CN110880555A - Coating equipment and method for mixed solution of precursor and surfactant - Google Patents
Coating equipment and method for mixed solution of precursor and surfactant Download PDFInfo
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- CN110880555A CN110880555A CN201811028438.5A CN201811028438A CN110880555A CN 110880555 A CN110880555 A CN 110880555A CN 201811028438 A CN201811028438 A CN 201811028438A CN 110880555 A CN110880555 A CN 110880555A
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- H—ELECTRICITY
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Abstract
The invention relates to coating equipment of a mixed solution of a precursor and a surfactant, which comprises a coating die head, a die head lifting table, a post-treatment device, a coating platform and a conveying device, wherein a substrate to be coated is conveyed to the post-treatment device by the conveying device for post-treatment after being coated by the coating die head, and the die head lifting table and the coating platform generate relative movement under the driving of the conveying device; the coating die head is communicated with an injection pump with a mixing cavity through a conduit, the injection pump is communicated with at least two raw material bottles, one raw material bottle is filled with a divalent precursor solution, the other raw material bottle is filled with a surfactant solution, the injection pump respectively and simultaneously pumps the divalent precursor solution and the surfactant solution to be injected into the mixing cavity for mixing, and the mixed solution is conveyed to the coating die head for use. The invention also discloses a using method and application of the coating equipment. The invention improves the coverage rate of the coating film and the flatness of the surface of the coating film, and obtains the perovskite thin film with more uniform film thickness distribution.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to coating equipment and a coating method for a mixed solution of a precursor and a surfactant.
Background
At present, the perovskite solar cell is mainly prepared by a spraying method, a blade method, a slit coating method, an ink printing method, an ink-jet printing method and the like. Slit Die Coating (slit Die Coating) is one of the simplest methods for preparing perovskite solar cells in large scale in industrialization, and has the advantages of short preparation process period, raw material saving, simple process operation and the like. However, the perovskite solar cell prepared by the traditional slit coating has the defects of more holes, serious uneven film thickness of the thin film and the like, and the large-area preparation and the commercial application of the slit coating for the perovskite solar cell are seriously restricted.
The general perovskite solar cell fabrication process includes a one-step process and a two-step process. In the one-step perovskite solution film forming process, the crystallization speed of perovskite is high and the morphology of the perovskite film is difficult to control. Compared with a one-step method, the two-step method for preparing the perovskite thin film has more technological methods and adjusting means. The two-step process is to first prepare a divalent precursor thin film layer on a substrate by using a divalent precursor (also called divalent metal halide) solution of perovskite, and then prepare a monovalent precursor thin film layer by using a monovalent precursor (also called monovalent cation halide) solution on the basis. In the two-step method, the reaction degree of the perovskite thin film and the performance of the perovskite thin film can be effectively regulated and controlled by regulating and controlling the film forming process of the divalent metal halide and the deposition process of the monovalent cation halide on the divalent metal halide thin film.
In chinese patent publication No. CN107437587A entitled method for preparing perovskite active layer of perovskite solar cell in air, it is disclosed that when preparing perovskite active layer by two-step method, a proper amount of pyridine organic small molecules are added into lead iodide solution as additive to reduce the influence of humidity during preparation of perovskite active layer, so as to realize preparation of perovskite solar cell in air. The micromolecule additive can not achieve the leveling effect of the precursor solution in the film forming process, and can not really solve the defects of holes, uneven film thickness and the like caused by the divalent metal halide coating in the air environment.
As shown in fig. 1, a schematic cross-section of each layer of a conventional perovskite solution-coated battery is shown, in which 11 is a substrate, an oleophilic electron/hole transport layer 12-2 is prepared on the conductive layer 11, and the oleophilic electron/hole transport layer 12-2 is prepared using, for example, any one of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) and poly (3-hexylthiophene-2, 5-diyl) (P3 HT). 16 is a coating layer of the perovskite solution. Under normal coating conditions, the perovskite solution is hydrophilic, is difficult to infiltrate into an oleophilic electron/hole transport layer, cannot be paved on the surface of the electron/hole transport layer, and is easy to generate a lot of necking after being coated. If at higher preparation temperatures, for example: by the temperature of 100 ℃ and 180 ℃, a plurality of pinholes are easily generated, which not only seriously affects the quality of the perovskite battery, but also reduces the conversion efficiency of the perovskite battery.
Disclosure of Invention
The invention aims to provide a coating device and a coating method for a mixed solution of a precursor and a surfactant, which can improve the coverage rate of a coating film and the flatness of the surface of the coating film and obtain a perovskite thin film with more uniform film thickness distribution.
The invention is realized in such a way, and provides a coating device of a mixed solution of a precursor and a surfactant, which comprises a coating die head, a die head lifting platform, a coating platform, a conveying device and a post-treatment device, wherein the coating die head is arranged on the die head lifting platform, the coating die head and the post-treatment device are mutually separated and respectively arranged above the coating platform, a substrate to be coated placed on the coating platform is conveyed to the post-treatment device by the conveying device for post-treatment after being coated by the coating die head, the die head lifting platform and the coating platform generate relative movement under the driving of the conveying device, and the die head lifting platform adjusts the height between the coating die head and the substrate to be coated; the coating die head is communicated with an injection pump with a mixing cavity through a conduit, the mixing cavity of the injection pump is respectively communicated with at least two raw material bottles through pipelines, at least one raw material bottle contains a divalent precursor solution of perovskite, at least one other raw material bottle contains a surfactant solution, the injection pump respectively and simultaneously pumps the divalent precursor solution of perovskite and the surfactant solution according to a set volume ratio, the two raw material bottles and the surfactant solution are injected into the mixing cavity to be mixed, and the mixed solution obtained through mixing is conveyed to the coating die head through the conduit for use.
The invention is realized in such a way that a preparation method of a mixed solution of a precursor and a surfactant is provided, and the preparation method is characterized in that the precursor is a divalent precursor solution of perovskite, and the divalent precursor solution comprises a divalent metal halide BX2And a divalent precursor solvent, the formulation method comprising:
injecting a divalent precursor solution into one raw material bottle, injecting a surfactant solution into the other raw material bottle, respectively communicating the two raw material bottles with an injection pump through pipelines, simultaneously and respectively pumping the divalent precursor solution and the surfactant solution into a mixing cavity by the injection pump according to a set volume ratio for mixing, and stirring to obtain a mixed solution of a precursor and the surfactant, wherein,
the divalent metal halide BX2B in (A) is Pb2+、Sn2+、Ze2+At least one of (1), X is Cl-、Br-、I-At least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL); the concentration of the divalent precursor solution is 0.5-1.5mol/L, and the mass ratio of the surfactant to the divalent precursor solution is 0.05-5%;
the mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution comprises an active agent solute and an active agent solvent, the active agent solute is a nonionic, cationic, anionic or amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone;
pumping a divalent precursor solution and a surfactant solution at a set volume ratio of 1-1000; the ambient set temperature during stirring was 10-60 ℃.
The present invention is achieved in such a way that there is provided a method for using the apparatus for coating a mixed solution of a precursor and a surfactant as described above, the method comprising the steps of:
firstly, injecting a divalent precursor solution and a surfactant solution of perovskite prepared according to the preparation method of the mixed solution of the precursor and the surfactant into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pump simultaneously and respectively pumps the divalent precursor solution and the surfactant solution according to a set volume ratio, the divalent precursor solution and the surfactant solution are injected into a mixing cavity for mixing, and the mixed solution of the precursor and the surfactant is obtained after stirring;
secondly, placing the substrate to be coated on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, driving the die head lifting platform and the coating platform to move relatively, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;
and thirdly, starting the post-treatment device, conveying the coated substrate to the post-treatment device by the conveying device for post-treatment, and preparing a film layer containing a divalent precursor on the surface of the substrate.
The present invention is achieved in this way, and provides a method for manufacturing a perovskite solar cell, characterized in that a coating apparatus of a mixed solution of a precursor and a surfactant as described above is used in the process of manufacturing the perovskite solar cell, and the method includes the steps of:
s1, pouring a divalent precursor solution of the perovskite and a surfactant solution prepared according to the preparation method of the mixed solution of the precursor and the surfactant into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pump simultaneously and respectively pumps the divalent precursor solution of the calcium and the surfactant solution according to a set volume ratio, the calcium and the surfactant solution are injected into a mixing cavity to be mixed, and the mixed solution of the precursor and the surfactant is obtained after stirring;
s2, placing the substrate with the conductive layer and the electron/hole transport layer prepared on the surface on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, generating relative movement between the die head lifting platform and the coating platform under the driving of the conveying device, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;
s3, starting the post-processing device, conveying the coated substrate to the post-processing device by the conveying device for post-processing, and preparing a film layer containing a divalent precursor on the electron/hole transport layer on the surface of the substrate;
s4, continuously preparing a monovalent precursor thin film layer, a hole/electron transport layer and a back electrode layer of the perovskite on the surface of the thin film layer containing the divalent precursor of the substrate until the perovskite solar cell is prepared.
The present invention has been achieved by providing a perovskite solar cell including a perovskite thin film layer prepared by using the apparatus for coating a mixed solution of a precursor and a surfactant as described above, or by using the method for preparing a perovskite solar cell as described above.
Compared with the prior art, the coating equipment and the coating method of the mixed solution of the precursor and the surfactant improve the film thickness uniformity of the divalent metal halide film and reduce the hole defects after the surfactant is added into the divalent metal halide precursor solution. By adopting the method of the mixing chamber, the content of the surfactant in the perovskite precursor is effectively adjusted according to the difference of the hydrophilicity of the substrate, the film forming appearance of the divalent metal halide precursor is adjusted, and the influence of the introduction of the surfactant on the reduction of the efficiency of the perovskite solar cell is reduced. The surfactant solution is added into the divalent precursor solution of the slit-type coated perovskite, so that the defects of shrinkage cavity caused by poor infiltration of the divalent precursor solution and the surface of the transmission layer of the substrate, pinholes caused by too fast volatilization of the solution, serious uneven film thickness caused by uneven distribution of the coating solution and the like are favorably reduced; the coating coverage rate and the coating surface flatness are improved, and the perovskite thin film layer with more uniform film thickness distribution is obtained, so that the efficiency of the perovskite solar cell is improved. The coating equipment and the method thereof are not only applied to the technical field of perovskite solar cells, but also widely applied to the technical field of organic solar cells, dye-sensitized solar cells and quantum dot solar cells.
Drawings
FIG. 1 is a schematic cross-sectional view of a prior art perovskite thin film layer after coating;
FIG. 2 is a schematic cross-sectional structure of a conventional perovskite solar cell;
FIG. 3 is a perspective view of a preferred embodiment of an apparatus for coating a mixed solution of a precursor and a surfactant according to the present invention;
FIG. 4 is a perspective view of the mixing chamber of FIG. 3;
FIG. 5 is a schematic of the morphology of a perovskite thin film layer prepared by a prior art method;
FIG. 6 is a schematic cross-sectional view of a coated perovskite thin film layer made of a mixed solution of a precursor and a surfactant;
FIG. 7 is a schematic view of the morphology of a first embodiment of a perovskite thin film layer prepared by a coating apparatus using a mixed solution of a precursor and a surfactant according to the present invention;
fig. 8 is a graph showing a comparison of efficiencies after fabrication into perovskite solar cells according to example one and example two of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Fig. 2 is a schematic cross-sectional structure diagram of a conventional perovskite solar cell. The conductive layer 11, the electron/hole transport layer 12, the perovskite thin film layer 13, the hole/electron transport layer 14 and the back electrode layer 15 are sequentially prepared on the substrate, wherein the most critical is the preparation of the perovskite thin film layer 13.
The present invention first discloses a coating apparatus for preparing a perovskite thin film layer 13, which is used to coat a divalent precursor solution containing a surfactant on an electron/hole transport layer 12 to make the perovskite thin film layer 13.
Referring to fig. 3 and 4, a preferred embodiment of the coating apparatus for a mixed solution of a precursor and a surfactant according to the present invention includes a coating die 101, a die lift 102, a coating platform 106, a conveyor 107, and a post-treatment device 105.
The coating die 101 is disposed on a die lift 102 and a substrate 108 to be coated is placed on a coating platform 106. The coating die 101 and the post-treatment device 105 are separated from each other and disposed above the coating stage 106, respectively. The die lifter 102 is disposed on both sides of the coating platform 106. The substrate 108 to be coated is conveyed by the conveying device 107 to the post-treatment device 105 for post-treatment after being coated by the coating die 101.
Driven by the conveying device 107, the die lifting platform 102 and the coating platform 106 are relatively moved, so that the coating die 101 coats the surface of the substrate 108 to be coated, which is placed on the coating platform 106. The die lift 102 adjusts the height between the coating die 101 and the substrate 108 to be coated. The coating die 101 is connected with a syringe pump 104 with a mixing chamber 111 through a conduit 103, and the mixing chamber 111 of the syringe pump 104 is connected with at least two raw material bottles through pipelines 112 and 115, wherein at least one raw material bottle 109 contains divalent precursor solution of perovskite, and at least another raw material bottle 110 contains surfactant solution. The injection pump 104 simultaneously pumps the divalent precursor solution of the perovskite and the surfactant solution according to a set volume ratio of 1-1000, respectively, and injects the two solutions into the mixing cavity 111 of the injection pump 104 for mixing, and the mixed solution is conveyed to the coating die head 101 through the conduit 103 for use.
The die lift 102, coating platform 106 and conveyor 107 are in two assembly coupling relationships. The first assembly coupling relationship is: the conveyor 107 drives the coating platform 106 to move, the coating die head 101 and the die head lifting platform 102 are kept static, and the die head lifting platform 102 and the coating platform 106 are relatively moved. The second assembling connection relation is as follows: the conveyor 107 drives the coating die 101 and the die lifting platform 102 to move, the coating platform 106 is kept still, and the die lifting platform 102 and the coating platform 106 are relatively moved.
The die head elevating table 102 is further provided with a film forming device (not shown) for forming a wet film on the surface of the substrate 108 immediately after the coating by the coating die head 101 is completed within 0 to 60 seconds. The film forming device comprises a heater, a blower or a suction fan, or a heater and a vacuum pump.
Specifically, the post-processing device comprises a heater, a vacuum pump and a closed cavity which is convenient to open and close.
Specifically, a stirring device or an ultrasonic oscillation device is further disposed in the mixing cavity 111. Referring to fig. 4, the mixing chamber 111 is respectively communicated with a raw material bottle 109 containing a perovskite solution and a raw material bottle 110 containing a surfactant solution through pipelines 112 and 115, and the injection pump 104 respectively pumps the perovskite solution and the surfactant solution into the mixing chamber 111 according to a volume ratio of 1-1000. The solution 114 in the mixing chamber 111 is mixed uniformly by the stirring device 113. The mixed solution 114 is quickly transported to the die 101 through the conduit 103 for coating.
After the divalent precursor solution is mixed with a certain amount of surfactant solution, the hydrophilicity of the surface of an electron/hole transport layer during coating is improved, the flatness of the surface which is in contact with air after the film is formed by the perovskite solution is adjusted, and the volatilization speed of the solvent in the divalent precursor solution is adjusted, so that the defects of shrinkage cavity, pin hole, uneven film thickness and the like during coating are reduced. After the complete solar cell is prepared, the interface defects between the perovskite layer and the transmission layer and the internal defects of the perovskite layer can be passivated, the carrier transmission performance of the perovskite solar cell is effectively improved, the recombination of electron-hole carrier pairs is inhibited, and therefore the efficiency of the perovskite solar cell is improved.
On the other hand, after the divalent precursor solution is mixed with a certain amount of surfactant solution, the surfactant solution can be quickly coated for use, and the process is characterized in that most of the surfactant cannot be completely dissolved in the divalent precursor solution, so that most of the surfactant can be quickly dispersed into the divalent precursor solution, and the phenomenon that the surfactant and the divalent precursor solution are layered due to incompatibility caused by long-time standing after the surfactant is directly added into the divalent precursor solution is avoided. In addition, the process method has the characteristics of wide variety of suitable surfactants for perovskite film formation, great improvement on the uniformity of the perovskite film after film formation, fewer defects of the perovskite film, longer storage time of a divalent precursor solution and the like.
In the slot type coating process of the coating equipment, the surfactant plays a role in leveling the divalent precursor solution, so that the defects of uneven film thickness and holes of the formed perovskite thin film are reduced, and the efficiency of the prepared perovskite solar cell is improved. Compared with the prior art, the invention also relates to the function of the surfactant in emulsifying, solubilizing and suspending in the perovskite solution.
The invention also discloses a preparation method of the mixed solution of the precursor and the surfactant, wherein the precursor is a divalent precursor solution of the perovskite, and the divalent precursor solution comprises a divalent metal halide BX2And a divalent precursor solvent, the preparation method comprises the following steps:
pouring a divalent precursor solution of perovskite with the concentration of 0.5-1.5mol/L into one raw material bottle 109, pouring a surfactant solution with the mass ratio of 0.05-5% to the divalent precursor solution into the other raw material bottle 110, wherein the two raw material bottles are respectively communicated with an injection pump 104 through pipelines 112 and 115, the injection pump 104 simultaneously and respectively pumps the divalent precursor solution and the surfactant solution into a mixing chamber 111 according to the set volume ratio of 1-1000 for mixing, and stirring to obtain a mixed solution of the precursor and the surfactant, wherein,
the divalent metal halide BX2B in (A) is Pb2+、Sn2+、Ze2+At least one of (1), X is Cl-、Br-、I-At least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL); the mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution comprises an active agent solute and an active agent solvent, the active agent solute is a nonionic, cationic, anionic or amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone; the ambient set temperature during stirring was 10-60 ℃.
Polyoxyethylene sorbitan, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan fatty acid methyl ammonium methosulfate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene lauryl ether, polyoxyethylene sorbitan polyoxyethylene lauryl ether, polyoxyethylene sorbitan fatty acid polyoxyethylene lauryl ether, polyoxyethylene sorbitan fatty alcohol polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty alcohol, polyoxyethylene ether, polyoxyethylene sorbitan fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty alcohol ether, polyoxyethylene sorbitan fatty acid polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan fatty alcohol, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene.
Specifically, a hydrophobic substance is added in a certain proportion in advance to the raw material bottle 110 of the surfactant solution to increase the surface leveling effect of the mixed divalent precursor solution. The hydrophobic substance is at least one of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer. The added hydrophobic substance accounts for 0-50% of the mass ratio of the surfactant.
The invention also discloses a use method of the coating equipment of the mixed solution of the precursor and the surfactant, which comprises the following steps:
firstly, pouring a divalent precursor solution and a surfactant solution of perovskite prepared according to the preparation method of the mixed solution of the precursor and the surfactant into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump 104 through pipelines 112 and 115, the injection pump 104 simultaneously and respectively pumps the divalent precursor solution and the surfactant solution according to a set volume ratio of 1-1000, and injects the two solutions into a mixing chamber 111 for mixing, and the mixed solution of the precursor and the surfactant is obtained after stirring.
Secondly, a substrate 108 to be coated is placed on a coating platform 106 with the surface facing upwards, an injection pump 104 and a conveying device 107 are started, the mixed solution is conveyed to the coating die head 101 through a conduit 103, the die head lifting platform 102 and the coating platform 106 are driven by the conveying device 107 to move relatively, the height between the coating die head 101 and the substrate 108 to be coated is adjusted through the die head lifting platform 102, the coating die head 101 coats the surface of the substrate 108 to be coated placed on the coating platform 106, and a wet film containing the mixed solution is obtained after the surface of the substrate 108 is coated.
And thirdly, opening the post-processing device, conveying the coated substrate 108 to the post-processing device 105 by the conveying device 107 for post-processing, and promoting the solvent in the wet film to be further volatilized, thereby preparing a thin film layer containing the divalent precursor on the surface of the substrate 108.
The invention also discloses a preparation method of the perovskite solar cell, and the preparation method uses the coating equipment of the mixed solution of the precursor and the surfactant in the preparation process of the perovskite solar cell, and comprises the following steps:
s1, injecting a divalent precursor and a surfactant solution prepared according to the preparation method of the mixed solution of the precursor and the surfactant into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pump simultaneously and respectively pumps the divalent precursor solution and the surfactant solution into a mixing cavity according to a set volume ratio of 1-1000 for mixing, and stirring to obtain the mixed solution of the precursor and the surfactant.
S2, the substrate 108 with the conductive layer and the electron/hole transport layer already prepared on the surface is placed on the coating platform 106. The injection pump 104 and the conveying device 107 are started, the mixed solution is conveyed to the coating die head 101 through the conduit 103, the die head lifting platform 102 and the coating platform 106 are driven by the conveying device 107 to generate relative movement, the height between the coating die head 101 and the substrate 108 to be coated is adjusted through the die head lifting platform 102, the coating die head 101 coats the surface of the substrate 108 to be coated, which is placed on the coating platform 106, and a wet film containing the mixed solution is obtained after the surface of the substrate 108 is coated.
S3, opening the post-processing device, and transporting the coated substrate 108 to the post-processing device 105 by the transport device 107 for post-processing to promote further evaporation of the solvent in the wet film, thereby preparing a thin film layer containing divalent precursor on the electron/hole transport layer on the substrate surface.
S4, continuously preparing a monovalent precursor thin film layer, a hole/electron transport layer and a back electrode layer of the perovskite on the surface of the thin film layer containing the divalent precursor of the substrate until the perovskite solar cell is prepared.
Specifically, in S2, when the coating die 101 coats, the operating setting parameter conditions of the coating die 101 are: the amount of the coating liquid is 0.2-2ul/cm2The coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 60-180 ℃, and the coating temperature is 60-180 ℃; the coating die head also meets the following environmental conditions when coating: the environment temperature is 15-30 ℃, the environment humidity is 0-50% RH, and the device is in the common atmospheric environment or the environment of inert protective atmosphere.
Specifically, a film forming device (not shown) for performing a film forming process on the wet film just coated on the surface of the substrate within 0 to 60 seconds after the coating of the coating die head is finished is further provided on the die head lifting table. The film forming device comprises a heater, a blower or a suction fan, or a heater and a vacuum pump.
Specifically, the film formation treatment heat treatment or drying treatment. The above-mentionedThe heat treatment means that the substrate coated with the wet film of the divalent precursor is placed at a low vacuum pressure 10-5-105Pa and air temperature of 25-150 ℃, and placing for 10-600s for annealing treatment. The drying treatment refers to rapidly drying the divalent precursor wet film by air convection caused by blowing or air draft, wherein the air speed caused by blowing or air draft is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.
At S4, the post-processing procedure performed by the post-processing device includes: putting the substrate coated with the wet film of the divalent precursor mixed solution in vacuum, dry air, nitrogen and H2At least one gas of O (water), DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), GBL (gamma-butyrolactone) and NMP (N-methylpyrrolidone) acts on the environment, and the environmental pressure is 10-5-106Pa, the ambient temperature is 100-150 ℃, and the standing time is 5-120min, so that the wet film is dried into a semi-dry film.
The invention also discloses a perovskite solar cell which comprises a perovskite thin film layer, wherein the perovskite thin film layer is prepared by adopting the coating equipment of the mixed solution of the precursor and the surfactant, or the perovskite thin film layer is prepared by adopting the preparation method of the perovskite solar cell.
The technical solution of the present invention will be further described with reference to specific embodiments.
Example one
The perovskite thin film layer is prepared by adopting the prior two-step method technology. Firstly, a substrate prepared with a PTAA electron/hole transport layer is coated with 1mol/L PbI by a slit coating mode2The method comprises the following steps of (1) carrying out post-treatment on a coated substrate to obtain a divalent precursor solution containing the perovskite, wherein a divalent precursor solvent in the divalent precursor solution of the perovskite is DMF and DMSO, and the volume ratio of the DMF to the DMSO is 9:12A thin film layer. Then in PbI2And preparing an MAI monovalent precursor thin film layer on the surface of the thin film layer to obtain the perovskite thin film layer.
Wherein, PbI2Slit coating conditions of the divalent precursor solution: the amount of the coating solution was 1ul/cm at a temperature of 25 ℃ and a humidity of 30% RH2The slit width was 100um, and the coating speed was 5 cm/s. Drying conditions after coating: drying with hot air blowing, wherein the wind speed near the substrate surface is 2m/s, the temperature near the substrate surface is 60 deg.C, and the coating contains PbI2The substrate of the thin film layer was annealed at 100 ℃ for 2 min.
As shown in FIG. 5, many white pores are formed in the perovskite thin film layer due to the PbI coating2PbI which is hydrophilic in solution2The solution is difficult to infiltrate the surface of the lipophilic PTAA electron/hole transport layer, PbI2The cohesion of the solution is greater than the adhesion to the surface of the portion in contact with the PTAA electron/hole transport layer, resulting in PbI2The solution has a tendency to "shrink" and create many holes.
Example two
By adopting a two-step process, adding a surfactant into the divalent precursor solution for coating the perovskite, and coating the monovalent precursor solution after coating to obtain the perovskite thin film layer coated cross-sectional schematic diagram shown in fig. 6.
The conductive layer 11 and the electron/hole transport layer 12-2 are sequentially formed on the substrate, and the perovskite thin film layer 16 formed on the electron/hole transport layer 12-2 is coated with a divalent precursor solution of a perovskite containing a surfactant on the electron/hole transport layer 12-2, and the surface active agent 17 is provided on the lower surface of the perovskite thin film layer 16. In the figure, the small dots of the surfactant 17 are hydrophilic groups and the curve is lipophilic groups. The hydrophilic groups are distributed on the side near the perovskite thin film layer 16, while the lipophilic groups are distributed on the lipophilic electron/hole transport layer 12-2 and the air side of the perovskite thin film layer 16. The addition of the surfactant 17 effectively improves the wettability of the perovskite thin film layer 16 on the oleophilic electron/hole transport layer 12-2, improves the flatness of the surface of the perovskite solution in contact with air, and improves the coverage rate of the perovskite thin film on the electron/hole transport layer 12-2 and the uniformity of the film thickness of the thin film.
The embodiment of preparing the perovskite thin film layer by adopting the coating equipment of the mixed solution of the precursor and the surfactant comprises the following steps:
firstly, preparing a mixed solvent of chlorobenzene and dimethylformamide with the volume ratio of 1:2, and adding a surfactant of N-dodecyl ethanolamine with the mass fraction of 10% of 5% of dimethyl silicone oil.
Secondly, preparing a mixed solvent of dimethyl sulfoxide and dimethylformamide with the volume ratio of 1:9 and the molar concentration of PbI of 1.2M2A perovskite divalent precursor solution.
Thirdly, the surfactant solution and PbI2The divalent precursor solution is respectively filled into two raw material bottles. The surfactant solution and the perovskite solution are stirred and mixed uniformly in the mixing cavity 211 according to the volume ratio of 1: 20. The volume ratio can be controlled by the solution injection flow rate of the draw.
Next, the prepared mixed solution was slot-coated on the PTAA electron/hole transport layer substrate using the coating apparatus of the mixed solution of the precursor and the surfactant as described above. Wherein, the slit coating conditions are as follows: the amount of the coating solution was 0.7ul/cm at a temperature of 25 ℃ and a humidity of 30% RH2The slit width was 100um, and the coating speed was 5 cm/s.
Next, the wet film on the substrate after the coating is heated to volatilize the solvent, thereby obtaining a semi-dry film of the thin film layer containing the divalent precursor. Wherein, the film forming processing conditions are as follows: drying by hot air blowing at a wind speed of 2m/s near the surface of the coated substrate and at a temperature of 60 ℃ near the surface of the substrate for 60 seconds. Dry film treatment conditions: coated with PbI2The substrate of the divalent precursor film is placed at 100 ℃ and 10 ℃ under pressure3And (4) annealing for 10min under a dry air environment at Pa.
Referring to fig. 7, it is clearly seen that, compared to the first embodiment, in addition to the existence of a small amount of shrinkage cavities, the coverage rate of the perovskite thin film layer of the present embodiment on the substrate of the oleophilic PTAA electron/hole transport layer is greatly improved, and the outer surface thereof is smoother and smoother.
Referring to FIG. 8, the first embodiment is shownAnd the perovskite thin film layer of the second embodiment is completely prepared into the efficiency graph of the perovskite solar cell in the same mode. The structure of the prepared perovskite solar cell is as follows: ITO/hole transport layer/perovskite layer/C60The effective cell area of the test is 1cm2. The test results show that the cell efficiencies of the first embodiment and the second embodiment are respectively as follows: 6.3 percent and 16.5 percent.
As can be seen from fig. 8, the coverage of the perovskite layer on the electron/hole transport layer substrate is low due to the large number of shrinkage cavities in the perovskite thin film in example one, resulting in poor short circuit current density JSC and fill factor FF of the cell. The existence of the holes may also cause the leakage of electricity of the battery, resulting in poor open-circuit voltage VOC.
The divalent precursor mixed solution is obtained by adding the surfactant into the divalent precursor solution of the perovskite, and in the slit type coating process by utilizing the coating equipment, the surfactant plays a role in leveling the divalent precursor solution of the perovskite, so that the defects of uneven film thickness and holes of the formed perovskite thin film are reduced, and the efficiency of the prepared perovskite solar cell is improved. Compared with the prior art, the invention also relates to the function of the surfactant in emulsifying, solubilizing and suspending in the perovskite solution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (20)
1. The coating equipment of the mixed solution of the precursor and the surfactant is characterized by comprising a coating die head, a die head lifting platform, a coating platform, a conveying device and a post-treatment device, wherein the coating die head is arranged on the die head lifting platform, the coating die head and the post-treatment device are separated from each other and are respectively arranged above the coating platform, a substrate to be coated placed on the coating platform is conveyed to the post-treatment device for post-treatment by the conveying device after being coated by the coating die head, the die head lifting platform and the coating platform are driven by the conveying device to generate relative movement, and the die head lifting platform adjusts the height between the coating die head and the substrate to be coated; the coating die head is communicated with an injection pump with a mixing cavity through a conduit, the mixing cavity of the injection pump is respectively communicated with at least two raw material bottles through pipelines, at least one raw material bottle contains a divalent precursor solution of perovskite, at least one other raw material bottle contains a surfactant solution, the injection pump respectively and simultaneously pumps the divalent precursor solution of perovskite and the surfactant solution according to a set volume ratio, the two raw material bottles and the surfactant solution are injected into the mixing cavity to be mixed, and the mixed solution obtained through mixing is conveyed to the coating die head through the conduit for use.
2. The apparatus and method for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein the conveyor moves a coating platform, the coating die and a die lifting platform are kept stationary, and the die lifting platform and the coating platform move relatively.
3. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein the conveyor moves a coating die and a die lift, the coating platform is kept stationary, and the die lift and the coating platform are moved relatively to each other.
4. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 2 or 3, wherein a film-forming device for forming a film on a wet film on the surface of the substrate immediately after the coating of the coating die is completed within 0 to 60 seconds is further provided on the die lift, and the film-forming device comprises a heater, and a blower or an exhaust fan, or a heater and a vacuum pump.
5. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 2 or 3, wherein the post-treatment means comprises a heater, a vacuum pump, and a closed chamber which is easy to open and close.
6. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein a stirring device or an ultrasonic oscillation device is further provided in the mixing chamber.
7. The preparation method of the mixed solution of the precursor and the surfactant is characterized in that the precursor is a divalent precursor solution of perovskite, and the divalent precursor solution comprises a divalent metal halide BX2And a divalent precursor solvent, the formulation method comprising:
injecting a divalent precursor solution into one raw material bottle, injecting a surfactant solution into the other raw material bottle, respectively communicating the two raw material bottles with an injection pump through pipelines, simultaneously and respectively pumping the divalent precursor solution and the surfactant solution into a mixing cavity by the injection pump according to a set volume ratio for mixing, and stirring to obtain a mixed solution of a precursor and the surfactant, wherein,
the divalent metal halide BX2B in (A) is Pb2+、Sn2+、Ze2+At least one of (1), X is Cl-、Br-、I-The divalent precursor solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and gamma-butyrolactone; the concentration of the divalent precursor solution is 0.5-1.5mol/L, and the mass ratio of the surfactant to the divalent precursor solution is 0.05-5%;
the mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution comprises an active agent solute and an active agent solvent, the active agent solute is a nonionic, cationic, anionic or amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone;
pumping a divalent precursor solution and a surfactant solution at a set volume ratio of 1-1000; the ambient set temperature during stirring was 10-60 ℃.
8. Polyoxyethylene sorbitan, polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene.
9. The method according to claim 7, wherein a hydrophobic substance is added to the raw material bottle of the surfactant in advance in a predetermined proportion, and the hydrophobic substance is at least one of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, and polyether polysiloxane copolymer.
10. Use of a device for coating a mixed solution of a precursor and a surfactant according to any one of claims 1 to 6, characterized in that it comprises the following steps:
firstly, injecting a divalent precursor solution and a surfactant solution of perovskite prepared according to the preparation method of the mixed solution of the precursor and the surfactant as claimed in claim 7, 8 or 9 into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pump simultaneously and respectively pumps the divalent precursor solution and the surfactant solution according to a set volume ratio, the divalent precursor solution and the surfactant solution are injected into a mixing cavity for mixing, and the mixed solution of the precursor and the surfactant is obtained after stirring;
secondly, placing the substrate to be coated on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, driving the die head lifting platform and the coating platform to move relatively, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;
and thirdly, starting the post-treatment device, conveying the coated substrate to the post-treatment device by the conveying device for post-treatment, and preparing a film layer containing a divalent precursor on the surface of the substrate.
11. The method of using a coating apparatus of a mixed solution of a precursor and a surfactant according to claim 10, wherein in the second step, when the coating die is coated, the operating setting parameter conditions of the coating die are as follows: the amount of the coating liquid is 0.2-2ul/cm2The coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 60-180 ℃, and the coating temperature is 60-180 ℃; the coating die head also meets the following environmental conditions when coating: the environment temperature is 15-30 ℃, the environment humidity is 0-50% RH, and the device is in the common atmospheric environment or the environment of inert protective atmosphere.
12. The method of using a coating apparatus for a mixed solution of a precursor and a surfactant according to claim 10, wherein a film-forming device for forming a film on a wet film on a substrate surface immediately after coating of the coating die is completed within 0 to 60 seconds is further provided on the die lift, and the film-forming device includes a heater and a blower or an exhaust fan, or a heater and a vacuum pump.
13. The method of using the apparatus for coating a mixed solution of a precursor and a surfactant according to claim 12, wherein the film forming process comprises a heat treatment of placing the substrate coated with the wet film of the divalent precursor at a low vacuum pressure of 10 or a drying process-5-105Pa, airPlacing at 25-150 deg.C for 10-600s for annealing; the drying treatment refers to rapidly drying the divalent precursor wet film by air convection caused by blowing or air draft, wherein the air speed caused by blowing or air draft is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.
14. The method for using a coating apparatus of a mixed solution of a precursor and a surfactant according to claim 10, wherein in the fourth step, the post-treatment process performed by the post-treatment device includes: placing the substrate coated with the wet film of the mixed solution in an environment under the action of at least one gas selected from vacuum, dry air, nitrogen, water, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone and N-methylpyrrolidone, wherein the environmental pressure is 10-5-106Pa, the ambient temperature is 100-150 ℃, and the standing time is 5-120min, so that the wet film is dried into a semi-dry film.
15. A method for manufacturing a perovskite solar cell, characterized in that a coating apparatus of a mixed solution of a precursor according to any one of claims 1 to 6 and a surfactant is used in the process of manufacturing the perovskite solar cell, comprising the steps of:
s1, pouring a divalent precursor solution of perovskite and a surfactant solution prepared according to the preparation method of the mixed solution of the precursor and the surfactant as claimed in claim 7, 8 or 9 into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pumps simultaneously and respectively pump the divalent precursor solution of calcium and the surfactant solution according to a set volume ratio and inject the divalent precursor solution of calcium and the surfactant solution into a mixing cavity for mixing, and stirring to obtain a mixed solution of the precursor and the surfactant;
s2, placing the substrate with the conductive layer and the electron/hole transport layer prepared on the surface on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, generating relative movement between the die head lifting platform and the coating platform under the driving of the conveying device, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;
s3, starting the post-processing device, conveying the coated substrate to the post-processing device by the conveying device for post-processing, and preparing a film layer containing a divalent precursor on the electron/hole transport layer on the surface of the substrate;
s4, continuously preparing a monovalent precursor thin film layer, a hole/electron transport layer and a back electrode layer of the perovskite on the surface of the thin film layer containing the divalent precursor of the substrate until the perovskite solar cell is prepared.
16. The method for producing a perovskite solar cell as claimed in claim 15, wherein in S2, the coating die is coated under the conditions of the operating parameters of the coating die: the amount of the coating liquid is 0.2-2ul/cm2The coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 60-180 ℃, and the coating temperature is 60-180 ℃; the coating die head also meets the following environmental conditions when coating: the environment temperature is 15-30 ℃, the environment humidity is 0-50% RH, and the device is in the common atmospheric environment or the environment of inert protective atmosphere.
17. The method for producing a perovskite solar cell as claimed in claim 15, wherein a film forming device for performing a film forming process on a wet film on the surface of the substrate just before coating within a time of 0 to 60 seconds after the coating of the coating die is completed is further provided on the die lift, and the film forming device comprises a heater and a blower or a suction fan, or a heater and a vacuum pump.
18. The method for producing the perovskite solar cell as claimed in claim 17, wherein the film forming process comprises a heat treatment of placing the substrate coated with the wet film of the divalent precursor at a low vacuum pressure of 10 a or a drying process-5-105Pa, air temperature 25-150 deg.CThen, the mixture is placed for 10 to 600 seconds to carry out annealing treatment; the drying treatment refers to rapidly drying the divalent precursor wet film by air convection caused by blowing or air draft, wherein the air speed caused by blowing or air draft is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.
19. The method for producing a perovskite solar cell as claimed in claim 15, wherein in S4, the post-treatment process performed by the post-treatment apparatus comprises: placing the substrate coated with the wet film of the mixed solution in an environment under the action of at least one gas selected from vacuum, dry air, nitrogen, water, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone and N-methylpyrrolidone, wherein the environmental pressure is 10-5-106Pa, the ambient temperature is 100-150 ℃, and the standing time is 5-120min, so that the wet film is dried into a semi-dry film.
20. A perovskite solar cell comprising a perovskite thin film layer, characterized in that the perovskite thin film layer is produced using the coating apparatus of the mixed solution of the precursor and the surfactant according to any one of claims 1 to 6, or the use method of the coating apparatus of the mixed solution of the precursor and the surfactant according to any one of claims 10 to 14, or the production method of the perovskite solar cell according to any one of claims 15 to 19.
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