CN109524551B - Liquid film fast coating air knife fast drying method climbing-restraining in-situ crystallization continuous preparation method of suede uniform perovskite film - Google Patents
Liquid film fast coating air knife fast drying method climbing-restraining in-situ crystallization continuous preparation method of suede uniform perovskite film Download PDFInfo
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Abstract
The invention discloses a liquid film fast coating air knife fast drying method climbing-restraining in-situ crystallization continuous preparation method of a suede uniform perovskite film, which comprises the following steps: firstly, uniformly coating a perovskite liquid film; secondly, rapid drying of the copying perovskite liquid film: drying the copying perovskite liquid film by adopting 5-20 air flow channels of the multi-flow air knife; thirdly, hot gas annealing treatment of the perovskite liquid film: and (3) carrying out heat treatment on the perovskite film for 10-30 min by adopting 30-50 airflow channels of the multi-flow air knife and gas with the temperature of 80-160 ℃, removing residual solvent and growing crystal grains to obtain the uniform perovskite film fully covering the textured surface of the pseudo-pyramid. According to the invention, under the condition that the silicon pyramid suede is not polished and ground, the preparation of fully covering the uniform profiling perovskite thin film on the pyramid suede substrate with fluctuation in micron scale is realized by adopting a solution deposition method, and the advantage of high efficiency of the silicon solar cell is maintained.
Description
Technical Field
The invention belongs to the technical field of preparation of silicon-perovskite laminated solar cells, and particularly relates to a preparation method of a perovskite film.
Background
The perovskite material is typically of the structure ABX3(A is an organic cation, e.g. CH)3NH3,CH(NH2)2Etc.; b is a metal cation such as Pb, Sn, etc.; x is F, Cl, Br, I). By 11 months in 2018, the highest efficiency of certified single-junction perovskite solar cells has been reachedReaching 23.4 percent. Higher photoelectric conversion efficiency has always been one of the core goals of the development of photovoltaic cell technology. However, the photoelectric conversion efficiency of a single-junction perovskite solar cell cannot exceed the theoretical limit efficiency of the Shockley-Queti. The multi-junction solar cell, namely the laminated cell, is composed of solar sub-cells with different band gaps, is a mature and effective mode for breaking through the ultimate theoretical efficiency of Shockley-Quieituse, and is widely applied to the traditional silicon and gallium arsenide solar cells. Silicon solar cells are currently the predominant photovoltaic technology that occupies the greatest market share. The band gap of monocrystalline silicon is about 1.1eV, and the monocrystalline silicon is an ideal narrow-band-gap sub-cell. The organic-inorganic hybrid perovskite material and the all-inorganic perovskite material have the characteristic of continuously adjustable band gap (1.25-2.0 eV). Based on the above characteristics, the silicon-perovskite tandem photovoltaic cell technology becomes one of the major topics for realizing the ultra-efficient and low-cost photovoltaic power generation technology.
High efficiency commercial silicon solar cells typically employ pyramidal textured light trapping structures. The undulation height of the silicon pyramid texture is usually 1-20 mu m, and the light capture capacity can be effectively increased, so that the short-circuit current density of the cell is improved. However, it is difficult to deposit perovskite films of uniform thickness on such complex surface textures. When perovskite thin films with the thickness of less than 1 μm are deposited by a solution method, the solution accumulates in valleys between the "pyramids" so that the tips of the pyramids are not covered with liquid, which results in the final perovskite thin film not completely covering the top corners and edges of the pyramids. This phenomenon will cause cell shorting, which in turn reduces the photoelectric conversion efficiency of the perovskite/crystalline silicon tandem solar cell. In order to avoid this problem, the prior art carries out polishing and smoothing treatment on the pyramid texture of the silicon cell. However, the photoelectric conversion efficiency of the silicon solar cell after polishing is reduced to about 50% of the original value, compared to the silicon cell having the pyramid textured light trapping structure. Therefore, the technical scheme has the following defects: firstly, polishing and grinding the suede of the silicon pyramid greatly reduces the photoelectric conversion efficiency of the silicon solar cell; second, the added polishing and smoothing process increases the production cost of the tandem solar cell, increases the processes and time, and reduces the production efficiency. Therefore, how to prepare a full-coverage uniform profiling perovskite thin film on a micron-scale fluctuating pyramid textured substrate becomes a core problem for realizing a high-efficiency low-cost silicon-perovskite two-end laminated photovoltaic cell technology.
Disclosure of Invention
The invention aims to provide a liquid film fast-coating air knife fast-drying method climbing-restraining in-situ crystallization continuous preparation method of a suede uniform perovskite film, and the method is used for solving the technical problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the liquid film fast coating air knife fast drying method climbing-restraining in-situ crystallization continuous preparation method of the suede uniform perovskite film comprises the following steps:
step one, uniformly coating a perovskite liquid film: coating the perovskite precursor sol or solution on a substrate with the pyramid texture morphology to form a uniform profiling perovskite liquid film with the thickness less than 60% of the average feature height of the pyramid;
secondly, rapid drying of the copying perovskite liquid film: drying the copying perovskite liquid film by adopting 5-20 air flow channels of the multi-flow air knife;
thirdly, hot gas annealing treatment of the perovskite liquid film: and (3) carrying out heat treatment on the perovskite film for 10-30 min by adopting 30-50 airflow channels of the multi-flow air knife and gas with the temperature of 80-160 ℃, removing residual solvent and growing crystal grains to obtain the uniform perovskite film fully covering the textured surface of the pseudo-pyramid.
Furthermore, in the second step, after the perovskite liquid film is coated and in the drying process, the drying of the profiling perovskite liquid film is completed before the ratio of the total amount of solute in the local external normal solid phase and the liquid phase at the edge to the design amount is not lower than the ratio of the bearable minimum thickness and the design thickness of the local external normal perovskite film at the edge. The design thickness is not less than 50 nm; the ratio of the minimum thickness to the design thickness that can be tolerated is not less than 10%.
Further, the total amount of solute in the solid and liquid phases includes solid phase perovskites that have nucleated crystals and perovskites that have not crystallized in the liquid phase.
Further, the solid phase perovskite with the nucleated crystals comprises solid phase perovskite and perovskite existing in a complex form.
Furthermore, the substrate with the pyramid suede appearance is a silicon pyramid suede.
Furthermore, the substrate with the pyramid suede appearance is a silicon gold pyramid suede deposited with a profiling tunneling layer, a silicon gold pyramid suede coated with a profiling hole transmission layer or a silicon gold pyramid suede coated with a profiling electron transmission layer.
Further, in the second step, drying the copying perovskite liquid film by adopting 5-20 air flow channels of a multi-flow air knife in a multi-flow air knife liquid film rapid drying device; in the case of aeration, the gas to be introduced is a gas which does not react with the perovskite liquid film.
Further, the gas which does not react with the perovskite liquid film is air, nitrogen or argon.
Furthermore, the chemical general formula of the solute in the perovskite precursor sol or solution is ABX3Wherein A is selected from alkylamines, alkali metals or combinations thereof, B is selected from lead, tin or combinations thereof, and X is selected from Br, Cl, I or combinations thereof.
Further, the thickness of the profiling perovskite liquid film coated in the first step is less than 60% of the average feature height of the pyramid. The pyramid average feature height ranges from 5-20 microns.
And further, in the second step, drying the liquid film by adopting a multi-flow air knife method within the time corresponding to that the thickness of the liquid film at the pyramid edges and corners is reduced to 50-95% of the original thickness when the perovskite liquid film creeps on the texture surface.
Further, the fast coating means that after the first coating step is completed, the perovskite liquid film is subjected to air-exhaust drying treatment within 8 seconds. After coating, the coating is transferred to a drying device for about 5 seconds, and the total time is about 8 seconds after drying for 3 seconds.
Compared with the prior art, the invention has the following beneficial effects:
(1) after the perovskite liquid film is quickly coated, the perovskite liquid film creeps on the texture surface to reduce the thickness of the liquid film at the edges and corners of the pyramid to be within the time corresponding to 50-95% of the original thickness; the creeping time of the liquid film is shortened by utilizing a multi-flow air knife method, and the quick drying of the liquid film is realized; continuous rapid annealing of perovskite thin films is achieved using high temperature multi-stream gases.
(2) Under the condition that the silicon pyramid suede is not polished and ground, a solution method can be adopted to prepare a full-coverage uniform profiling perovskite thin film on a pyramid suede substrate with fluctuating micron scale, the advantage of high efficiency of a silicon solar cell can be kept, and the silicon-perovskite two-end laminated solar cell technology with photoelectric conversion efficiency of more than 35% is realized;
(3) the invention avoids polishing and grinding treatment of the suede of the silicon pyramid, reduces the production cost of the silicon-perovskite laminated solar cell, reduces the waste of time and improves the actual production speed.
(4) The invention provides a continuous production manufacturing method, which can continuously complete coating, drying and heat treatment of a perovskite liquid film, reduce time waste and improve the actual production speed.
Detailed Description
The following examples are provided to further illustrate the practice of the present invention.
Example 1
The preparation method of the suede uniform perovskite film comprises the following steps:
(1) preparing perovskite precursor sol: using DMF as solvent, PbI2And CH3NH3I is solute, perovskite sol is prepared, CH in the perovskite sol3NH3PbI3The mass percentage concentration of (A) is 40%.
(2) Uniform coating of the perovskite liquid film: coating the perovskite precursor sol on a silicon solar cell with a pyramid texture surface shape by adopting a soft brush coating mode to form a faint yellow uniform profiling perovskite liquid film with the thickness of 2 mu m; the thickness of the coated profiling perovskite liquid film is less than 60% of the average feature height of the pyramid;
(3) fast drying treatment of the perovskite liquid film: drying the perovskite liquid film by using 5 air flow channels of multi-flow air knife perovskite liquid film rapid drying equipment within 3s, thereby obtaining a uniform and full-coverage gold-like tower-shaped perovskite thin film with the thickness of 400 nm; during ventilation, the ventilated gas is air;
(4) heat treatment of the perovskite thin film: and (3) carrying out heat treatment on the perovskite film for 10min by adopting a multi-flow air knife method and 30 air flow channels of a multi-flow air knife and gas with the temperature of 100 ℃, removing residual solvent and growing crystal grains so as to obtain the uniform and full-coverage imitated-golden-tower-shaped perovskite film.
Example 2
The preparation method of the suede uniform perovskite film comprises the following steps:
(1) preparing perovskite precursor sol: using DMSO as a solvent, PbI2And CH3NH3I is solute, perovskite sol is prepared, CH in the perovskite sol3NH3PbI3The mass percentage concentration of (A) is 35%.
(2) Uniform coating of the perovskite liquid film: coating the perovskite precursor sol on a silicon solar cell with a pyramid texture surface shape by adopting a soft brush coating mode to form a faint yellow uniform profiling perovskite liquid film with the thickness of 1 mu m; the thickness of the coated profiling perovskite liquid film is less than 60% of the average feature height of the pyramid;
(3) fast drying treatment of the perovskite liquid film: drying the perovskite liquid film by using 20 air flow channels of multi-flow air knife perovskite liquid film rapid drying equipment within 3s, thereby obtaining a uniform and full-coverage gold-like tower-shaped perovskite thin film with the thickness of 200 nm; during the aeration, the gas to be aerated is argon;
(4) heat treatment of the perovskite thin film: and (3) carrying out heat treatment on the perovskite film for 30min by adopting a multi-flow air knife method and 50 air flow channels of a multi-flow air knife and gas with the temperature of 120 ℃, removing residual solvent and growing crystal grains so as to obtain the uniform and full-coverage imitated-golden-tower-shaped perovskite film.
Example 3
The preparation method of the suede uniform perovskite film comprises the following steps:
(1) preparing perovskite precursor sol: with DMF as solvent, PbI2And CH3NH3I is solute, perovskite sol is prepared, CH in the perovskite sol3NH3PbI3The mass percentage concentration of (A) is 40%.
(2) Uniform coating of the perovskite liquid film: coating the perovskite precursor sol on a silicon solar cell with a pyramid texture surface shape by adopting a soft brush coating mode to form a faint yellow uniform profiling perovskite liquid film with the thickness of 2 mu m; the thickness of the coated profiling perovskite liquid film is less than 60% of the average feature height of the pyramid;
(3) fast drying treatment of the perovskite liquid film: drying the perovskite liquid film by using 15 air flow channels of multi-flow air knife perovskite liquid film rapid drying equipment within 3s, thereby obtaining a uniform and full-coverage gold-like tower-shaped perovskite thin film with the thickness of 400 nm; during aeration, the aerated gas is nitrogen;
(4) heat treatment of the perovskite thin film: and (3) carrying out heat treatment on the perovskite film for 20min by adopting a multi-flow air knife method and 40 air flow channels of a multi-flow air knife and gas with the temperature of 160 ℃, removing residual solvent and growing crystal grains so as to obtain the uniform and full-coverage imitated-golden-tower-shaped perovskite film.
Example 4
The preparation method of the suede uniform perovskite film comprises the following steps:
(1) preparing perovskite precursor sol: using DMF as solvent, PbI2And CH3NH3I is solute, perovskite sol is prepared, CH in the perovskite sol3NH3PbI3The mass percentage concentration of (A) is 40%.
(2) Uniform coating of the perovskite liquid film: coating the perovskite precursor sol on a silicon solar cell with a pyramid texture surface shape by adopting a soft brush coating mode to form a faint yellow uniform profiling perovskite liquid film with the thickness of 2 mu m; the thickness of the coated profiling perovskite liquid film is less than 60% of the average feature height of the pyramid;
(3) fast drying treatment of the perovskite liquid film: drying the perovskite liquid film by using 10 air flow channels of multi-flow air knife perovskite liquid film rapid drying equipment within 3s, thereby obtaining a uniform and full-coverage gold-like tower-shaped perovskite thin film with the thickness of 400 nm; during ventilation, the ventilated gas is air;
(4) heat treatment of the perovskite thin film: and (3) carrying out heat treatment on the perovskite film for 15min by adopting a multi-flow air knife method and 45 air flow channels of a multi-flow air knife and gas with the temperature of 80 ℃, removing residual solvent and growing crystal grains so as to obtain the uniform and full-coverage imitated-golden-tower-shaped perovskite film.
In summary, the above is only a preferred embodiment of the present invention, and all equivalent modifications made in the claims and the specification of the present invention are within the scope of the present invention.
Claims (8)
1. The liquid film fast coating air knife fast drying method climbing-restraining in-situ crystallization continuous preparation method of the suede uniform perovskite film is characterized by comprising the following steps:
step one, uniformly coating a perovskite liquid film: coating the perovskite precursor sol or solution on a substrate with the shape of the texture of the pyramid to form a layer of uniform profiling perovskite liquid film;
secondly, rapid drying of the copying perovskite liquid film: drying the copying perovskite liquid film by adopting 5-20 air flow channels of the multi-flow air knife;
thirdly, hot gas annealing treatment of the perovskite liquid film: carrying out heat treatment on the perovskite thin film for 10-30 min by adopting 30-50 airflow channels of a multi-flow air knife and gas with the temperature of 80-160 ℃, removing residual solvent and growing crystal grains to obtain a full-coverage textured uniform perovskite thin film imitating a pyramid shape;
secondly, in the process of coating and drying the perovskite liquid film, drying the profiling perovskite liquid film before the ratio of the total amount of solute in the local external normal solid phase and the liquid phase at the edge to the design amount is not lower than the ratio of the bearable minimum thickness and the design thickness of the local external normal perovskite thin film at the edge;
the thickness of the profile modeling perovskite liquid film coated in the first step is less than 60% of the average characteristic height of the pyramid;
the pyramid average feature height ranges from 5-20 microns.
2. The method for continuously preparing the suede uniform perovskite film by the liquid film fast coating air knife fast drying method for inhibiting creeping in-situ crystallization according to claim 1, wherein the total amount of solute in the solid phase and the liquid phase comprises solid-phase perovskite with nucleation crystallization and perovskite not yet crystallized in the liquid phase.
3. The liquid film fast-coating air knife fast-drying method creeping-inhibiting in-situ crystallization continuous preparation method of the suede uniform perovskite film according to claim 2, characterized in that the solid phase perovskite with the shaped-core crystallization comprises solid phase perovskite and perovskite existing in a complex form.
4. The liquid film fast-coating air knife fast-drying method creeping-inhibiting in-situ crystallization continuous preparation method of the suede uniform perovskite film according to claim 1, characterized in that the substrate of the pyramid suede morphology is a silicon-gold-shaped pyramid suede.
5. The liquid film fast-coating air knife fast-drying method climbing-restraining in-situ crystallization continuous preparation method of the suede uniform perovskite film according to claim 1, characterized in that a substrate of the pyramid suede morphology is a silicon gold-shaped tower suede deposited with a profiling tunneling layer, a silicon gold-shaped tower suede coated with a profiling hole transmission layer or a silicon gold-shaped tower suede coated with a profiling electron transmission layer.
6. The liquid film fast-coating air knife fast-drying method creeping-inhibiting in-situ crystallization continuous preparation method of the suede uniform perovskite film according to claim 1, which is characterized in that in the second step, 5-20 air flow channels of a multi-flow air knife are adopted in multi-flow air knife liquid film fast-drying equipment to complete the drying of the profiling perovskite liquid film; in the case of aeration, the gas to be introduced is a gas which does not react with the perovskite liquid film.
7. The liquid film fast-coating air knife fast-drying method creeping-inhibiting in-situ crystallization continuous preparation method of the suede uniform perovskite film according to claim 6, characterized in that the gas which does not react with the perovskite liquid film is air, nitrogen or argon.
8. The method for continuously preparing the suede uniform perovskite film through liquid film fast coating air knife fast drying method creeping-inhibiting in-situ crystallization according to claim 1, which is characterized in that the chemical general formula of the solute in the perovskite precursor sol or solution is ABX3Wherein A is selected from alkylamines, alkali metals or combinations thereof, B is selected from lead, tin or combinations thereof, and X is selected from Br, Cl, I or combinations thereof.
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