CN113461483B - Perovskite material, solar cell device and preparation method - Google Patents

Perovskite material, solar cell device and preparation method Download PDF

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CN113461483B
CN113461483B CN202110599221.5A CN202110599221A CN113461483B CN 113461483 B CN113461483 B CN 113461483B CN 202110599221 A CN202110599221 A CN 202110599221A CN 113461483 B CN113461483 B CN 113461483B
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perovskite
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linking agent
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CN113461483A (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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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 body material and a hydrophobic micromolecular crosslinking agent; the main material is organic-inorganic perovskite; the hydrophobic small molecule cross-linking agent is trifluoropropyl biaziridine compound. The perovskite material disclosed by the invention is uniform and compact in film formation, excellent in water vapor stability, high in operation stability of the solar cell device, and simple and feasible in preparation method of the perovskite material and the solar cell device.

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
The organic-inorganic hybrid perovskite material and the device thereof are easy to degrade in the environment of water vapor, illumination or high temperature. 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, formamidine) of the perovskite material, solidifying the organic components through weak interaction of the hydrogen bonds, and inhibiting movement or degradation of the organic components in the perovskite; (2) introducing a cross-linker polymer. The cross-linking agent polymer can exist at the perovskite film grain boundary, and the migration/diffusion channel of ions inside the perovskite along the grain 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 stability improvement, so that the perovskite material is difficult to adapt to severe environments. For example, the method of forming hydrogen bonds with perovskite, since hydrogen bonds belong to weaker interactions, are easily broken in severe environments, and the stability improvement is limited; the method of introducing the self-crosslinking type cross-linking agent polymer mainly improves the stability of the perovskite material by inhibiting the movement of crystal boundary ions, but the self-crosslinking type cross-linking agent polymer has no interaction with the perovskite component in nature, can only play a role of blocking the movement of ions in the crystal boundary, and cannot effectively solidify the movable component, so that the self-crosslinking type cross-linking polymer has difficulty in inhibiting the movement of ions in other defects such as vacancies and Frenkel defects, and the improvement of the stability is limited. In addition, the existing stability improving method is mainly used for researching the storage stability of devices, and is also important for inspecting the running stability of commercial solar cells.
Disclosure of Invention
In view of the shortcomings 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 producing 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 producing the solar cell device. The perovskite material disclosed by the invention is uniform and compact in film formation, excellent in water vapor stability, high in operation stability of the solar cell device, and simple and feasible in preparation method of the perovskite material and the solar cell device.
In order to achieve the first object of the present invention, the present invention provides a perovskite material, which is prepared by crosslinking a host material with a hydrophobic small molecule crosslinking agent; the main material is organic-inorganic perovskite; the hydrophobic small molecule cross-linking agent is a trifluoropropyl biaziridine compound, and the trifluoropropyl biaziridine compound has the structural formula:
wherein R is an organic group, preferably a hydrophobic organic group.
Preferably, the trifluoropropyl bisaziridine compound is selected from at least one of the following compounds:
the trifluoropropyl bisaziridine compound has the advantages of relatively easily available raw materials, good hydrophobicity of small molecules of the cross-linking agent, high chemical stability and the like.
Preferably, the hydrophobic small molecule cross-linker is dispersed throughout the host material; or hydrophobic small molecules dispersed in a first portion of the host material and contacted with a second portion of the remaining host material for re-crosslinking.
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 monovalent cation is at least one selected from methylamine ion, formamidine ion and cesium ion; the divalent cations are at least one of lead ions and tin ions; the anions are halogen anions.
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 a perovskite material comprising a host material and a hydrophobic small molecule cross-linking agent is formed into a thin film and cross-linked by ultraviolet irradiation and/or heating.
Preferably, the following steps are included prior to crosslinking: step A: preparing perovskite precursor liquid, and adding a solution of a hydrophobic small molecule cross-linking agent into the perovskite precursor liquid for dispersion; and (B) step (B): and (C) coating and annealing the perovskite precursor solution treated in the step (A) to prepare the perovskite film.
More preferably, in step a, the perovskite precursor solution is prepared by adding CsI in DMSO to a mixed solution of iodoformamidine, bromomethylamine, lead bromide and lead iodide in a solvent having a volume ratio of dimethylformamide to dimethylsulfoxide of 4:1; the solution of the hydrophobic small molecule cross-linking agent is DMF solution of the hydrophobic small molecule cross-linking agent, and the concentration of the hydrophobic small molecule cross-linking agent in the DMF solution is 100-200 mg/mL; the solution of the hydrophobic small molecule cross-linking agent is added into the perovskite precursor solution for dispersion under the light-shielding condition.
More preferably, in step B, the method of coating is spin coating; the annealing temperature is 100 ℃ and the annealing time is 60min.
More preferably, after the step B, the hydrophobic small molecule cross-linking agent is cross-linked with the host material by ultraviolet irradiation, or the hydrophobic small molecule cross-linking agent is cross-linked with the host material 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: preparing lead iodide precursor solution and organic salt solution respectively, and adding the solution of the hydrophobic micromolecular crosslinking 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: the organic salt solution is further prepared into a perovskite film on the basis of being coated on the lead iodide layer.
More preferably, in step a, the lead iodide precursor solution is a solution of lead iodide in a solvent having a volume ratio of N, N-dimethylformamide to dimethylsulfoxide of 9:1; the solution of the hydrophobic small molecule cross-linking agent is DMF solution of the hydrophobic small molecule cross-linking agent, and the concentration of the hydrophobic small molecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic micromolecular cross-linking agent into the lead iodide precursor solution, and dispersing under the light-proof condition; the organic salt solution is isopropyl alcohol solution of iodoformamidine, bromomethylamine and chloromethylamine.
More preferably, the method of coating is spin coating; the annealing temperature was 70℃and the annealing time was 1min.
More preferably, the method of coating is spin coating.
More preferably, annealing is performed by heating and the hydrophobic small molecule cross-linking agent is cross-linked with the host material, the heating temperature is 140-150 ℃ and the heating time is 10-20 min; or after annealing by heating, the hydrophobic small molecule cross-linking agent is cross-linked with the main body material by ultraviolet irradiation.
The grain condition and the film property can be well controlled by adopting the conditions in each step, 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, which comprises 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 schemes, or the perovskite material prepared by the method according to any one of the above schemes.
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 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; step 3: forming a film-shaped crosslinked perovskite material on the electron transport layer by the method of any one of the above, thereby preparing a perovskite light absorption layer; step 4: spin coating is carried out on the perovskite light absorption layer to prepare a hole transport layer; step 5: and evaporating a second electrode on the hole transport layer.
Compared with the prior art, the invention has the following beneficial effects:
the perovskite solar cell obtained based on the method can have good stability in the working state of illumination and external load, and provides a new scheme for the perovskite solar cell which can stably work. Specifically, the trifluoromethyl biazetidine compound is introduced to be intersected with the perovskite material to form a covalent bond under ultraviolet irradiation or high temperature, so that the degradation of the perovskite material is effectively prevented. Because the trifluoromethyl biazetidine compound is intersected with the perovskite at the grain boundary, the perovskite crystallization is promoted, and therefore, the perovskite film is uniform and compact and has no obvious holes. Meanwhile, the perovskite film contains small molecules of a hydrophobic cross-linking agent, the cross-linking small molecules have excellent water vapor stability, the cross-linking agent can act on organic components at a crystal boundary, and is coated on the surface of the perovskite crystal boundary to play a role of a protective layer, so that external water vapor is prevented from invading through the crystal boundary, the decomposition of the perovskite caused by the water vapor is avoided, and the stability of the perovskite in the air is improved. In addition, under the action of light and heat, ion migration/diffusion in the perovskite is an important factor affecting the light and heat stability of the perovskite, and the crosslinked micromolecules can crosslink with organic components (methylamine and formamidine) at the crystal boundary of the perovskite, solidify the organic components and inhibit the decomposition and migration of the organic components. Meanwhile, as the small molecules of the cross-linking agent are attached to the grain boundary, migration/diffusion channels of other ions in the perovskite along the grain boundary are also blocked, and the photo-thermal stability of the perovskite is further improved. Therefore, the small molecule of the cross-linking agent can improve the tolerance of the perovskite film to air, high temperature and illumination, and further improve the water vapor stability, thermal stability and light stability of the perovskite film.
Drawings
FIG. 1 is a chemical reaction structural formula of an example of a crosslinking agent participating in a crosslinking reaction in 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 perovskite solar cell of example 1 and comparative example 1 of the present invention in actual operation.
Fig. 4 is a graph comparing the stability of perovskite solar cell of example 2 and comparative example 2 of the present invention in actual operation.
FIG. 5 is a graph showing the results of water stability tests of perovskite thin films prepared in example 1 and comparative example 1 of the present invention.
The invention is described in further detail below with reference to the drawings and detailed description.
Detailed Description
The invention introduces the hydrophobic small molecule cross-linking agent of the trifluoromethyl bisaziridine compound into the traditional organic/inorganic perovskite material, the chemical structural formula of the hydrophobic small molecule cross-linking agent can be a compound shown in the figure 1, but the hydrophobic small molecule cross-linking agent is not limited to the compound, and other organic groups, preferably hydrophobic groups, can be adopted as R in the figure 1. The hydrophobic small molecule cross-linking agent is capable of undergoing a cross-linking reaction with perovskite organic components such as methylamine, formamidine, and the like. The small molecule cross-linking agent can be intersected with an organic matter under the condition of ultraviolet irradiation or heating to form a covalent bond with stronger interaction, and as shown in figure 1, the hydrophobic small molecule cross-linking agent can abstract hydrogen atoms in the organic matter and further cross-link with the organic matter. Unlike the self-crosslinking mode of conventionally used crosslinker molecules, the introduction of trifluoromethyl biaziridine compound crosslinker molecules into the perovskite material can crosslink the same at the grain boundaries with the organic components of the perovskite material to form relatively strongly interacted covalent bonds, thereby solidifying the organic components in the perovskite and inhibiting movement thereof in the grain boundaries, vacancies, frenkel defects and other defects. And simultaneously, the organic components near the grain boundary are prevented from volatilizing and escaping in the photo-thermal environment. Because the introduced trifluoromethyl biaziridine compound crosslinking agent small molecules have hydrophobicity, such as the hydrophobicity brought by trifluoromethyl groups, the small molecules of the crosslinking agent are adsorbed in perovskite crystal boundaries, so that the invasion of external water vapor can be effectively blocked, and the water vapor stability of the perovskite material is improved.
The structure of a solar cell device prepared by using the organic-inorganic hybrid perovskite material 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 a second electrode layer.
Example 1
The organic-inorganic hybrid perovskite material is prepared and the perovskite solar cell is prepared by 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 180nm; the hole transport layer is Spiro-OMeTAD with the thickness of 40nm; the modification layer is formed by interaction after spin coating of the acetic acid; perovskite layer main bodyThe main component is Cs 0.05 (MA 0.13 FA 0.87 ) 0.95 Pb(I 0.87 Br 0.13 ) 3 The thickness is 580nm; the electron transport layer is SnO 2 The thickness is 30nm; the second electrode layer is gold with a thickness of 80nm. The perovskite solar cell is prepared by the following steps:
(1) The ITO conductive glass is sequentially cleaned by glass cleaning liquid, acetone and ethanol, and after drying, residual organic matters are removed by an ultraviolet ozone cleaner.
(2) 360. Mu.L SnO 2 Mixing with 2.4mL deionized water, and preparing SnO by spin coating 2 And (3) after spin coating, placing the sample in an oven at 80 ℃ and carrying out vacuum annealing for 1h.
(3) Preparation of perovskite material, namely perovskite layer: and adding iodoformamidine, bromomethylamine, lead bromide and lead iodide into the mixed solution of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, wherein the mass of the lead iodide, the lead bromide, the bromomethylamine and the iodoformamidine is 117.97mg, 22.39mg,80.74mg and 507.1mg respectively. Another 45. Mu.L of CsI in DMSO was added at a concentration of 194.86mg/0.5 mL. Stirring for 2h at a constant temperature of 60 ℃ in a glove box to form a yellow uniform perovskite precursor solution. 22mg of the small molecule of the cross-linking agent shown in FIG. 1 was dissolved in 100. Mu.L of DMF solution and stirred at room temperature for 2 hours in a glove box. 15. Mu.L of the crosslinker solution was taken in the perovskite precursor solution and stirred for 1h in the dark. Spin-coating the obtained perovskite precursor solution onto the modified electron transport layer by an inverse solution method to form a uniform perovskite film, annealing at 100 ℃ for 60min, and assisting with UV illumination to crosslink the crosslinking agent and the perovskite, thereby obtaining a compact and stable perovskite light absorption layer. The perovskite layer with different cross-linking agent dosage can be obtained by changing the dosage of the cross-linking agent small molecules.
(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 a concentration of 520mg/mL, 29. Mu.L of 4-t-butylpyridine at a concentration of 300mg/mL, and the mixture was stirred at room temperature for 3 hours to form a hole transporting layer solution. And spin-coating the obtained hole transport layer solution on the perovskite light absorption layer to form the hole transport layer.
(5) Finally, evaporating a gold electrode on the hole transport layer by thermal evaporation, wherein the thickness of the gold electrode is 85nm, and thus the perovskite solar cell is prepared.
Example 2
The organic-inorganic hybrid perovskite material is prepared and the perovskite solar cell is prepared by 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 180nm; the electron transport layer is SnO 2 The thickness is 30nm; the perovskite layer is (FAPbI) 3 ) 1-x-y (MAPbBr 3 ) x )(MAPbCl 3 ) y ) Wherein x, y and 1-x-y are respectively more than or equal to 0 and less than or equal to 1, and the thickness is 700nm; the hole transport layer is a Spiro-OMeTAD with the thickness of 100nm; the second electrode layer is gold with a thickness of 80nm. The perovskite solar cell of this example was prepared as follows:
(1) The ITO conductive glass is sequentially cleaned by glass cleaning liquid, acetone and ethanol, and after drying, residual organic matters are removed by an ultraviolet ozone cleaner.
(2) 360uL of SnO 2 Mixing with 2.4mL deionized water, and preparing SnO by spin coating 2 And (3) after the spin coating of the electron transport layer is finished, placing the sample in an 80-DEG oven, and carrying out vacuum annealing for 1h.
(3) Preparation of perovskite material, namely perovskite layer: 600mg of lead iodide is added into a mixed solution of dimethylformamide and dimethyl sulfoxide in a volume ratio of 9:1, the mixed solution is stirred for 12 hours at a constant temperature of 60 ℃ in a glove box to form yellow uniform lead iodide precursor solution, and after the solution is cooled to room temperature, 11 mu L of a cross-linking agent molecular solution containing bistrifluoromethyl biaziridine groups with a concentration of 155mg/mL is added, wherein the solvent is DMF. In addition, 2mL of IPA (isopropyl alcohol) was added with iodoformamidine, bromomethylamine and chloromethylamine in amounts of 120mg, 12mg and 12mg, respectively, to obtain organic salt solutions. Preparing a perovskite solar cell by utilizing a two-step spin coating method, spin-coating a layer of lead iodide on an electron transport layer, annealing for 1min on a heat table at 70 ℃, spin-coating an organic salt solution on the lead iodide layer to form a uniform perovskite film, and maintaining the perovskite film at 150 ℃ for 15min to crosslink a perovskite organic component and a crosslinking agent, thereby obtaining a compact and stable perovskite light absorption layer.
(4) 72.3mg of Spiro-OMeTAD, 17.5. Mu.L of lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI) and 25. Mu.L of FK209 with a concentration of 520mg/mL and 29. Mu.L of 4-t-butylpyridine with a concentration of 300mg/mL were added to 1mL of chlorobenzene, and the mixture was stirred at room temperature for 3 hours to form a hole transporting layer solution; and spin-coating the obtained hole transport layer solution on the perovskite light absorption layer to form the hole transport layer.
(5) Finally, evaporating a gold electrode on the hole transport layer by thermal evaporation, wherein the thickness of the gold electrode is 85nm, and thus the perovskite solar cell is prepared.
Comparative example 1
Comparative example 1 the same conditions as in example 1 were used, except that the perovskite precursor solution of comparative example 1 did not contain a trifluoromethyl bisaziridine compound, and the resulting perovskite thin film did not contain the small molecule of the crosslinking agent.
Comparative example 2
Comparative example 2 the same conditions as in example 2 were followed except that the perovskite precursor solution of comparative example 2 did not contain a trifluoromethyl bisaziridine compound, and the resulting perovskite thin film did not contain the small molecule of the crosslinking agent.
The perovskite thin films and solar cell devices obtained in examples 1 to 2 and comparative examples 1 to 2 were tested:
(1) Comparison of the stability of the perovskite solar cell of example 1 and comparative example 1 in actual operation.
The working conditions are as follows: AM1.5G solar illumination (100 mW/cm) 2 ) The operating stability actually includes light stability and heat stability at 45 ℃. Results as shown in fig. 3, 0.5mol% or 0.25mol% crosslinker (UV) in fig. 3 corresponds to two UV-crosslinked two solar cell device examples obtained by adjusting the concentration of the crosslinking agent in the perovskite precursor solution in example 1; 0.5mol% or 0.25mol% of cross-linking agent corresponds to two solar cell devices which are not ultraviolet cross-linked and are obtained by adjusting the concentration of the cross-linking agent in the perovskite precursor solution in example 1, and the two solar cell devices are used as comparison; control devices and control devices (UV) correspondenceIs a comparative example of two solar cell devices in comparative example 1 to which no crosslinking agent was added and which were not irradiated with ultraviolet light and irradiated with ultraviolet light, respectively. In the figure, mol% refers to the mole percent of the cross-linking agent in the perovskite layer.
As can be seen from fig. 3, the operation stability of the perovskite solar cell device added with the small molecule of the cross-linking agent is greatly improved after ultraviolet irradiation, which indicates that the interaction between the cross-linking agent molecule and the perovskite component inhibits the decomposition and movement of the perovskite organic component, thereby improving the working stability of the perovskite solar cell. And the perovskite solar cell device which is not subjected to ultraviolet irradiation and added with the cross-linking agent micromolecule has reduced operation stability because the cross-linking agent molecules are not crosslinked.
(2) Comparison of the stability of the perovskite solar cell of example 2 and comparative example 2 in actual operation.
The working conditions are as follows: AM1.5G solar illumination (100 mW/cm) 2 ) The temperature was 45 ℃. Results as shown in fig. 4, 0.5% of fig. 4 corresponds to the example of the thermally crosslinked solar cell device obtained by adjusting the concentration of the crosslinking agent in the perovskite precursor solution in example 2, the mole percentage of the crosslinking agent in the perovskite layer being 0.5%; control corresponds to the solar cell device comparative example of comparative example 3, in which no crosslinking agent was added.
As can be seen from fig. 4, the perovskite solar cell using the perovskite thin film with the small molecule of the cross-linking agent improved has significantly improved stability under the actual working state.
(3) Water stability test of 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 test time is 130 hours. As a result, as shown in FIG. 5, (a) in FIG. 5 is the perovskite thin film without ultraviolet irradiation of comparative example 1, (b) is the perovskite thin film with ultraviolet irradiation of comparative example 1, (c) is the perovskite thin film without ultraviolet irradiation of example 1, and (d) is the perovskite thin film with ultraviolet irradiation of example 1.
As can be seen from FIG. 5, the perovskite film added with the small molecules of the cross-linking agent has no obvious change after water stability test no matter whether the perovskite film is irradiated by ultraviolet light or not. Whereas the film of comparative example 1 turned yellow in color due to degradation of the organic components, lead iodide was produced. Since the cross-linking agent has hydrophobicity, the hydrophobic group of the cross-linking agent is a main reason for improving the stability of the film, and whether the cross-linking agent and perovskite undergo a cross-linking reaction has less influence on the water stability.
Finally, it should be emphasized that the above description is merely of a preferred embodiment of the invention, and is not intended to limit the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The perovskite material is characterized by being prepared by crosslinking a main body material with a hydrophobic micromolecular crosslinking agent; the main material is organic-inorganic hybridization perovskite; the hydrophobic small molecule cross-linking agent is a trifluoropropyl bisaziridine compound, and the trifluoropropyl bisaziridine compound has a structural formula as follows:
wherein R is an organic group.
2. A perovskite material according to claim 1, characterized in that the trifluoropropyl bisaziridine compound is selected from at least one of the following compounds:
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 portion of the host material and contact a second portion of the remaining host material for re-crosslinking.
4. A perovskite material according to claim 1 or 2, characterized in that the mole percentage of the hydrophobic small molecule cross-linker in the perovskite material is 0.2% -0.5%.
5. A perovskite material according to claim 1 or 2, characterized in that the host material comprises monovalent cations, divalent cations and anions; the monovalent cation is at least one selected from methylamine ion, formamidine ion and cesium ion; the divalent cations are at least one of lead ions and tin ions; the anions are halogen anions.
6. A method for preparing a perovskite material according to any one of claims 1 to 5, characterized in that a perovskite material comprising said host material and said hydrophobic small molecule cross-linker is formed into a film and cross-linked by means of uv irradiation and/or heating.
7. The method according to claim 6, characterized in that it comprises the following steps before crosslinking: step A: preparing perovskite precursor liquid, and adding the solution of the hydrophobic small molecule cross-linking agent into the perovskite precursor liquid for dispersion; and (B) step (B): coating and annealing the perovskite precursor solution treated in the step A to prepare a perovskite film;
or the following steps are included before crosslinking: step a: preparing lead iodide precursor solution and organic salt solution respectively, adding the solution of the hydrophobic micromolecular crosslinking agent into the lead iodide precursor solution for dispersion, wherein the organic salt solution is isopropyl alcohol solution of iodoformamidine, bromomethylamine and chloromethylamine; step b: coating and annealing the lead iodide precursor solution treated in the step a to prepare a lead iodide layer; step c: the organic salt solution is further prepared into a perovskite film on the basis of being coated on a lead iodide layer.
8. The method according to claim 7, wherein:
in the step A, the perovskite precursor solution is prepared by adding a mixed solution of CsI (methyl iodide) into a mixed solution formed by iodoformamidine, bromomethylamine, lead bromide and lead iodide in a solvent with the volume ratio of N, N-Dimethylformamide (DMF) to dimethyl sulfoxide (DMSO) of 4:1; the solution of the hydrophobic small molecule cross-linking agent is DMF solution of the hydrophobic small molecule cross-linking agent, and the concentration of the hydrophobic small molecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic small molecule cross-linking agent into the perovskite precursor solution, and dispersing under the light-proof condition;
in the step B, the coating method is spin coating; the annealing temperature is 100 ℃, and the annealing time is 60min;
after the step B, the hydrophobic micromolecular cross-linking agent is cross-linked with the main body material through ultraviolet irradiation, or the hydrophobic micromolecular cross-linking agent is cross-linked with 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 small molecule cross-linking agent is DMF solution of the hydrophobic small molecule cross-linking agent, and the concentration of the hydrophobic small molecule cross-linking agent in the DMF solution is 100-200 mg/mL; adding the solution of the hydrophobic small molecule cross-linking agent into the lead iodide precursor solution, and dispersing under the light-proof condition;
in step b, the coating method is spin coating; the annealing temperature is 70 ℃, and the annealing time is 1min;
in step c, the coating method is spin coating;
after the step c, annealing is carried out by heating, and the hydrophobic micromolecular 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 after heating and annealing, the hydrophobic small molecule cross-linking agent is cross-linked with the main body material through ultraviolet irradiation.
9. A solar cell device comprising a transparent substrate, a first electrode layer, an electron transport layer, a perovskite light absorbing layer, a hole transport layer and a second electrode layer, which are laminated in this order, characterized in that the perovskite light absorbing layer is the perovskite material according to any one of claims 1 to 5, or the perovskite material produced by the method according to any one of claims 6 to 8.
10. A method of fabricating a solar cell device, comprising the steps of:
step 1: cleaning 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;
step 3: forming a film-like crosslinked perovskite material on the electron transport layer by the method of any one of claims 6 to 8, thereby producing a perovskite light absorbing layer;
step 4: spin-coating a hole transport layer on the perovskite light absorption layer;
step 5: and evaporating a second electrode on the hole transport layer.
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CN105470403A (en) * 2015-12-29 2016-04-06 苏州大学 Preparation method of cross-linked fullerene bulk heterojunction perovskite solar cell
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