating ultraviolet light to enable the hydrophobic small molecule cross-linking agent to be cross-linked with the main body material.
9. A solar cell device comprising a transparent substrate, a first electrode layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second electrode layer, which are laminated in this order, characterized in that the perovskite light absorption layer is a perovskite material as set forth in any one of claims 1 to 5 or a perovskite material produced by the method as set forth in any one of claims 6 to 8.
10. A method for manufacturing a solar cell device is characterized by comprising the following steps:
step 1: cleaning the conductive glass; the conductive glass comprises a transparent substrate and a first conductive layer deposited on the transparent substrate;
step 2: spin coating an electron transport layer on the first conductive layer;
and step 3: forming a film-like crosslinked perovskite material on the electron transport layer by the method according to any one of claims 6 to 8 to prepare a perovskite light absorption layer;
and 4, step 4: a hole transport layer is coated on the perovskite light absorption layer in a spinning mode;
and 5: and evaporating a second electrode on the hole transport layer.
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US20200308149A1 (en) * 2017-12-22 2020-10-01 Energy Everywhere, Inc. Fused and cross-linkable ionic hole transport materials for perovskite solar cells
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