WO2018219152A1

WO2018219152A1 - Perovskite thin film coating apparatus, using method, and application

Info

Publication number: WO2018219152A1
Application number: PCT/CN2018/087346
Authority: WO
Inventors: 姚冀众; 颜步一
Original assignee: 杭州纤纳光电科技有限公司
Priority date: 2017-06-02
Filing date: 2018-05-17
Publication date: 2018-12-06
Also published as: CN108970913A; CN108970913B

Abstract

A perovskite thin film coating apparatus, comprising a conveying device for conveying a substrate (2), a perovskite solution coating device, an anti-solvent spray coating device, and an air drying device or heat drying device (6). The perovskite solution coating device is provided with a perovskite coating head (3). The anti-solvent spray coating device is provided with an anti-solvent spray coating mouth (4). The substrate (2) is carried by the conveying device to sequentially pass by the perovskite solution coating device, the anti-solvent spray coating device, and the air drying device or heat drying device (6); wind from an air outlet (5) simultaneously dries a perovskite solution and an anti-solvent on the surface of the substrate (2) by means of evaporation to form a perovskite thin film. Also provided are a using method for and an application of the coating apparatus. By improving the existing apparatuses of a one-step solution method and a two-step solution method, using methods and applications, and performing air drying or infrared heat drying on a substrate spray-coated or coated with a perovskite solution, the present invention improves the film forming quality while ensuring low production cost, and is suitable for large-scale production of perovskite thin films of substrates.

Description

Perovskite film coating device and using method and application thereof

Technical field

The invention belongs to the technical field of solar cells, and particularly relates to a perovskite film coating device and a using method and application thereof.

Background technique

In recent years, perovskite solar cells have received extensive attention, and various methods and apparatuses for preparing perovskite films are available. At present, a common method for preparing a perovskite film is a one-step solution method, a two-step solution method, a gas phase assisted solution method, and co-evaporation deposition. Among them, the co-evaporation deposition and the gas phase auxiliary solution method are costly due to the vacuum equipment, which is not conducive to large-scale production and cost reduction.

The conventional one-step solution process is to first arrange the perovskite solution, and then take a certain amount of solution for spin coating. Finally, the spin-coated perovskite wet film is subjected to high temperature annealing to form a perovskite film. Although this method is convenient, fast, and inexpensive, the film produced by this method is not dense enough and it is difficult to scale production.

In the two-step solution method, the first step is to deposit a layer of perovskite film with a solution. The quality of the pre-formed film directly determines the quality of the perovskite film obtained in the subsequent process. The film obtained by the conventional perovskite film pre-layer coating process is uneven, not dense, and has many defects. The specific thickness of the film is uneven in various places, the surface of the film has many pinholes, the roughness is large, and the repeatability between batches is poor. Wait. Moreover, in the existing two-step solution method, there is a problem that the prepreg layer cannot be quickly and uniformly dried and the liquid convection is easily affected during the drying process, and the film produced by this method is also difficult to be produced on a large scale.

Summary of the invention

The technical problem to be solved by the present invention is to provide a perovskite film coating device, a use method and application thereof, an improved perovskite film coating device and a process, and a novel perovskite film coating device and process, Make up for its shortcomings. In this way, under the premise of ensuring low production cost, the film forming quality is improved, the scale production process is improved, and the film forming efficiency of the perovskite is greatly improved.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for conveying a substrate, a perovskite solution coating device, an anti-solvent spraying device, and an air drying device or a heating and drying device, the substrate A bottom electrode layer is prepared in advance, the transfer device is provided with a conveyor belt or a transfer shaft, and the perovskite solution coating device is provided with a coating head, which is a perovskite coating head, the anti-solvent The spraying device is provided with a spraying nozzle, the spraying nozzle is an anti-solvent spraying nozzle, the air drying device is provided with an air outlet, the heating drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft Driving the perovskite solution coating device, the anti-solvent spraying device, and the air drying device or the heating and drying device, wherein the perovskite coating head coats the perovskite solution on the surface of the substrate, the anti-solvent spraying nozzle Spraying an anti-solvent on the surface of the substrate, the wind of the air outlet simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the heating and drying device The infrared heaters are simultaneously heated from the upper and lower sides of the substrate, respectively, and the perovskite solution and the anti-solvent on the surface thereof are evaporated together to form a perovskite film.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for conveying a substrate, a perovskite solution spraying device, an anti-solvent coating device, and an air drying device or a heating drying device, the substrate A bottom electrode layer is prepared in advance, the conveying device is provided with a conveyor belt or a conveying shaft, the perovskite solution spraying device is provided with a spray nozzle, the spray nozzle is a perovskite spray nozzle, and the anti-solvent coating device is provided There is a coating head which is an anti-solvent coating head, the air drying device is provided with an air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft Driving the perovskite solution spraying device, the anti-solvent coating device, and the air drying device or the heating and drying device, wherein the perovskite spray nozzle sprays the perovskite solution on the surface of the substrate, and the anti-solvent coating head will The anti-solvent is coated on the surface of the substrate, and the wind at the air outlet simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the heating and drying device Outside the heater from both upper and lower substrates, respectively, while heating it together with the solution was evaporated to dryness which on the surface of a perovskite and perovskite antisolvent to form a thin film.

The above two perovskite film coating apparatuses of the present invention are all improved by the existing one-step solution method, and the substrate sprayed or coated with the perovskite solution is subjected to wind blowing or infrared heating drying to ensure low At the same time of production cost, the film-forming quality is improved, and the perovskite film of the substrate is suitable for large-scale production.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for conveying a substrate, a precursor solution coating device, an activation layer spraying device, and an air drying device or a heating drying device, wherein the substrate is advanced A bottom electrode layer is prepared, the transfer device is provided with a conveyor belt or a transfer shaft, the precursor solution coating device is provided with a coating head, the coating head is a precursor coating head, and the activation layer spraying device is provided There is a spray nozzle, the spray nozzle is an activation spray nozzle, the air drying device is provided with an air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the transmission shaft and driven by the precursor a body solution coating device, an activation layer coating device, and an air drying device or a heating and drying device, the precursor coating head coating a precursor solution on a surface of the substrate, the activated spray nozzle spraying the activation solution on the surface of the substrate Above, the wind of the air outlet simultaneously volatilizes the precursor solution and the activation solution on the surface of the substrate to form a perovskite film, and the heating and drying device Outside the heater from both upper and lower substrates, respectively, while heating it to its evaporation was dried with precursor solution and activation solution on the surface and form a thin film of perovskite.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying substrate conveying device, a precursor solution coating device, an activation layer coating device, an anti-solvent spraying device, and an air drying device or a heating drying device. The substrate is prepared in advance with a bottom electrode layer, the transfer device is provided with a conveyor belt or a transfer shaft, the precursor solution coating device is provided with a coating head, and the coating head is a precursor coating head. The activation layer coating device is provided with a coating head, the coating head is an activated coating head, the anti-solvent spraying device is provided with a spraying nozzle, and the spraying nozzle is an anti-solvent spraying nozzle, and the air drying device is provided with An air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer coating device, the anti-solvent spraying device and the air drying device. Or heating the drying device, the precursor coating head coating a precursor solution on the surface of the substrate, the activated coating head coating the activation solution on the surface of the substrate, the The solvent spraying nozzle sprays the anti-solvent on the surface of the substrate, and the wind of the air outlet simultaneously volatilizes and dryes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the heating and drying device The infrared heater is simultaneously heated from the upper and lower sides of the substrate to evaporate and dry the precursor solution, the activation solution and the anti-solvent on the surface thereof to form a perovskite film.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying substrate conveying device, a precursor solution coating device, an activation layer spraying device, an anti-solvent coating device, and an air drying device or a heating drying device. The substrate is prepared in advance with a bottom electrode layer, the transfer device is provided with a conveyor belt or a transfer shaft, the precursor solution coating device is provided with a coating head, and the coating head is a precursor coating head. The anti-solvent coating device is provided with a coating head, the coating head is an anti-solvent coating head, the activation layer spraying device is provided with a spray nozzle, and the spray nozzle is an activated spray nozzle, and the air drying device is provided with An air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer spraying device, the anti-solvent coating device and the air drying device. Or heating the drying device, the precursor coating head coating a precursor solution on the surface of the substrate, the activated spray nozzle spraying the activation solution on the surface of the substrate, the reverse The coating head coats the anti-solvent on the surface of the substrate, and the wind at the air outlet simultaneously volatilizes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate to form a perovskite film, which is dried by heating. The infrared heater of the device is simultaneously heated from the upper and lower sides of the substrate to evaporate and dry the precursor solution, the activation solution and the anti-solvent on the surface thereof to form a perovskite film.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for transporting a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer spraying device, and a rear section air drying a device or a post-stage heating and drying device, the substrate is prepared with a bottom electrode layer in advance, the transfer device is provided with a conveyor belt or a transfer shaft, and the precursor solution coating device is provided with a coating head, and the coating head is a precursor coating head, the front air drying device is provided with a front air outlet, the front heating drying device is provided with an infrared heater, the active layer spraying device is provided with a spray nozzle, and the spray nozzle is an activated spray nozzle. The rear air drying device is provided with a rear air outlet, and the rear heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft, and then driven by the precursor solution coating device, and the front portion is air-dried. a device or a front heating drying device, an activation layer spraying device, and a rear air drying device or a rear heating drying device, the precursor coating head The body solution is coated on the surface of the substrate, and the activated spray nozzle sprays the activation solution on the surface of the substrate, and the wind of the front portion of the air outlet volatilizes the precursor solution on the surface of the substrate to form a precursor film. The infrared heater of the front-stage heating and drying device heats the precursor solution on the upper and lower sides of the substrate, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind of the rear air outlet is on the surface of the substrate. The activation solution is volatilized to dry and form a perovskite film, and the infrared heater of the subsequent stage heating and drying device heats the activation solution on the surface from both the upper and lower sides of the substrate to evaporate and form a perovskite film.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for conveying a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer coating device, an anti-solvent a spraying device and a rear air drying device or a rear heating drying device, wherein the substrate is prepared with a bottom electrode layer, the conveying device is provided with a conveyor belt or a conveying shaft, and the precursor solution coating device is provided with a coating head. The coating head is a precursor coating head, the front air drying device is provided with a front air outlet, the front heating drying device is provided with an infrared heater, and the activation layer coating device is provided with a coating head, The coating head is an activated coating head, the anti-solvent spraying device is provided with a spraying nozzle, the spraying nozzle is an anti-solvent spraying nozzle, the rear air drying device is provided with a rear air outlet, and the rear heating drying device An infrared heater is disposed, and the substrate is placed on the conveyor belt or the conveying shaft, and is driven by the precursor solution coating device, the front air drying device or the front portion to be dried. a device, an activation layer coating device, an anti-solvent spraying device, and a rear air drying device or a rear heating drying device, the precursor coating head coating a precursor solution on a surface of the substrate, the activated coating head The activation solution is coated on the surface of the substrate, and the anti-solvent spray nozzle sprays the anti-solvent on the surface of the substrate, and the wind at the outlet of the front section volatilizes the precursor solution on the surface of the substrate to form a precursor film. The infrared heater of the front-stage heating and drying device heats the precursor solution on the upper and lower sides of the substrate, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind of the rear air outlet is on the surface of the substrate. The activation solution and the anti-solvent simultaneously volatilize and dry to form a perovskite film, and the infrared heater of the latter heating and drying device simultaneously heats the upper and lower sides of the substrate to evaporate the activation solution and the anti-solvent on the surface thereof. Dry and form a perovskite film.

The present invention is achieved by providing a perovskite film coating apparatus comprising a conveying device for conveying a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer spraying device, and an anti-solvent coating. a cloth device and a rear air drying device or a rear heating drying device, wherein the substrate is prepared with a bottom electrode layer, the conveying device is provided with a conveyor belt or a conveying shaft, and the precursor solution coating device is provided with a coating head. The coating head is a precursor coating head, the anti-solvent coating device is provided with a coating head, the coating head is an anti-solvent coating head, and the front air drying device is provided with a front air outlet, The front heating drying device is provided with an infrared heater, the activation layer spraying device is provided with a spraying nozzle, the spraying nozzle is an activated spraying nozzle, the rear air drying device is provided with a rear air outlet, and the rear heating drying device An infrared heater is disposed, and the substrate is placed on the conveyor belt or the conveying shaft, and is driven by the precursor solution coating device, the front air drying device or the front portion to be dried. a device, an active layer spraying device, an anti-solvent coating device, and a rear air drying device or a rear heating drying device, the precursor coating head coating a precursor solution on the surface of the substrate, the activated spray nozzle will be activated The solution is sprayed on the surface of the substrate, and the anti-solvent coating head coats the anti-solvent on the surface of the substrate, and the wind of the front portion of the air outlet volatilizes the precursor solution on the surface of the substrate to form a precursor film. The infrared heater of the front-stage heating and drying device heats the precursor solution on the upper and lower sides of the substrate, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind of the rear air outlet is on the surface of the substrate. The activation solution and the anti-solvent simultaneously volatilize and dry to form a perovskite film, and the infrared heater of the latter heating and drying device simultaneously heats the upper and lower sides of the substrate to evaporate the activation solution and the anti-solvent on the surface thereof. Dry and form a perovskite film.

The above six perovskite film coating apparatuses of the present invention are all improved by the existing two-step solution method, and the substrate sprayed or coated with the perovskite solution is subjected to wind blowing or infrared heating to dry the base. The airflow on the surface of the sheet is controlled, the drying speed of the precursor film is accelerated, the precursor film is more uniform and dense, and the film forming quality is improved while ensuring low production cost, and the perovskite film suitable for the substrate is large. Large-scale production.

The present invention is achieved by providing a method of using a perovskite film coating apparatus comprising the following steps:

A1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

A2. The substrate is sequentially passed through a perovskite solution coating device, and the perovskite coating head coats the perovskite solution on the surface of the substrate, and the anti-solvent spraying device sprays the anti-solvent on the substrate through an anti-solvent spraying device. On the surface of the sheet, the perovskite solution and the anti-solvent are quickly volatilized or evaporated by an air drying device or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

A3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

A4. The substrate is sequentially passed through a perovskite solution spraying device, and the perovskite spray nozzle sprays the perovskite solution on the surface of the substrate, and the anti-solvent coating head coats the anti-solvent on the substrate through an anti-solvent coating device. On the surface of the sheet, the perovskite solution and the anti-solvent are quickly volatilized or evaporated by an air drying device or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

The method for using the above two perovskite film coating apparatuses of the present invention is to improve the existing one-step solution method, and the substrate sprayed or coated with the perovskite solution is subjected to wind blowing or infrared heating drying. While ensuring low production cost and improving film formation quality, it is suitable for large-scale large-scale production of perovskite film of substrate.

B1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B2. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation spray coating device activates the spray nozzle to spray the activation solution on the surface of the substrate. The precursor solution and the activation solution are quickly volatilized or evaporated by an air outlet or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

B3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B4. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation coating solution is applied to the substrate by the activation layer coating device. On the surface, the anti-solvent spraying device sprays the anti-solvent on the surface of the substrate through an anti-solvent spraying device, and the precursor solution, the activation solution and the anti-solvent are quickly volatilized together by an air drying device or a heating and drying device, an air outlet or an infrared heater. Or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

B6. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B7. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation spray coating device activates the spray nozzle to spray the activation solution on the surface of the substrate. Through the anti-solvent coating device, the anti-solvent coating head coats the anti-solvent on the surface of the substrate, and the precursor solution, the activation solution and the anti-solvent are quickly volatilized together by an air drying device or a heating and drying device, an air outlet or an infrared heater. Or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

C1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the anti-solvent coating device conveying device;

C2. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is quickly volatilized or evaporated, and the activation solution is sprayed on the surface of the substrate by the activation layer spraying device, and the activation solution is quickly sprayed through the rear air drying device or the rear heating drying device, and the rear air outlet or the infrared heater is used to quickly activate the solution. Volatilization or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.

C3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

C4. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is rapidly volatilized or evaporated. The activation coating solution is applied to the surface of the substrate by an activation layer coating device. The anti-solvent spraying device sprays the anti-solvent on the surface of the substrate through an anti-solvent spraying device. The rear air drying device or the rear heating drying device, the rear air outlet or the infrared heater rapidly volatilizes or evaporates the activation solution together with the anti-solvent, and finally obtains a substrate with a perovskite film attached to the surface and stores it.

C5. placing the substrate to which the bottom electrode layer is attached on the conveyor belt or the conveying shaft of the conveying device;

C6. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is rapidly volatilized or evaporated, and the activation solution is sprayed on the surface of the substrate by the activation layer spraying device, and the anti-solvent coating head is used to coat the anti-solvent on the surface of the substrate through the anti-solvent coating device. The rear air drying device or the rear heating drying device, the rear air outlet or the infrared heater rapidly volatilizes or evaporates the activation solution together with the anti-solvent, and finally obtains a substrate with a perovskite film attached to the surface and stores it.

The above six perovskite film coating apparatuses of the present invention are all used to improve the existing two-step solution method, and the substrate sprayed or coated with the perovskite solution is subjected to wind blowing or infrared heating and drying. The airflow on the surface of the substrate is controlled, the drying speed of the precursor film is accelerated, the precursor film is more uniform and dense, and the film forming quality is improved while ensuring low production cost, and the substrate is suitable for perovskite. Large-scale production of large-scale film.

The present invention is achieved by providing an application of a perovskite film coating apparatus which can also be used for coating a solution containing at least one of the following materials:

Vanadium pentoxide (V ₂ O ₅ ), tungsten oxide (WO ₃ ), molybdenum oxide (MoOx), copper sulfide (CuS), cuprous thiocyanate (CuSCN), copper oxide (CuO), cuprous iodide ( CuI), cuprous oxide (Cu ₂ O), iron disulfide (FeS ₂ ), CDO ₂ type copper-iron semiconductor, lead sulfide (PbS), cobalt oxide (CoOx), cobalt sulfide (CoS), magnesium-doped and lithium-doped Nickel oxide (NiMgLiO), nickel oxide (NiOx), polyethylene dioxythiophene-poly(styrene sulfonate) and its highly conductive derivative (PEDOT:PSS), poly[bis(4-phenyl)( 2,4,6-trimethylphenyl)amine] (poly-triaryamine, PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino] -9,9'-Spiro-OMeTAD, 3-hexyl-substituted polythiophene (P3HT), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), cadmium selenide (CdSe), bismuth sulfide (Bi ₂ S _3), indium sulfide (In ₂ S _3), indium oxide (In ₂ O _3), antimony sulfide (Sb ₂ S _3), two Molybdenum sulfide (MoS ₂ ), selenium disulfide (SnS ₂ ), tin oxide (SnO ₂ ), PCBM, aluminum-doped zinc oxide (AZO), cerium oxide (CeOx), cerium oxide (NbOx), barium titanate (BaTiO _{3 )} ), fullerenes (C60, C70), zinc-doped cadmium sulfide (Zn _1-x Cd) _x S), chromium oxide (CrOx), copper-doped chromium oxide (Cu _x Cr _y O ₂ ),

Among them, C=Cu or Ag in the CDO type ₂ copper-iron semiconductor, and D= one or more of Cr, Ga, Al, Sc, In, Y, and Fe.

The present invention is achieved by providing an application of a method of using a perovskite film coating apparatus which can also be used for coating a solution containing at least one of the following materials:

Vanadium pentoxide (V ₂ O ₅ ), tungsten oxide (WO ₃ ), molybdenum oxide (MoOx), copper sulfide (CuS), cuprous thiocyanate (CuSCN), copper oxide (CuO), cuprous iodide ( CuI), cuprous oxide (Cu ₂ O), iron disulfide (FeS ₂ ), CDO ₂ type copper-iron semiconductor, lead sulfide (PbS), cobalt oxide (CoOx), cobalt sulfide (CoS), magnesium-doped and lithium-doped Nickel oxide (NiMgLiO), nickel oxide (NiOx), polyethylene dioxythiophene-poly(styrene sulfonate) and its highly conductive derivative (PEDOT:PSS), poly[bis(4-phenyl)( 2,4,6-trimethylphenyl)amine] (poly-triaryamine, PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino] -9,9'-Spiro-OMeTAD, 3-hexyl-substituted polythiophene (P3HT), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), cadmium selenide (CdSe), bismuth sulfide (Bi ₂ S _3), indium sulfide (In ₂ S _3), indium oxide (In ₂ O _3), antimony sulfide (Sb ₂ S _3), two Molybdenum sulfide (MoS ₂ ), selenium disulfide (SnS ₂ ), tin oxide (SnO ₂ ), PCBM, aluminum-doped zinc oxide (AZO), cerium oxide (CeOx), cerium oxide (NbOx), barium titanate (BaTiO _{3 )} ), fullerenes (C60, C70), zinc-doped cadmium sulfide (Zn _1-x C d _x S), chromium oxide (CrOx), copper-doped chromium oxide (Cu _x Cr _y O ₂ ),

Compared with the prior art, the perovskite film coating device and the using method and application of the invention adopt the novel coating equipment and the process to make up for the deficiency of the one-step method, and improve the formation under the premise of ensuring low production cost. Membrane quality and scale production process.

DRAWINGS

1 is a schematic perspective view of a first preferred embodiment of a perovskite film coating apparatus of the present invention;

Figure 2 is a perspective view showing a second preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 3 is a perspective view showing a third preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 4 is a perspective view showing a fourth preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 5 is a perspective view showing a fifth preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 6 is a perspective view showing a sixth preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 7 is a perspective view showing a seventh preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 8 is a perspective view showing the eighth preferred embodiment of the perovskite film coating apparatus of the present invention;

Figure 9 is an SEM image of a perovskite film obtained by using the method of using the perovskite film coating apparatus of the present invention;

Figure 10 is a J-V graph of a perovskite thin film solar cell module obtained by using the method of using the perovskite film coating apparatus of the present invention;

Figure 11 is a schematic perspective view showing the undulation of the surface of the PbI ₂ film prepared by the step meter without the air drying device and the air drying device;

Figure 12 is a schematic view showing the comparison of the thickness of the PbI ₂ film prepared in the absence of an air drying device and an air drying device;

Figure 13 is a SEM image of a perovskite film obtained by using the perovskite film coating apparatus of the present invention without opening the anti-solvent coating and drying;

Fig. 14 is a SEM image of a perovskite film obtained by using an anti-solvent coating and drying method using the perovskite film coating apparatus of the present invention.

detailed description

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Referring to FIG. 1, a first preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a perovskite solution coating device, an anti-solvent spraying device, and an air drying device. As another example, the air drying device can be replaced with a heated drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The perovskite solution coating device is provided with a coating head, the coating head is a perovskite coating head 3, the anti-solvent spraying device is provided with a spray nozzle, and the spray nozzle is an anti-solvent spray nozzle 4 The air drying device is provided with an air outlet 5. The heating and drying device is provided with an infrared heater (not shown).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the perovskite solution coating device, the anti-solvent spraying device, and the air drying device or the heating drying device. The perovskite coating head 3 coats a perovskite solution on the surface of the substrate 2, and the anti-solvent spray nozzle 4 sprays an anti-solvent on the surface of the substrate 2. The wind of the air outlet 5 simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heaters of the heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, and the perovskite solution on the surface thereof and the anti-solvent are evaporated together to form a perovskite film.

The perovskite solution is a mixture of BX ₂ , AX, a primary solvent, a solvent additive, and/or an organic polymer additive. Among them, B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, At least one cation of lanthanum, cerium and lanthanum. X is at least one anion of iodine (I), bromine (Br), chlorine (Cl), or acetate (CH ₃ COO). A is at least one cation of an anthracene, an anthracene, an amine group, a fluorenyl group or an alkali group. The main solvent includes at least one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent. The solvent additive is at least one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon. The organic polymer additive is polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, polylactic acid, polyvinyl alcohol, polyacrylic acid, polyurethane, polyethyleneimine, polypropylene thiamine, polystyrene sulfonic acid, polyvinylpyrrolidone. At least one of a polyvinyl butyral resin and a fluorine-based polymer. The anti-solvent is at least one of a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent, and has a molecular weight ranging from 200 to 100,000.

Wherein the solution concentration of the BX ₂ is 0.2-5 mol/L, the molar ratio of the AX to BX ₂ is 0.1-10, and the molar concentration of the BX ₂ in the main solvent is 0.2-2 mol/L. The molar ratio of the solvent additive to BX ₂ is from 0 to 1, and the molar ratio of the organic polymer additive to BX ₂ is from 0.05 to 5.

Referring to FIG. 2, a second preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a perovskite solution spraying device, an anti-solvent coating device and a heating and drying device. 6. As another embodiment, the heat drying device 6 can be replaced with an air drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The perovskite solution spraying device is provided with a spray nozzle, the spray nozzle is a perovskite spray nozzle 3', the anti-solvent coating device is provided with a coating head, and the coating head is an anti-solvent coating head 4', the heating and drying device is provided with an infrared heater 6. The air drying device is provided with an air outlet (not shown).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the perovskite solution spraying device, the anti-solvent coating device, and the air drying device or the heating drying device. The perovskite spray nozzle 3' sprays a perovskite solution on the surface of the substrate 2, and the anti-solvent coating head 4' coats the anti-solvent on the surface of the substrate 2. The wind at the air outlet simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heaters 6 of the heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, and the perovskite solution and the anti-solvent on the surface thereof are evaporated together to form a perovskite film.

Others are the same as the first embodiment and will not be described again.

Referring to FIG. 3, a third preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, an activation layer spraying device, and an air drying device. As another example, the air drying device can be replaced with a heated drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, the coating head is a precursor coating head 7, the activation layer spraying device is provided with a spray nozzle, and the spray nozzle is an activation spray nozzle 8, The air drying device is provided with an air outlet 5. The heating and drying device is provided with an infrared heater (not shown).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer spraying device, and the air drying device or the heating drying device. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, and the activated spray nozzle 8 sprays the activation solution on the surface of the substrate 2. The wind of the air outlet 5 simultaneously volatilizes the precursor solution and the activation solution on the surface of the substrate 2 to form a perovskite film. The infrared heaters of the heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, and the precursor solution and the activation solution on the surface thereof are evaporated together to form a perovskite film.

The precursor solution includes a BX ₂ solute, a main solvent, and a solvent additive, and the activation solution includes an AX solute, a main solvent, and an organic polymer additive. Among them, B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, At least one cation of lanthanum, cerium and lanthanum. X is at least one anion of iodine (I), bromine (Br), chlorine (Cl), or acetate (CH ₃ COO). A is at least one cation of an anthracene, an anthracene, an amine group, a fluorenyl group or an alkali group. The main solvent includes at least one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent. The solvent additive is at least one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The polymer additives are polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, polylactic acid, polyvinyl alcohol, polyacrylic acid, polyurethane, polyethyleneimine, polypropylene thiamine, polystyrene sulfonic acid, polyvinylpyrrolidone, polyethylene. At least one of an butyral resin and a fluorine-based polymer. The anti-solvent is at least one of a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent, and has a molecular weight ranging from 200 to 100,000.

Wherein, the solution concentration of the BX ₂ is 0.2-5 mol/L, the solution concentration of the AX is 0.1 mg/ml to 100 mg/ml, and the molar concentration of the BX ₂ in the main solvent is 0.2 to 2 mol/L. The molar ratio of the solvent additive to BX ₂ is 0 to 1, and the volume ratio of the organic polymer additive to the AX main solvent is 0 to 1.

Referring to FIG. 4, a fourth preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, an activation layer coating device, and an anti-solvent spraying. Device and air drying device. As another example, the air drying device can be replaced with a heated drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, which is a precursor coating head 7, and the activation layer coating device is provided with a coating head, which is an activated coating head 8', the anti-solvent spraying device is provided with a spray nozzle, and the spray nozzle is an anti-solvent spray nozzle 4, and the air dryer is provided with an air outlet 5. The heating and drying device is provided with an infrared heater (not shown).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer coating device, the anti-solvent spraying device, and the air drying device or the heating drying device. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, and the activated coating head 8' coats the activation solution on the surface of the substrate 2, and the anti-solvent spraying nozzle 4 will be reversed. The solvent is sprayed onto the surface of the substrate. The wind of the air outlet 5 simultaneously volatilizes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heater of the heating and drying device is simultaneously heated from the upper and lower sides of the substrate 2 to evaporate and dry the precursor solution, the activation solution and the anti-solvent on the surface thereof to form a perovskite film.

Others are the same as the third embodiment and will not be described again.

Referring to FIG. 5, a fifth preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, an activation layer spraying device, and an anti-solvent coating. Device and air drying device. As another example, the air drying device can be replaced with a heated drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, which is a precursor coating head 7, and the anti-solvent coating device is provided with a coating head, which is an anti-solvent coating The head 4', the activation layer spraying device is provided with a spray nozzle, the spray nozzle is an activation spray nozzle 8, the air dryer is provided with an air outlet 5, and the heating and drying device is provided with an infrared heater (not shown) Out).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer spraying device, the anti-solvent coating device, and the air drying device or the heating drying device. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, the activated spray nozzle 8 sprays an activation solution on the surface of the substrate, and the anti-solvent coating head 4' coats the anti-solvent The cloth is placed on the surface of the substrate 2. The wind of the air outlet 5 simultaneously volatilizes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heater of the heating and drying device is simultaneously heated from the upper and lower sides of the substrate 2 to evaporate and dry the precursor solution, the activation solution and the anti-solvent on the surface thereof to form a perovskite film.

Others are the same as the third embodiment and will not be described again.

Referring to FIG. 6, a sixth preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, a front air drying device, an activation layer spraying device, and Rear air drying device. As another embodiment, the front air drying device may be replaced by a front heating drying device, and the rear air drying device may be replaced with a rear heating drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, the coating head is a precursor coating head 7, the front air drying device is provided with a front air outlet 9, and the front heating drying device is provided with an infrared heater (not shown in the figure), the activation layer spraying device is provided with a spray nozzle, the spray nozzle is an activation spray nozzle 8, the rear air drying device is provided with a rear air outlet 10, and the rear heating drying device An infrared heater (not shown) is provided.

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft to be sequentially driven by the precursor solution coating device, the front air drying device or the front heating drying device, the activation layer spraying device and the rear air drying device or the rear heating drying device. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, and the activated spray nozzle 8 sprays the activation solution on the surface of the substrate 2. The wind of the front air outlet 9 volatilizes the precursor solution on the surface of the substrate 2 to form a precursor film. The infrared heaters of the front stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film. The wind of the rear air outlet 10 volatilizes the activation solution on the surface of the substrate 2 to form a perovskite film. The infrared heaters of the rear stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, to evaporate and dry the activated solution on the surface thereof to form a perovskite film.

Others are the same as the third embodiment and will not be described again.

Referring to FIG. 7, a seventh preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, a front air drying device, and an activation layer coating device. , anti-solvent spraying device and rear air drying device. As another embodiment, the front air drying device may be replaced by a front heating drying device, and the rear air drying device may be replaced with a rear heating drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, the coating head is a precursor coating head 7, the front air drying device is provided with a front air outlet 9, and the front heating drying device is provided with an infrared heater (not shown in the drawings), the activation layer coating device is provided with a coating head, the coating head is an activated coating head 8', and the anti-solvent spraying device is provided with a spray nozzle, and the spray nozzle is Anti-solvent spray nozzle 4. The rear air drying device is provided with a rear air outlet 10, and the rear heating drying device is provided with an infrared heater (not shown).

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft, and is sequentially driven by the precursor solution coating device, the front air drying device or the front heating drying device, the activation layer coating device, the anti-solvent spraying device and the rear air drying device or The latter section is heated and dried. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, and the activated coating head 8' coats the activation solution on the surface of the substrate 2, and the anti-solvent spraying nozzle 4 will be reversed. The solvent is sprayed on the surface of the substrate 2. The wind of the front air outlet 9 volatilizes the precursor solution on the surface of the substrate 2 to form a precursor film. The infrared heaters of the front stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film. The wind of the rear air outlet 10 simultaneously volatilizes the activation solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heaters of the rear stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, and the activation solution and the anti-solvent on the surface thereof are evaporated together to form a perovskite film.

Others are the same as the third embodiment and will not be described again.

Referring to FIG. 8, an eighth preferred embodiment of the perovskite film coating apparatus of the present invention comprises a conveying device for conveying the substrate 2, a precursor solution coating device, a front heating drying device, and an activation layer spraying device. , an anti-solvent coating device and a rear heating drying device. As another embodiment, the front stage heating and drying device may be replaced by a front air drying device, and the rear stage heating and drying device may also be replaced with a rear air drying device.

The substrate 2 is previously prepared with a bottom electrode layer, and the transfer device is provided with a conveyor belt 1 or a conveying shaft (not shown). The precursor solution coating device is provided with a coating head, which is a precursor coating head 7, and the anti-solvent coating device is provided with a coating head, which is an anti-solvent coating Head 4'. The front air drying device is provided with a front air outlet (not shown), and the front heating and drying device is provided with an infrared heater 11. The activation layer spraying device is provided with a spray nozzle, which is an activated spray nozzle 8. The rear air drying device is provided with a rear air outlet (not shown), and the rear heating drying device is provided with an infrared heater 12.

The substrate 2 is placed on the conveyor belt 1 or the conveying shaft, and is sequentially driven by the precursor solution coating device, the front air drying device or the front heating drying device, the activation layer spraying device, the anti-solvent coating device and the rear air drying device or The latter section is heated and dried. The precursor coating head 7 coats a precursor solution on the surface of the substrate 2, and the activated spray nozzle 8 sprays an activation solution on the surface of the substrate 2, and the anti-solvent coating head 4' will have an anti-solvent It is coated on the surface of the substrate 2. The wind of the front air outlet volatilizes the precursor solution on the surface of the substrate 2 to form a precursor film. The infrared heaters 11 of the front stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film. The wind of the rear air outlet simultaneously volatilizes the activation solution and the anti-solvent on the surface of the substrate 2 to form a perovskite film. The infrared heaters 12 of the rear stage heating and drying device are simultaneously heated from the upper and lower sides of the substrate 2, respectively, and the activation solution and the anti-solvent on the surface thereof are evaporated together to form a perovskite film.

Others are the same as the third embodiment and will not be described again.

In the foregoing embodiments, the moving speed of the conveyor belt 1 or the conveying shaft may be constant speed or shifting, and the speed is controlled in the range of 0 to 5000 mm/min. The top and bottom heights of the coating head (where the coating head includes the perovskite coating head 3, the anti-solvent coating head 4', the precursor coating head 7 and the activated coating head 8') are adjustable, which is the lowest The vertical distance between the dots and the substrate is from 1 to 1000 microns, and the fluid flow rate of the coating head ranges from 4 to 10 ⁵ ml/hr. The height of the spray nozzle (where the spray nozzle includes the anti-solvent spray nozzle 4, the perovskite spray nozzle 3' and the activated spray nozzle 8) can be adjusted, and the lowest point of the spray nozzle from the substrate is 1 to 10000 micrometers. The fluid flow rate of the spray nozzle ranges from 0 to 20 liters per minute, and the fluid temperature of the spray nozzle is a constant value, which is 0 to 300 ° C. The upper and lower heights of the air outlet can be adjusted, and the vertical distance between the lowest point and the substrate is 100 micrometers to 20 centimeters, and the air outlet (the air outlet includes an air outlet 5 of the air drying device, a front air outlet 9 and a rear section) The wind speed of the air outlet 10) may be constant speed or variable speed, the wind speed is controlled in the range of 0 to 20 m/s, the wind temperature is a fixed value, and the fixed value is -10 ° C to 500 ° C, and the wind blowing direction of the air outlet is It is at least one of vertical, parallel and inclined to the surface of the substrate. The temperature of the heating and drying device is controlled to a constant value, which is 30 to 500 °C.

The coating head is provided with a slit through which the fluid passes, and the width of the slit is a constant value, which is 0.0001 cm to 1 cm.

A first embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

A1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device.

Referring to FIG. 9, it can be seen from the figure that the perovskite film produced in this manner is dense and has a large crystal grain. Referring to FIG. 10, 222.9 mW can be made on an area of 16.368 cm ² , that is, a conversion efficiency of 13.6% can be achieved, indicating that the perovskite film coating apparatus of the present invention has a large-scale mass production capability.

A second embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

A3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a transfer shaft of the conveyor.

A third embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

B1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a transfer shaft of the conveyor.

A fourth embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

B3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device.

A fifth embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

B6. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a transfer shaft of the conveyor.

A sixth embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

C1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a transfer shaft of the anti-solvent coating device transfer device.

A seventh embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

C3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device.

An eighth embodiment of a method of using a perovskite film coating apparatus of the present invention comprises the following steps:

C5. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a transfer shaft of the conveyor.

In an embodiment of the application of the perovskite film coating apparatus of the present invention, the perovskite film coating apparatus can also be used to coat a solution containing at least one of the following materials:

In an application example of a method of using a perovskite film coating apparatus of the present invention, the perovskite film coating apparatus can also be used for coating a solution containing at least one of the following materials:

Vanadium pentoxide (V ₂ O ₅ ), tungsten oxide (WO ₃ ), molybdenum oxide (MoOx), copper sulfide (CuS), cuprous thiocyanate (CuSCN), copper oxide (CuO), cuprous iodide ( CuI), cuprous oxide (Cu ₂ O), iron disulfide (FeS ₂ ), CDO ₂ type copper-iron semiconductor, lead sulfide (PbS), cobalt oxide (CoOx), cobalt sulfide (CoS), magnesium-doped and lithium-doped Nickel oxide (NiMgLiO), nickel oxide (NiOx), polyethylene dioxythiophene-poly(styrene sulfonate) and its highly conductive derivative (PEDOT:PSS), poly[bis(4-phenyl)( 2,4,6-trimethylphenyl)amine] (poly-triaryamine, PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino] -9,9'-Spiro-OMeTAD, 3-hexyl-substituted polythiophene (P3HT), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), cadmium selenide (CdSe), bismuth sulfide (Bi ₂ S _3), indium sulfide (In ₂ S _3), indium oxide (In ₂ O _3), antimony sulfide (Sb ₂ S _3), two Molybdenum sulfide (MoS ₂ ), selenium disulfide (SnS ₂ ), tin oxide (SnO ₂ ), PCBM, aluminum-doped zinc oxide (AZO), cerium oxide (CeOx), cerium oxide (NbOx), barium titanate (BaTiO _{3 )} ), fullerenes (C60, C70), zinc-doped cadmium sulfide (Zn _1-x C d _x S), chromium oxide (CrOx), copper-doped chromium oxide (Cu _x Cr _y O ₂ ). Among them, C=Cu or Ag in the CDO type ₂ copper-iron semiconductor, and D= one or more of Cr, Ga, Al, Sc, In, Y, and Fe.

Hereinafter, a method of using the perovskite film coating apparatus of the present invention will be specifically described with reference to the examples.

Example 1

(1) PbBr ₂ and MAI are dissolved in 1 ml of DMF according to a molar ratio of 1:1 and 0.1 wt% of DIO additive is added to form a 0-2 mol/L perovskite solution, and then the perovskite solution is charged into calcium. In the titanium ore solution coating apparatus, a coating flow rate of 100 ml/hr was set, and the coating head height was 50 μm.

(2) The anti-solvent chlorobenzene was charged into the spraying device, and the spraying flow rate was set to 5 liters/min, the spraying fluid temperature was 60 ° C, and the nozzle height was 200 μm.

(3) Turn on the air blowing device, set the height of the tuyere to 1cm, the wind speed to 3m/s, the wind temperature to 170°C, and the wind direction to be perpendicular to the substrate.

(4) The substrate to which the underlying electrode layer FTO/CuI is attached is placed on the conveyor of the conveyor.

(5) Turning on the conveying device, the conveyor belt sequentially applies the perovskite solution through the perovskite solution coating device, sprays the anti-solvent through the anti-solvent spraying device, and rapidly volatilizes various solvents and anti-solvents through the air blowing device. A substrate to which a MAPbIBr ₂ perovskite film was attached was obtained.

Example 2

(1) PbI ₂ and MAI are dissolved in 1 ml of DMF according to a molar ratio of 1:1 and 0.1 wt% of HI additive is added to prepare a 1 mol/L perovskite solution, and then the perovskite solution is charged into the perovskite. The solution spraying device was set to have a spray flow rate of 10 liters/min, a sprayed fluid temperature of 130 ° C, and a nozzle height of 300 μm.

(2) The anti-solvent toluene was placed in an anti-solvent coating device, and a coating flow rate of 100 ml/hr was set, and the coating head height was 120 μm.

(3) Turn on the heating device and set the heating temperature to 160 °C.

(4) The substrate to which the bottom electrode layer ITO/PEDOT:PSS was attached was placed on a conveyor of a conveyor.

(5) Turning on the conveying device, the conveyor belt sprays the substrate on the perovskite solution through the perovskite solution spraying device, applies the anti-solvent through the anti-solvent coating device, and rapidly evaporates the perovskite solution and the anti-solvent through the heating device. A substrate to which a MAPbI ₃ perovskite film was attached was obtained.

Referring to FIG. 11, the film surface undulation obtained by the airless device is significantly larger than that of the air outlet of the air drying device. As shown in Fig. 12, the film thickness measured at the beginning, the middle and the end of the sample respectively at the beginning, the middle and the end, and the thickness of the film measured at the beginning, the middle and the end of the sample is relatively uniform after the air drying device is used, and no air drying is performed. The film thickness of the device is not uniform and the difference is large. As shown in Fig. 13, an SEM image of a perovskite film obtained by coating and treating without an anti-solvent has many pores on the surface. Figure 14 is a SEM image of a perovskite film obtained by coating and treating with an anti-solvent, wherein the crystal grains are flat and dense.

Example 3

(1) PbI ₂ powder was added to a DMSO solvent to prepare a PbI ₂ solution having a concentration of 1.7 mol/liter, and then the prepared precursor solution PbI ₂ solution was charged into a precursor solution coating device.

(2) CsBr was mixed with isopropyl alcohol to prepare a CsBr solution having a concentration of 10 mg/ml. Thereafter, the prepared CsBr solution was charged into the spraying device.

(3) Place the FTO substrate on which the hole transport layer CuI is deposited on the conveyor of the conveyor, set the transmission speed to 800 mm/min, the height of the coating head to 0.5 cm, the flow rate of the PbI ₂ solution to the flow rate of 3 ml/min, and the CsBr solution. The spray flow rate is 1 liter/min, the nozzle temperature is 30 ° C, the air outlet height is 2 cm, the wind speed is 10 m/s, the wind temperature is 160 ° C, and the wind direction is vertical downward.

(4) Opening the transmission device, the substrate is sequentially coated with the PbI ₂ solution through the precursor solution coating device, and the CsBr solution is sprayed through the activation layer spraying device, and the reaction between the precursor solution and the activation solution is promoted by the wind blowing device. Thus, a CsPbI ₂ Br perovskite film is formed.

Example 4

(1) PbCl ₂ powder was added to a DMF solvent to prepare a PbCl ₂ solution having a concentration of 1.2 mol/liter, and then the prepared precursor solution PbCl ₂ solution was charged into the precursor solution coating device 7. The MAI was mixed with isopropyl alcohol to prepare a MAI solution having a concentration of 10 mg/ml. Thereafter, the prepared MAI solution is charged into the coating device 8'.

(2) The ITO substrate on which the underlying electrode layer PEDOT:PSS was deposited was placed on a conveyor belt of a conveyor, the transmission speed was set to 1000 mm/min, the height of the coating head was 1 cm, and the flow rate of the PbCl ₂ solution was 20 ml/min, MAI. The solution delivery rate is 2 liters/min, the air outlet height is 2 cm, the wind speed is 10 m/s, the air temperature is 160 ° C, and the wind direction is vertically downward.

(3) The anti-solvent chlorobenzene was charged into the spraying device, and the spraying flow rate was set to 12 ml/min, and the spraying fluid temperature was 50 °C.

(4) Turning on the conveying device, the conveyor belt applies the PbCl ₂ solution through the precursor solution coating device in sequence, applies the activation solution MAI solution through the coating device, sprays the chlorobenzene through the anti-solvent spraying device, and promotes by the wind blowing device. The formation of a perovskite film and the volatilization of various solvents gave a substrate to which a MAPbICl ₂ perovskite film was attached.

Example 5

(1) The SnCl ₂ powder was dissolved in a NMP solvent to prepare a solution having a concentration of 1.3 mol/liter. Then, the SnCl ₂ solution was placed in the coating device 7, and the anti-solvent benzene was charged into the coating device 4'.

(2) The RbSCN powder was dissolved in an isopropanol solvent to prepare an activation layer solution RbSCN solution and the solution was placed in a spray apparatus.

(3) Place the FTO glass with P3HT deposited on the conveyor of the conveyor, set the transmission speed to 1100mm/min, the height of the coating head is 0.35cm, the flow rate of SnCl ₂ solution is 6ml/min, and the flow rate of anti-solvent is 0.3. L / min, spray nozzle height of 3cm, RbSCN solution delivery flow of 1.2 l / min, nozzle temperature of 25 ° C, air outlet height of 2cm, wind speed of 10m / s, wind temperature of 160 ° C, wind direction vertically downward.

(4) The transfer device is turned on, the substrate is sequentially coated with the SnCl ₂ solution by the precursor coating device, the RbSCN solution is sprayed by the spray device, the benzene is coated by the anti-solvent coating device, and the wind is blown through the fan port. Thus, a RbSnCl ₂ SCN perovskite film was produced.

Example 6

(1) The SnBr ₂ powder was dissolved in DMSO to prepare a 1.8 mol/L CsBr ₂ solution, and then the SnBr ₂ solution was placed in a coating apparatus.

(2) The CsBr powder was dissolved in an isopropyl alcohol solvent to prepare a CsBr solution and charged into a spray apparatus.

(3) The ITO glass deposited with the electron transport layer TiO2 was placed on a conveyor belt of the transport device, and the height of the coating head was set to 0.06 cm, the transport volume of the SnBr ₂ solution was 0.8 liter/min, the height of the spraying device was 3 cm, and the flow rate of the CsBr solution was 1 liter/ Minutes, the nozzle temperature is 50 °C, the front fan port 9 and the rear fan port 10 are both 5 cm high, the wind speed is 6 m / s, the front fan air temperature is 60 ° C, the rear fan air temperature is 160 ° C, the direction is vertical downward.

(4) The transfer device is turned on, and the substrate is sequentially coated with the SnBr ₂ solution through the precursor solution coating device, and passed through the front fan, through the CsBr solution spraying device, and through the rear fan. Thus, a CsSnBr ₃ perovskite film is formed.

Example 7

(1) PbI ₂ powder was added to a DMF solvent to prepare a PbI ₂ solution having a concentration of 1.1 mol/liter, and then the prepared precursor solution PbI ₂ solution was charged into the precursor solution coating device 7. The MAI was mixed with isopropyl alcohol to prepare a MAI solution having a concentration of 10 mg/ml. Thereafter, the prepared MAI solution is charged into the coating device 9.

(2) loading the anti-solvent toluene into the spraying device;

(3) The ITO substrate on which the underlying electrode layer PEDOT:PSS was deposited was placed on a conveyor belt of a conveyor, the transmission speed was set to 2000 mm/min, the height of the coating head I was 1.8 cm, and the flow rate of the PbI ₂ solution was 3 ml/min. The height of the cloth head II is 2cm, the flow rate of the MAI solution is 3 liters/min, the flow rate of the toluene spray is 2 liters/min, the nozzle temperature is 25°C, the height of the front and rear air outlets is 2cm, the wind direction is vertical downward, and the wind speed of the front fan is vertical. 7m / s and wind temperature of 100 ° C, the downstream fan wind speed of 3 m / s and wind temperature of 150 ° C.

(4) Opening the transmission device, the substrate is sequentially coated with the precursor solution PbI ₂ solution through the coating device I, the solvent is volatilized through the fan mouth, the precursor solution is changed into a preset film, and the activation solution MAI solution is coated by the coating device. The anti-solvent toluene is sprayed by a spraying device, and the formation of the perovskite film is accelerated by the rear air drying device.

Example 8

(1) PbI ₂ powder was added to a NMP solvent to prepare a PbI ₂ solution having a concentration of 1.0 mol/liter, and then the prepared precursor solution PbI ₂ solution was charged into the precursor solution coating device 7. The anti-solvent toluene was charged into the coating device 4'.

(2) FAI was mixed with isopropyl alcohol to prepare a FAI solution having a concentration of 15 mg/ml. Thereafter, the prepared FAI solution is charged into the spraying device.

(3) The ITO substrate deposited with the hole transport layer PTAA was placed on a conveyor belt of a conveyor, and the transmission speed was set to 1500 mm/min, the height of the coating head I was 1.8 cm, and the flow rate of the PbI ₂ solution was 1 ml/min. The height of the cloth head II is 2cm, the flow rate of toluene is 3 liters/min, the flow rate of the FAI solution is 2 liters/min, the nozzle temperature is 25°C, the height of the front and rear outlets is 2cm, the wind direction is vertical downward, and the wind speed of the front fan is 8m. /s and wind temperature 50 °C, the rear fan wind speed 3m / s and wind temperature 150 ° C.

(4) Opening the transmission device, the substrate is sequentially coated with the PbI ₂ solution of the precursor solution through the coating device I, the solvent is volatilized by the heating device, the precursor solution becomes a preset film adhered to the substrate, and the activation solution is sprayed by the spraying device. The FAI solution was coated with anti-solvent toluene by a coating device, and the formation of the perovskite film was accelerated by a post-stage heating device.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims

A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a perovskite solution coating device, an anti-solvent spraying device, and an air drying device or a heating drying device, wherein the substrate is prepared in advance An electrode layer, the conveying device is provided with a conveyor belt or a conveying shaft, the perovskite solution coating device is provided with a coating head, the coating head is a perovskite coating head, and the anti-solvent spraying device is provided with a spray nozzle, the spray nozzle is an anti-solvent spray nozzle, the air drying device is provided with an air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the transmission shaft, and the calcium is sequentially driven by the calcium a titanium ore solution coating device, an anti-solvent spraying device, and an air drying device or a heating and drying device, the perovskite coating head coating a perovskite solution on the surface of the substrate, the anti-solvent spraying nozzle spraying the anti-solvent On the surface of the substrate, the wind of the air outlet simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the infrared heater of the heating and drying device Respectively from both upper and lower substrates while heating it together with the solution was evaporated to dryness which on the surface of a perovskite and perovskite antisolvent to form a thin film.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a perovskite solution spraying device, an anti-solvent coating device, and an air drying device or a heating drying device, wherein the substrate is prepared in advance An electrode layer, the conveying device is provided with a conveyor belt or a conveying shaft, the perovskite solution spraying device is provided with a spray nozzle, the spray nozzle is a perovskite spray nozzle, and the anti-solvent coating device is provided with a coating head The coating head is an anti-solvent coating head, the air drying device is provided with an air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft to drive through the calcium in sequence. a titanium ore solution spraying device, an anti-solvent coating device, and an air drying device or a heating and drying device, the perovskite spray nozzle spraying a perovskite solution on the surface of the substrate, the anti-solvent coating head coating the anti-solvent On the surface of the substrate, the wind of the air outlet simultaneously volatilizes the perovskite solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the infrared heater of the heating and drying device Respectively from both upper and lower substrates while heating it together with the solution was evaporated to dryness which on the surface of a perovskite and perovskite antisolvent to form a thin film.
A perovskite film coating apparatus comprising: a conveying device for conveying a substrate, a precursor solution coating device, an activation layer spraying device, and an air drying device or a heating drying device, wherein the substrate is prepared with a bottom electrode in advance a layer, the conveying device is provided with a conveyor belt or a conveying shaft, the precursor solution coating device is provided with a coating head, the coating head is a precursor coating head, and the activation layer spraying device is provided with a spray nozzle, The spraying nozzle is an activated spraying nozzle, the air drying device is provided with an air outlet, the heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft, and is sequentially driven by the precursor solution. a device, an activation layer spraying device and an air drying device or a heating and drying device, the precursor coating head coating a precursor solution on a surface of the substrate, the activated spray nozzle spraying the activation solution on the surface of the substrate, The wind at the air outlet simultaneously volatilizes the precursor solution and the activation solution on the surface of the substrate to form a perovskite film, and the infrared heater of the heating and drying device Respectively from both upper and lower substrates while heating it together with the precursor solution was evaporated to dryness on its surface, and activating solution to form a thin film of perovskite.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a precursor solution coating device, an activation layer coating device, an anti-solvent spraying device, and an air drying device or a heating drying device, wherein the base The sheet is previously prepared with a bottom electrode layer, the transfer device is provided with a conveyor belt or a transfer shaft, the precursor solution coating device is provided with a coating head, the coating head is a precursor coating head, and the activation layer is coated The cloth device is provided with a coating head, the coating head is an activated coating head, the anti-solvent spraying device is provided with a spraying nozzle, the spraying nozzle is an anti-solvent spraying nozzle, and the air drying device is provided with an air outlet, The heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer coating device, the anti-solvent spraying device, the air drying device or the heating drying device. The precursor coating head coats a precursor solution on the surface of the substrate, and the activated coating head coats the activation solution on the surface of the substrate, and the anti-solvent spray nozzle will The anti-solvent is sprayed on the surface of the substrate, and the wind of the air outlet simultaneously volatilizes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the infrared heaters of the heating and drying device respectively The precursor solution, the activation solution and the anti-solvent on the surface are simultaneously evaporated from the upper and lower sides of the substrate to form a perovskite film.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a precursor solution coating device, an activation layer spraying device, an anti-solvent coating device, and an air drying device or a heating drying device, wherein the base The sheet is previously prepared with a bottom electrode layer, the transfer device is provided with a conveyor belt or a transfer shaft, the precursor solution coating device is provided with a coating head, the coating head is a precursor coating head, and the anti-solvent coating The cloth device is provided with a coating head, the coating head is an anti-solvent coating head, the activation layer spraying device is provided with a spraying nozzle, the spraying nozzle is an activated spraying nozzle, and the air drying device is provided with an air outlet, The heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft to be sequentially driven by the precursor solution coating device, the activation layer spraying device, the anti-solvent coating device, the air drying device or the heating drying device. The precursor coating head coats a precursor solution on the surface of the substrate, the activated spray nozzle spraying the activation solution on the surface of the substrate, and the anti-solvent coating head will The solvent is coated on the surface of the substrate, and the wind at the air outlet simultaneously volatilizes the precursor solution, the activation solution and the anti-solvent on the surface of the substrate to form a perovskite film, and the infrared heaters of the heating and drying device respectively The precursor solution, the activation solution and the anti-solvent on the surface are simultaneously evaporated from the upper and lower sides of the substrate to form a perovskite film.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer spraying device, and a rear air drying device or a rear portion Heating the drying device, the substrate is prepared in advance with a bottom electrode layer, the transfer device is provided with a conveyor belt or a transfer shaft, and the precursor solution coating device is provided with a coating head, which is a precursor coating The front air drying device is provided with a front air outlet, the front heating and drying device is provided with an infrared heater, the active layer spraying device is provided with a spray nozzle, the spray nozzle is an activated spray nozzle, and the rear portion is air-dried The device is provided with a rear air outlet, and the rear heating and drying device is provided with an infrared heater, and the substrate is placed on the conveyor belt or the conveying shaft, and is driven by the precursor solution coating device, the front air drying device or the front heating portion. Drying device, activation layer spraying device and rear air drying device or rear heating drying device, the precursor coating head coating the precursor solution Deploying on the surface of the substrate, the activated spray nozzle sprays an activation solution on the surface of the substrate, and the wind at the front outlet vents volatilizes the precursor solution on the surface of the substrate to form a precursor film, and the front section heats The infrared heater of the drying device is simultaneously heated from the upper and lower sides of the substrate to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind at the outlet air outlet volatilizes the activation solution on the surface of the substrate. The perovskite film is dried and formed, and the infrared heater of the subsequent stage heating and drying device heats the active solution on the upper and lower sides of the substrate, respectively, to evaporate and dry the surface and form a perovskite film.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer coating device, an anti-solvent spraying device, and the like a section air drying device or a rear stage heating and drying device, the substrate is prepared with a bottom electrode layer in advance, the conveying device is provided with a conveyor belt or a conveying shaft, and the precursor solution coating device is provided with a coating head, the coating The head is a precursor coating head, the front air drying device is provided with a front air outlet, the front heating drying device is provided with an infrared heater, and the activation layer coating device is provided with a coating head, and the coating head is The coating head is activated, the anti-solvent spraying device is provided with a spraying nozzle, the spraying nozzle is an anti-solvent spraying nozzle, the rear air drying device is provided with a rear air outlet, and the rear heating drying device is provided with infrared heating The substrate is placed on the conveyor belt or the conveying shaft and driven by the precursor solution coating device, the front air drying device or the front heating drying device, and activated. a coating device, an anti-solvent spraying device and a rear air drying device or a rear heating drying device, the precursor coating head coating a precursor solution on a surface of the substrate, the activated coating head coating the activation solution On the surface of the substrate, the anti-solvent spray nozzle sprays an anti-solvent on the surface of the substrate, and the wind of the front air outlet vapor volatilizes the precursor solution on the surface of the substrate to form a precursor film, and the front section is heated. The infrared heaters of the drying device are simultaneously heated from the upper and lower sides of the substrate, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind at the rear outlet air outlet activates the activation solution on the surface of the substrate. The anti-solvent is simultaneously volatilized and dried to form a perovskite film, and the infrared heater of the latter heating and drying device is simultaneously heated from the upper and lower sides of the substrate, and the activation solution and the anti-solvent on the surface are evaporated and dried to form calcium. Titanium ore film.
A perovskite film coating apparatus, comprising: a conveying device for conveying a substrate, a precursor solution coating device, a front air drying device or a front heating drying device, an activation layer spraying device, an anti-solvent coating device, and a rear a section air drying device or a rear stage heating and drying device, the substrate is prepared with a bottom electrode layer in advance, the conveying device is provided with a conveyor belt or a conveying shaft, and the precursor solution coating device is provided with a coating head, the coating The head is a precursor coating head, the anti-solvent coating device is provided with a coating head, the coating head is an anti-solvent coating head, the front air drying device is provided with a front air outlet, and the front heating drying device An infrared heater is disposed, the activation layer spraying device is provided with a spray nozzle, the spray nozzle is an activated spray nozzle, the rear air drying device is provided with a rear air outlet, and the rear heating and drying device is provided with infrared heating The substrate is placed on the conveyor belt or the conveying shaft and driven by the precursor solution coating device, the front air drying device or the front heating drying device, and activated. a spraying device, an anti-solvent coating device and a rear air drying device or a rear heating drying device, the precursor coating head coating a precursor solution on the surface of the substrate, the activated spray nozzle spraying the activation solution on the base On the surface of the sheet, the anti-solvent coating head coats the anti-solvent on the surface of the substrate, and the wind of the front portion of the air outlet volatilizes the precursor solution on the surface of the substrate to form a precursor film, and the front portion is heated. The infrared heaters of the drying device are simultaneously heated from the upper and lower sides of the substrate, respectively, to evaporate and dry the precursor solution on the surface thereof to form a precursor film, and the wind at the rear outlet air outlet activates the activation solution on the surface of the substrate. The anti-solvent is simultaneously volatilized and dried to form a perovskite film, and the infrared heater of the latter heating and drying device is simultaneously heated from the upper and lower sides of the substrate, and the activation solution and the anti-solvent on the surface are evaporated and dried to form calcium. Titanium ore film.
The perovskite film coating apparatus according to any one of claims 1 to 8, wherein the moving speed of the conveyor belt or the conveying shaft can be constant speed or variable speed, and the speed is controlled at 0 to 5000 mm/ In the range of min; the upper and lower heights of the coating head are adjustable, the lowest point of the coating head is from 1 to 1000 micrometers, and the fluid flow rate of the coating head is in the range of 4 to 10 5 ml / hour; The upper and lower heights of the spray nozzle are adjustable, the lowest point of the spray nozzle is from 1 to 10000 micrometers, the fluid flow rate of the spray nozzle is from 0 to 20 liters per minute, and the fluid temperature of the spray nozzle is constant. The setting value is 0-300 ° C; the upper and lower heights of the air outlet can be adjusted, and the vertical distance between the lowest point and the substrate is 100 micrometers to 20 centimeters, and the wind speed of the air outlet can be constant speed or variable speed, wind speed The control is in the range of 0 to 20 m/s, the wind temperature is a constant value, the value is -10 ° C to 500 ° C, and the wind blowing direction of the air outlet is at least one of vertical, parallel and inclined to the surface of the substrate. The temperature of the heating and drying device is controlled at a certain value, The value is 30 to 500 °C.
The perovskite film coating apparatus according to any one of claims 1 to 8, wherein the coating head is provided with a slit through which a fluid passes, and the width of the slit is a constant value. The value is 0.0001 cm to 1 cm.
The perovskite film coating apparatus according to claim 1 or 2, wherein the perovskite solution is a mixture of BX 2 , AX, a main solvent, a solvent additive, and/or an organic polymer additive, wherein B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, At least one cation of cerium and lanthanum; X is at least one anion of iodine (I), bromine (Br), chlorine (Cl), acetate (CH 3 COO); A is ruthenium, osmium, amine, sulfhydryl Or at least one cation in the alkali group; the main solvent includes an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic At least one of a hydrocarbon solvent; the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, an aromatic hydrocarbon At least one; the organic polymer additive is polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, polylactic acid, polyvinyl alcohol, polypropylene At least one of acid, polyurethane, polyethyleneimine, polypropylene thiamine, polystyrene sulfonic acid, polyvinylpyrrolidone, polyvinyl butyral resin, fluorine-based polymer; the anti-solvent is a halogenated hydrocarbon At least one of a solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent has a molecular weight in the range of 200 to 100,000.
The perovskite film coating apparatus according to claim 11, wherein the solution concentration of the BX 2 is 0.2-5 mol/L, and the molar ratio of the AX to BX 2 is 0.1-10, the BX 2 The molar concentration in the main solvent is 0.2 to 2 mol/L, the molar ratio of the solvent additive to BX 2 is 0 to 1, and the molar ratio of the organic polymer additive to BX 2 is 0.05 to 5.
The perovskite film coating apparatus according to any one of claims 3 to 8, wherein the precursor solution comprises a BX 2 solute, a main solvent and a solvent additive, and the activation solution comprises an AX solute. Main solvent and organic polymer additive; wherein B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, antimony At least one cation of ruthenium, rhodium, platinum, gold, mercury, ruthenium, osmium, iridium; X is at least one anion of iodine (I), bromine (Br), chlorine (Cl), acetate (CH 3 COO); A is at least one cation of ruthenium, osmium, amino group, sulfhydryl group or alkali group; main solvent includes amide solvent, sulfone/sulfoxide solvent, ester solvent, hydrocarbon, halogenated hydrocarbon solvent, alcohol At least one of a solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent; the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; the organic polymer additive is polyethylene glycol or polypropylene glycol At least polyvinylpyrrolidone, polylactic acid, polyvinyl alcohol, polyacrylic acid, polyurethane, polyethyleneimine, polypropylene thiamine, polystyrene sulfonic acid, polyvinylpyrrolidone, polyvinyl butyral resin, fluorine polymer The anti-solvent is at least one of a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent, and has a molecular weight ranging from 200 to 100,000.
The perovskite film coating apparatus according to claim 13, wherein the solution concentration of the BX 2 is 0.2-5 mol/L, and the solution concentration of the AX is 0.1 mg/ml to 100 mg/ml. The molar concentration of BX2 in the main solvent is 0.2 to 2 mol/L, the molar ratio of the solvent additive to BX 2 is 0 to 1, and the volume ratio of the organic polymer additive to the main solvent of AX is 0 to 1.
A method of using a perovskite film coating apparatus according to claim 1, comprising the steps of:

A1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

A2. The substrate is sequentially passed through a perovskite solution coating device, and the perovskite coating head coats the perovskite solution on the surface of the substrate, and the anti-solvent spraying device sprays the anti-solvent on the substrate through an anti-solvent spraying device. On the surface of the sheet, the perovskite solution and the anti-solvent are quickly volatilized or evaporated by an air drying device or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 2, comprising the steps of:

A3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

A4. The substrate is sequentially passed through a perovskite solution spraying device, and the perovskite spray nozzle sprays the perovskite solution on the surface of the substrate, and the anti-solvent coating head coats the anti-solvent on the substrate through an anti-solvent coating device. On the surface of the sheet, the perovskite solution and the anti-solvent are quickly volatilized or evaporated by an air drying device or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 3, comprising the steps of:

B1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B2. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation spray coating device activates the spray nozzle to spray the activation solution on the surface of the substrate. The precursor solution and the activation solution are quickly volatilized or evaporated by an air outlet or a heating and drying device, an air outlet or an infrared heater, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 4, comprising the steps of:

B3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B4. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation coating solution is applied to the substrate by the activation layer coating device. On the surface, the anti-solvent spraying device sprays the anti-solvent on the surface of the substrate through an anti-solvent spraying device, and the precursor solution, the activation solution and the anti-solvent are quickly volatilized together by an air drying device or a heating and drying device, an air outlet or an infrared heater. Or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 5, comprising the steps of:

B6. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

B7. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and the activation spray coating device activates the spray nozzle to spray the activation solution on the surface of the substrate. Through the anti-solvent coating device, the anti-solvent coating head coats the anti-solvent on the surface of the substrate, and the precursor solution, the activation solution and the anti-solvent are quickly volatilized together by an air drying device or a heating and drying device, an air outlet or an infrared heater. Or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 6, comprising the steps of:

C1. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the anti-solvent coating device conveying device;

C2. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is quickly volatilized or evaporated, and the activation solution is sprayed on the surface of the substrate by the activation layer spraying device, and the activation solution is quickly sprayed through the rear air drying device or the rear heating drying device, and the rear air outlet or the infrared heater is used to quickly activate the solution. Volatilization or evaporation, and finally a substrate having a perovskite film attached to the surface is obtained and stored.
A method of using a perovskite film coating apparatus according to claim 7, comprising the steps of:

C3. The substrate to which the bottom electrode layer is attached is placed on a conveyor belt or a conveying shaft of the conveying device;

C4. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is rapidly volatilized or evaporated. The activation coating solution is applied to the surface of the substrate by an activation layer coating device. The anti-solvent spraying device sprays the anti-solvent on the surface of the substrate through an anti-solvent spraying device. The rear air drying device or the rear heating drying device, the rear air outlet or the infrared heater rapidly volatilizes or evaporates the activation solution together with the anti-solvent, and finally obtains a substrate with a perovskite film attached to the surface and stores it.
A method of using a perovskite film coating apparatus according to claim 8, comprising the steps of:

C5. placing the substrate to which the bottom electrode layer is attached on the conveyor belt or the conveying shaft of the conveying device;

C6. The substrate is sequentially passed through a precursor solution coating device, and the precursor coating head coats the precursor solution on the surface of the substrate, and passes through the front air drying device or the front heating drying device, and the front air outlet or the infrared heater drives the precursor The body solution is rapidly volatilized or evaporated, and the activation solution is sprayed on the surface of the substrate by the activation layer spraying device, and the anti-solvent coating head is used to coat the anti-solvent on the surface of the substrate through the anti-solvent coating device. The rear air drying device or the rear heating drying device, the rear air outlet or the infrared heater rapidly volatilizes or evaporates the activation solution together with the anti-solvent, and finally obtains a substrate with a perovskite film attached to the surface and stores it.
The method of using a perovskite film coating apparatus according to any one of claims 15 to 22, wherein the moving speed of the conveyor belt or the conveying shaft can be constant speed or variable speed, and the speed is controlled at 0. In the range of ～5000 mm/min; the upper and lower heights of the coating head can be adjusted, the lowest point of the coating head is from 1 to 1000 μm, and the fluid flow rate of the coating head ranges from 4 to 10 5 ml/hour. The upper and lower heights of the spray nozzle are adjustable, the lowest point of the spray nozzle is from 1 to 10000 micrometers, the fluid flow rate of the spray nozzle is 0-20 liters/minute, and the fluid temperature of the spray nozzle is The fixed value is 0-300 ° C; the upper and lower heights of the air outlet can be adjusted, and the vertical distance between the lowest point and the substrate is 100 micrometers to 20 centimeters, and the wind speed of the air outlet can be uniform or Variable speed, wind speed control in the range of 0 ~ 20m / s, the wind temperature is a fixed value, the value is -10 ° C ~ 500 ° C, the wind blowing direction of the air outlet is vertical, parallel and inclined in the surface of the substrate At least one; the temperature of the heating and drying device is controlled at Value, the setpoint is 30 ~ 500 ℃.
A method of using a perovskite film coating apparatus according to claim 15 or 16, wherein the perovskite solution is a mixture of BX 2 , AX, a main solvent, a solvent additive and/or an organic polymer additive. , wherein B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury At least one cation of ruthenium, osmium, iridium; X is at least one anion of iodine (I), bromine (Br), chlorine (Cl), acetate (CH 3 COO); A is ruthenium, osmium, amine At least one cation in the sulfhydryl group or the alkali group; the main solvent includes an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether At least one of a solvent and an aromatic hydrocarbon solvent; the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, At least one of aromatic hydrocarbons; the organic polymer additive is polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polylactic acid, polyethyl At least one of an enol, a polyacrylic acid, a polyurethane, a polyethyleneimine, a polypropylene thiamine, a polystyrene sulfonic acid, a polyvinylpyrrolidone, a polyvinyl butyral resin, or a fluorine-based polymer; At least one of a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent has a molecular weight in the range of 200 to 100,000.
The method of using a perovskite film coating apparatus according to claim 24, wherein the solution concentration of the BX 2 is 0.2-5 mol/L, and the molar ratio of the AX to BX 2 is 0.1-10. The molar concentration of the BX 2 in the main solvent is 0.2 to 2 mol/L, the molar ratio of the solvent additive to BX 2 is 0 to 1, and the molar ratio of the organic polymer additive to BX 2 is 0.05 to 5.
The method of using a perovskite film coating apparatus according to any one of claims 17 to 22, wherein the precursor solution comprises a BX 2 solute, a main solvent, and a solvent additive, the activation solution comprising Containing AX solute, main solvent and organic polymer additive; wherein B is lead (Pb), tin (Sn), tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, At least one cation of ruthenium, osmium, iridium, platinum, gold, mercury, ruthenium, osmium, iridium; X is at least one of iodine (I), bromine (Br), chlorine (Cl), acetate (CH 3 COO) Anion; A is at least one cation of ruthenium, osmium, amine, sulfhydryl or alkali; the main solvent includes amide solvent, sulfone/sulfoxide solvent, ester solvent, hydrocarbon, halogenated hydrocarbon solvent At least one of an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent; the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol At least one of a solvent-like solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; the organic polymer additive is polyethylene glycol , polypropylene glycol, polyvinylpyrrolidone, polylactic acid, polyvinyl alcohol, polyacrylic acid, polyurethane, polyethyleneimine, polypropylene thiamine, polystyrene sulfonic acid, polyvinylpyrrolidone, polyvinyl butyral resin, fluorine At least one of the polymers; the anti-solvent is at least one of a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent, an amide solvent, an ether solvent, and an ester solvent, and has a molecular weight range of 200- 100000.
The perovskite film coating apparatus according to claim 26, and a method and application method thereof, wherein the solution concentration of the BX 2 is 0.2-5 mol/L, and the solution concentration of the AX is 0.1 mg/ml. 100 mg/ml, the molar concentration of the BX 2 in the main solvent is 0.2 to 2 mol/L, the molar ratio of the solvent additive to BX 2 is 0 to 1, and the volume ratio of the organic polymer additive to the main solvent of AX It is 0 to 1.
Use of a perovskite film coating apparatus according to any one of claims 1 to 8, characterized in that the perovskite film coating apparatus can also be used for coating a solution containing at least one of the following materials :

Vanadium pentoxide (V 2 O 5 ), tungsten oxide (WO 3 ), molybdenum oxide (MoOx), copper sulfide (CuS), cuprous thiocyanate (CuSCN), copper oxide (CuO), cuprous iodide ( CuI), cuprous oxide (Cu 2 O), iron disulfide (FeS 2 ), CDO 2 type copper-iron semiconductor, lead sulfide (PbS), cobalt oxide (CoOx), cobalt sulfide (CoS), magnesium-doped and lithium-doped Nickel oxide (NiMgLiO), nickel oxide (NiOx), polyethylene dioxythiophene-poly(styrene sulfonate) and its highly conductive derivative (PEDOT:PSS), poly[bis(4-phenyl)( 2,4,6-trimethylphenyl)amine] (poly-triaryamine, PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino] -9,9'-spiro-OMeTAD, 3-hexyl-substituted polythiophene (P3HT), titanium dioxide (TiO 2 ), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), cadmium selenide (CdSe), bismuth sulfide (Bi 2 S 3), indium sulfide (In 2 S 3), indium oxide (In 2 O 3), antimony sulfide (Sb 2 S 3), two Molybdenum sulfide (MoS 2 ), selenium disulfide (SnS 2 ), tin oxide (SnO 2 ), PCBM, aluminum-doped zinc oxide (AZO), cerium oxide (CeOx), cerium oxide (NbOx), barium titanate (BaTiO 3 ) ), fullerenes (C60, C70), zinc-doped Cadmium (Zn 1-x Cd x S ), chromium oxide (CrOx), chromium oxide doped with copper (Cu x Cr y O 2) ,

Among them, C=Cu or Ag in the CDO type 2 copper-iron semiconductor, and D= one or more of Cr, Ga, Al, Sc, In, Y, and Fe.
Use of a method of using a perovskite film coating apparatus according to any one of claims 15 to 22, characterized in that the method of using the perovskite film coating apparatus can also be used for coating comprising the following a solution of at least one material:

Vanadium pentoxide (V 2 O 5 ), tungsten oxide (WO 3 ), molybdenum oxide (MoOx), copper sulfide (CuS), cuprous thiocyanate (CuSCN), copper oxide (CuO), cuprous iodide ( CuI), cuprous oxide (Cu 2 O), iron disulfide (FeS 2 ), CDO 2 type copper-iron semiconductor, lead sulfide (PbS), cobalt oxide (CoOx), cobalt sulfide (CoS), magnesium-doped and lithium-doped Nickel oxide (NiMgLiO), nickel oxide (NiOx), polyethylene dioxythiophene-poly(styrene sulfonate) and its highly conductive derivative (PEDOT:PSS), poly[bis(4-phenyl)( 2,4,6-trimethylphenyl)amine] (poly-triaryamine, PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino] -9,9'-spiro-OMeTAD, 3-hexyl-substituted polythiophene (P3HT), titanium dioxide (TiO 2 ), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), cadmium selenide (CdSe), bismuth sulfide (Bi 2 S 3), indium sulfide (In 2 S 3), indium oxide (In 2 O 3), antimony sulfide (Sb 2 S 3), two Molybdenum sulfide (MoS 2 ), selenium disulfide (SnS 2 ), tin oxide (SnO 2 ), PCBM, aluminum-doped zinc oxide (AZO), cerium oxide (CeOx), cerium oxide (NbOx), barium titanate (BaTiO 3 ) ), fullerenes (C60, C70), zinc-doped Cadmium (Zn 1-x Cd x S ), chromium oxide (CrOx), chromium oxide doped with copper (Cu x Cr y O 2) ,

Among them, C=Cu or Ag in the CDO type 2 copper-iron semiconductor, and D= one or more of Cr, Ga, Al, Sc, In, Y, and Fe.