Manufacturing device of perovskite solar cell and manufacturing method thereof

Abstract

The present application relates to a manufacturing apparatus for perovskite solar cells and a manufacturing method thereof. The object is to provide a manufacturing apparatus for perovskite solar cells, in which the crystallinity and film uniformity of a perovskite layer are excellent in the formation of the perovskite layer using an anti-solvent method. The manufacturing apparatus for perovskite solar cells includes: a perovskite precursor coating mechanism that coats a perovskite precursor ink on a substrate to form a perovskite precursor film; a drying mechanism that dries the perovskite precursor film; an anti-solvent coating mechanism that coats an anti-solvent from a slit nozzle in a direction perpendicular to the substrate without contacting the perovskite precursor film; a conveying mechanism that horizontally conveys the substrate on which the anti-solvent is coated; a removing mechanism that removes the anti-solvent from the horizontally conveyed perovskite precursor film; and a firing mechanism that fires the perovskite precursor film from which the anti-solvent is removed.

Description

Technical Field

[0001] This invention relates to an apparatus for manufacturing perovskite solar cells and a method for manufacturing perovskite solar cells. Background Technology

[0002] Previously, as a method for forming a perovskite layer in a perovskite solar cell, a method is known to obtain a perovskite crystalline film by coating a perovskite precursor ink onto a substrate and then drying it.

[0003] In particular, the following anti-solvent method is known: after coating the perovskite precursor ink, an anti-solvent (poor solvent) relative to the perovskite is provided, thereby causing a large number of perovskite crystal nuclei to precipitate and form a uniform crystalline film.

[0004] However, in order to form a uniform crystalline film using the existing antisolvent method, it is necessary to appropriately and uniformly adjust the coating amount of the antisolvent and the contact time with the antisolvent for the perovskite precursor ink.

[0005] When the coating amount of the antisolvent and the contact time with the antisolvent are inappropriate, the uniformity of the perovskite crystals decreases, leading to deviations in the conversion efficiency and durability of perovskite solar cells, and a high incidence of defective products. Therefore, previous antisolvent methods were mostly carried out manually, which presents a challenge in implementing them as manufacturing equipment for mass production.

[0006] [Existing technical documents]

[0007] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2023-148126 Summary of the Invention

[0009] One aspect of the present invention aims to provide an apparatus for manufacturing perovskite solar cells with excellent crystallinity and film uniformity of the perovskite layer in the formation of the perovskite layer using an anti-solvent method.

[0010] One aspect of the present invention, as a means of solving the problem, relates to a manufacturing apparatus for a perovskite solar cell, comprising:

[0011] The perovskite precursor coating mechanism coats a substrate with perovskite precursor ink to form a perovskite precursor film;

[0012] The drying unit dries the perovskite precursor film;

[0013] The antisolvent coating mechanism coats the dried perovskite precursor film with an antisolvent from a slit nozzle in a direction perpendicular to the substrate, without contacting the perovskite precursor film.

[0014] A conveying mechanism horizontally conveys the substrate coated with the antisolvent;

[0015] The antisolvent is removed from the perovskite precursor membrane transported horizontally; and

[0016] The sintering mechanism sinters the perovskite precursor film from which the antisolvent has been removed.

[0017] The effects of the present invention are explained below:

[0018] According to one aspect of the present invention, an apparatus for manufacturing a perovskite solar cell with excellent crystallinity and film uniformity of the perovskite layer in the formation of the perovskite layer using an anti-solvent method can be provided. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of an example of a perovskite solar cell unit.

[0020] Figure 2 It means Figure 1 A schematic diagram of an example of a manufacturing apparatus for a perovskite solar cell unit.

[0021] Figure 3 This is a schematic diagram illustrating another example of a manufacturing apparatus for a perovskite solar cell unit.

[0022] Figure 4 This is a schematic diagram illustrating yet another example of a manufacturing apparatus for a perovskite solar cell unit.

[0023] Figure 5 This is a perspective illustration of an example of a manufacturing apparatus for a perovskite solar cell according to an embodiment of the present invention.

[0024] Figure 6A This is a schematic diagram illustrating an example of a conveying mechanism in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0025] Figure 6B This is a schematic diagram illustrating another example of a conveying mechanism in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0026] Figure 7 This is an example of a configuration for optimizing the amount of antisolvent coating in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0027] Figure 8A This is an explanatory diagram of an example of an air outlet of a component constituting an air knife in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0028] Figure 8B This is an illustrative diagram of another example of the air outlet of a component constituting an air knife in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0029] Figure 9 This is an illustration of an existing removal mechanism.

[0030] Figure 10 This is an explanatory diagram of the antisolvent removal mechanism in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0031] Figure 11 This is an explanatory diagram of another example of the removal mechanism in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0032] Figure 12 This is an explanatory diagram illustrating an antisolvent coating mechanism with a slit nozzle in a perovskite solar cell manufacturing apparatus according to an embodiment of the present invention.

[0033] The symbols in the diagram are explained as follows:

[0034] 10: Manufacturing apparatus for perovskite solar cells

[0035] 11: Perovskite precursor coating methods (mechanism)

[0036] 12: Drying methods (mechanisms)

[0037] 13: Antisolvent coating method (mechanism)

[0038] 14: Conveying means (mechanisms)

[0039] 15: Antisolvent removal methods (mechanisms)

[0040] 16: Firing methods (mechanism)

[0041] 17: Antisolvent

[0042] 18: Substrate

[0043] 19: Precursor Ink Film

[0044] 22: Clamping roller

[0045] 24: Take-up roller

[0046] 25: Wheel Encoder

[0047] 26: Substrate delivery quantity detection device

[0048] 27: Precursor Ink Film Detection Device

[0049] 31: Unwinding roller

[0050] 32: Clamping strap

[0051] 40: Solar cell unit

[0052] 41: First electrode

[0053] 42: Electron transport layer

[0054] 43: Perovskite layer

[0055] 44: Hole transport layer

[0056] 45: Second electrode

[0057] 51: First electrode forming apparatus

[0058] 52: Electron transport layer formation apparatus

[0059] 53: Perovskite layer formation device

[0060] 54: Hole transport layer formation device

[0061] 55: Second electrode forming apparatus

[0062] 66-68: Substrate restriction measures (mechanisms)

[0063] 100: Air Knife

[0064] 110: Slit-shaped air outlet

[0065] 111: Multiple openings

[0066] 120: Slit nozzle

[0067] 201: Region in which a liquid film composed of antisolvent is formed Detailed Implementation

[0068] (Perovskite solar cells)

[0069] Figure 1 This is a schematic diagram of an example of a perovskite solar cell unit. The photoelectric conversion element 40 has a first electrode 41, an electron transport layer 42, a photoelectric conversion layer 43, a hole transport layer 44, and a second electrode 45. The first electrode 41 or the second electrode 45 has light transmittance that allows light that facilitates photoelectric conversion to pass through.

[0070] (Apparatus and method for manufacturing perovskite solar cells)

[0071] Figure 2This is a schematic diagram of a perovskite solar cell manufacturing apparatus. An embodiment of the perovskite solar cell manufacturing apparatus 10 of the present invention includes a perovskite precursor coating unit 11, a drying unit 12, an antisolvent coating unit 13, a conveying unit 14, an antisolvent removal unit 15, and a firing unit 16. The conveying unit 14 is equipped with a belt conveying mechanism capable of conveying sheet-like substrates.

[0072] Figure 3 This is a schematic diagram of another example of a perovskite solar cell manufacturing apparatus. An embodiment of the perovskite solar cell manufacturing apparatus 10 of the present invention can manufacture using a film-like substrate. It includes a perovskite precursor coating mechanism 11, a drying mechanism 12, an antisolvent coating mechanism 13, an antisolvent removal mechanism 15, and a firing mechanism 16. Furthermore, the mechanism for conveying the strip substrate includes an unwinding roller 31, a winding roller 24, and substrate restraining mechanisms 66-68. When the substrate is supplied in the direction of the arrow in the figure, the substrate is supplied from the unwinding roller 31, and the strip substrate is conveyed under tension. Additionally, the substrate restraining mechanisms 66-68 maintain the strip substrate in a horizontal state. Here, horizontal refers to a direction perpendicular to the direction of gravity. Furthermore, horizontal conveying refers to a structure capable of holding the liquid coated on the substrate 18 within an inclination angle that prevents it from detaching from the substrate, primarily meaning an inclination angle within ±10 degrees of the horizontal.

[0073] Figure 4 This is a schematic diagram illustrating an example of a manufacturing apparatus for fabricating perovskite solar cells using a strip of flexible substrate in a roll-to-roll manner. A strip of flexible substrate 18, rolled into a cylinder shape, passes sequentially from the portion where it is rolled into a cylinder through an unwinding roller 31 supplying the substrate, and through a device for sequentially forming layers on the substrate. Specifically, it passes sequentially through a first electrode forming device 51, an electron transport layer forming device 52, a perovskite layer forming device 53, a hole transport layer forming device 54, and a second electrode forming device 55. Then, it is retrieved by a take-up roller 24. These devices 51 to 55 are equipped with… Figure 2 The coating mechanism and drying mechanism shown are mechanisms for forming each layer.

[0074] This diagram illustrates the case where the unwinding roller 31 to the take-up roller 24 are continuous, but it can also be shown as follows: Figure 3 The device is appropriately separated as shown, the strip of flexible substrate is wound into a roll and stored, and the strip of flexible substrate is then supplied to the next device in a roll. Figure 4 This describes a situation where the material is supplied to the perovskite layer forming apparatus in a roll shape and then wound into a roll shape after the perovskite layer forming process is completed.

[0075] Next, a method for manufacturing the perovskite solar cell of the present invention will be described. One embodiment of the method for manufacturing the perovskite solar cell includes a conveying step, a perovskite precursor coating step, a drying step, an antisolvent coating step, a removal step, and a firing step. Another embodiment of the method for manufacturing the perovskite solar cell may, as needed, include a step of forming a layer other than the perovskite layer.

[0076] A method for manufacturing a perovskite solar cell according to one embodiment of the present invention can be performed using an apparatus for manufacturing a perovskite solar cell according to one embodiment of the present invention. Details will be described below.

[0077] <Perovskite Precursor Coating Mechanism>

[0078] This apparatus is used to coat a perovskite precursor ink onto a substrate to form a perovskite precursor film. There are no particular limitations on the perovskite precursor coating apparatus; it can be appropriately selected depending on the purpose. Examples include air knife coating, sprayer coating, wire rod coating, spin coating, roller coating, doctor blade coating, gravure coating, and inkjet nozzles. From the viewpoint of being able to form a perovskite precursor film at any location, an inkjet nozzle is preferred.

[0079] -Perovskite precursor ink-

[0080] The perovskite precursor ink contains a solvent and at least two of one or more monovalent cations, one or more divalent metal cations, and one or more halide anions, and may also contain other components as needed.

[0081] <Solvent>

[0082] There are no particular restrictions on solvents, as long as they are capable of dissolving compounds containing one or more monovalent cations, compounds containing one or more divalent metal cations, and compounds containing one or more halide anions. They can be selected appropriately according to the purpose.

[0083] Examples of solvents include alcohols, ketones, ethers, glycol ether solvents, sulfones, and amides.

[0084] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, octanol, cyclopentanol, and cyclohexanol.

[0085] Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone.

[0086] Examples of ethers include diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane, 4-methyldioxane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenethyl ether.

[0087] Examples of glycol ether solvents include glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether, glycol monoethyl ether acetate, and triethylene glycol dimethyl ether.

[0088] Examples of sulfones include dimethyl sulfoxide.

[0089] Examples of amines include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N,N-diethylacetamide.

[0090] Hydrogen atoms in the hydrocarbon portion of the solvent can be replaced by halogen atoms, including fluorine atoms.

[0091] There are no particular restrictions on the content of solvent, and it can be selected appropriately according to the purpose. Preferably, the total solvent content in the perovskite precursor ink is less than 50% by mass.

[0092] <Monovalent cation>

[0093] In the liquid composition for forming a perovskite layer, a monovalent cation exists in an ionized state in the compound containing the monovalent cation.

[0094] Examples of monovalent cations include monovalent organic cations and monovalent inorganic cations. Preferably, the cation includes at least two or more of both monovalent organic and monovalent inorganic cations. This allows for a more complex crystal structure of the perovskite layer, thus making it less prone to cracking and improving its durability.

[0095] Examples of monovalent organic cations include, for example, alkylamine compound ions.

[0096] There are no particular limitations on the alkylamine compound ions used, and they can be appropriately selected according to the purpose. For example, methylammonium ions (CH3NH3) can be listed. + ;MA), ethylammonium ion, n-butylammonium ion, formamidinium ion (CH3(NH3)) 2+ ;FA), etc. These can be used individually or in combination of two or more.

[0097] Examples of monovalent inorganic cations include cesium ions, potassium ions, and rubidium ions. These can be used individually or in combination of two or more.

[0098] <Divalent metal cations>

[0099] In the perovskite layer-forming liquid composition, divalent metal cations exist in an ionized state in the compound containing divalent metal cations.

[0100] As divalent metal cations, there are no particular restrictions, and appropriate choices can be made according to the purpose. Examples include lead ions, indium ions, antimony ions, tin ions, copper ions, and bismuth ions. One of these can be used alone, or two or more can be used in combination.

[0101] <Halide Anions>

[0102] In the perovskite layer-forming liquid composition, halide anions exist in an ionized state in the compound containing halide anions.

[0103] As a halide anion, there are no special restrictions as long as it belongs to the 17th column of the periodic table as defined by the International Union of Pure and Applied Chemistry (IUPAC). The appropriate type can be selected according to the purpose; for example, chloride ions, bromide ions, and iodide ions can be listed. One type can be used alone, or two or more can be used together.

[0104] The preferred ratio of monovalent cations, divalent metal cations, and halide anions in the liquid composition used to form the perovskite layer is 1:1:3. However, even if the ratio is not strictly consistent with this, due to crystal defects, it is acceptable as long as the layer functions as a photoelectric conversion layer.

[0105] <Drying Mechanism>

[0106] The drying unit is used to dry the perovskite precursor film. There is no particular limitation on the degree of drying, as long as at least a portion of the solvent in the coated film is removed.

[0107] There are no particular restrictions on the heating time of the drying mechanism; it can be selected appropriately according to the purpose and adjusted according to the ink ejection volume and the performance of the printing device.

[0108] As a drying mechanism, there are no particular restrictions, and it can be selected appropriately according to the purpose. For example, hot air heaters, infrared heaters, etc. can be listed.

[0109] <Antisolvent Coating Mechanism>

[0110] This mechanism is for coating the dried perovskite precursor film with an anti-solvent in a vertical direction relative to the substrate in a manner that does not contact the perovskite precursor film.

[0111] As an antisolvent coating mechanism, there are no particular restrictions as long as it has a slit nozzle and coats the liquid without contacting the substrate; the appropriate mechanism can be selected based on the purpose. A slit nozzle refers to a nozzle with a narrow, slit-shaped outlet that can spray liquid out in a relatively uniform film from the slit. For example… Figure 12 The nozzle shown in the figure indicates that the antisolvent coating mechanism 13 has a slit nozzle 120. The antisolvent coating mechanism 13 may have one slit nozzle or multiple slit nozzles.

[0112] When the antisolvent coating mechanism is a mechanism that applies droplets by water pressure or its own weight without the need for air, it is preferred from the viewpoint of preventing coating deviation caused by airflow.

[0113] Figure 5 This is a perspective illustration of an example of a manufacturing apparatus for a perovskite solar cell according to one embodiment of the present invention, showing antisolvent coating and removal performed using an antisolvent coating mechanism and an antisolvent removal mechanism.

[0114] On a precursor ink film 19, on which precursor ink has been coated by a perovskite precursor coating mechanism 11 and excess solvent has been removed by a drying mechanism, an antisolvent 17 is coated from above by an antisolvent coating mechanism 13. The precursor ink film 19 coated with antisolvent 17 is conveyed to an antisolvent removal mechanism 15 by a moving substrate 18 to remove the antisolvent 17.

[0115] By maintaining the substrate in a horizontal position, the antisolvent can be prevented from falling off the substrate before reaching the antisolvent removal mechanism. Furthermore, the antisolvent coating time is determined by the configuration of the antisolvent coating and removal mechanisms and the substrate transport speed; therefore, by controlling the transport speed, the antisolvent coating time can be controlled.

[0116] The antisolvent coating mechanism effectively utilizes a slit nozzle shape. For example, the antisolvent coating mechanism is designed to achieve uniform coating on a surface as the substrate is transported by means of linear coating through a slit nozzle, which is configured perpendicular to the transport direction of the substrate.

[0117] The anti-solvent coating mechanism effectively utilizes a slit nozzle shape and is configured perpendicular to the substrate transport direction, thereby enabling uniform coating on the surface as the substrate is transported.

[0118] <Conveying Mechanism>

[0119] The conveying mechanism 14 horizontally conveys the substrate at least after the antisolvent is applied by the antisolvent coating mechanism until the antisolvent is removed by the antisolvent removal mechanism. The conveying mechanism 14 is a roll-to-roll conveying mechanism. Figure 6A and Figure 6B The conveying mechanism 14 will be described.

[0120] Figure 6A This is a schematic diagram illustrating an example of a conveying mechanism in a perovskite solar cell manufacturing apparatus according to one embodiment of the present invention. Figure 6B This is a schematic diagram illustrating another example of a conveying mechanism in a perovskite solar cell manufacturing apparatus according to one embodiment of the present invention.

[0121] like Figure 6A As shown, the conveying mechanism 14 includes an unwinding roller 31, a take-up roller 24, and a clamping roller 22. The unwinding roller 31 rotates under the drive of a motor, thereby conveying the substrate before the formation of the perovskite precursor film. The take-up roller 24 rotates under the drive of a motor, thereby taking up the substrate after the formation of the perovskite precursor film. The clamping roller 22 is a roller that clamps the substrate on the upstream side of the take-up roller, contacts the substrate, and constrains the substrate at the contact surface by means of negative pressure adsorption or the like. In addition, the speed of the substrate can be controlled by controlling the roller with a drive motor.

[0122] In addition, such as Figure 6B As shown, the conveyor mechanism 14 can also be equipped with a clamping belt 32 instead. Figure 6A The conveying mechanism shown includes a clamping roller 22. The belt portion of the clamping belt 32 contacts the substrate, clamping the substrate via this contact portion. The substrate clamping mechanism uses a structure that constrains the substrate and belt using methods such as negative pressure adsorption.

[0123] The conveying mechanism is equipped with a wheel encoder 25 for detecting the conveying speed.

[0124] The conveying mechanism controls the motor based on the target value and the speed detection value obtained from the detection pulses of the sampling wheel encoder, thereby controlling the conveying speed.

[0125] In the antisolvent coating process of the present invention, it is effective to control the coating amount of antisolvent to the minimum required level in order to prevent the antisolvent from scattering into the air. Figure 7 An example of a configuration for optimizing the amount of antisolvent coating is shown.

[0126] The conveying mechanism can have a substrate delivery amount detection device 26 or a precursor ink film detection device 27 on the substrate delivery path. The conveying mechanism 14 can have a substrate delivery amount detection device 26 or a precursor ink film detection device 27 on the substrate delivery path. The substrate delivery amount detection device 26 can use a detection mechanism of a wheel encoder 25 set on the rotating shaft of the clamping belt 32. The clamping belt 32 contacts the substrate and rotates along with it through the substrate delivery amount detection device, thereby detecting the delivery amount of the substrate according to the rotation amount of the wheel encoder 25. Based on the detection result, the amount of movement from the perovskite precursor coating mechanism to the antisolvent coating mechanism is determined, and the spraying time of the antisolvent coating mechanism is controlled.

[0127] Furthermore, it is preferable to stop ejection after conveying the patterned amount of the perovskite precursor coating, and only coat the anti-solvent on the perovskite precursor film. In the precursor ink film inspection device, the anti-solvent coating is triggered by pre-setting inspection marks on the substrate or by detecting the start of printing of the perovskite precursor film.

[0128] <Antisolvent Removal Mechanism>

[0129] The antisolvent removal mechanism is a mechanism for removing the antisolvent from a perovskite precursor film coated with the antisolvent. There is no particular limitation on the extent of removal, as long as at least a portion of the antisolvent in the perovskite precursor or other films is removed.

[0130] There are no particular limitations on the antisolvent removal mechanism; it can be appropriately selected according to the purpose. For example, non-contact, linear air knives can be used effectively.

[0131] Antisolvent removal mechanisms can be implemented by applying external force to the antisolvent, such as using an air knife to blow air through a slit-like gap. Figure 5 In this configuration, the anti-solvent coating mechanism is parallel to the width direction of the substrate, but it can also be configured as follows: Figure 9 As shown, it is arranged with an inclined angle relative to the width direction of the substrate. In this case, if the inclination angles of the antisolvent coating mechanism and the removal mechanism are the same (parallel to each other), the antisolvent coating time in the width direction can be kept constant, which is therefore preferable.

[0132] Figure 8A and Figure 8B This is an explanatory diagram of the air nozzles of the components constituting air knives 100, 100a, and 100b. Figure 8A and Figure 8B And later Figure 9 The air knife 100a is the same. For example... Figure 8A As shown, a slit-shaped air nozzle 110 extending in the width direction of the air knife can be formed. Additionally, as... Figure 8B As shown, it can also be formed as multiple air nozzles 111 arranged in the width direction of the air knife.

[0133] A typical antisolvent removal mechanism sets the air knife 100 as follows: Figure 9 The diagram shows an inclination (angle β) relative to the width direction of the substrate. As indicated by arrow B, the removed antisolvent moves along the width direction of the substrate 18. The shaded area 201 is the area where a liquid film composed of the antisolvent is formed.

[0134] exist Figure 9In the example, the air knife 100 ejects air vertically from its side having an air nozzle. The angle between this side and the width direction of the substrate 18, and the angle between the air ejection direction A3 and the substrate transport direction A1 (the relative movement direction between the object being blown and the air knife), are both magnitude β. In this specification, the angle of inclination of the side of the air knife having the air nozzle relative to the direction perpendicular to the width direction of the substrate (the substrate transport direction A1) in the substrate surface is called the air knife angle.

[0135] In order to gain time to move the antisolvent a certain distance across the substrate width, the air knife angle needs to be increased. Therefore, a deviation occurs in the time until the antisolvent is removed along the width of the substrate.

[0136] Therefore, in this embodiment, such as Figure 10 As shown, by using an air knife 100 that changes the direction of air ejection at the center of the substrate width, the distance that the removed antisolvent moves, as indicated by arrow A2, is suppressed to about half the width of the substrate 18. Figure 10 The air knife 100 is a single-component structure, characterized in that the slit of the nozzle is inclined on the front and inner sides.

[0137] Specifically, the air is blown towards the ends of the liquid film in the width direction from the center, in a direction inclined relative to the conveying direction A1. Arrow A3 in the figure indicates the direction of air ejection. In the illustrated example, the air knife 100 also ejects air vertically from the side with the air nozzle, and the air knife angle and the angle of the air ejection direction A3 relative to the conveying direction A1 are both of the same magnitude α.

[0138] Therefore, the size of the air knife angle can be suppressed to a small degree, such as α (< β). This reduces the substrate width deviation during the time until the antisolvent is removed, thus improving the uniformity of the perovskite film.

[0139] In addition, such as Figure 11 As shown, by arranging short paired air knife components 100a and 100b in parallel, it is also possible to suppress the distance the removed antisolvent travels, reduce the substrate width direction deviation during the time until the antisolvent is removed, and improve the uniformity of the perovskite film.

[0140] The above is just one example; the invention has unique effects in all of the following embodiments.

[0141] In the description of each form, the symbol following the name is an example of the corresponding component, and this description includes but is not limited to such component example.

[0142] (Form 1)

[0143] The antisolvent removal mechanism 15 removes the antisolvent adhering to the plane of the substrate 18 by blowing air from the air knife 100. The air is blown towards the ends of the liquid film in the width direction perpendicular to the relative movement direction of the substrate 18 and the air knife 100, with the air blowing in an inclined direction relative to the relative movement direction.

[0144] In this specification, the “center” of the liquid film in the width direction perpendicular to the relative movement direction of the air knife refers to the central 1 / 3 of the width of the liquid film in the width direction perpendicular to the relative movement direction of the air knife after dividing the entire width of the liquid film in the width direction perpendicular to the relative movement direction of the air knife into three equal parts.

[0145] Therefore, by pushing the antisolvent liquid from the center of the liquid film toward both ends, the deviation in liquid contact time of the object in the width direction can be reduced.

[0146] (Form 2)

[0147] In the antisolvent removal mechanism 15 described in form 1, the center is the range of the central 1 / 7 after dividing the total width of the antisolvent in the width direction into seven equal parts.

[0148] This effectively reduces the deviation in liquid contact time along the width of the object.

[0149] (Form 3)

[0150] In the antisolvent removal mechanism 15 described in form 1 or 2, the air knife 100 has a slit-shaped air nozzle extending in the width direction or a plurality of open-shaped air nozzles arranged in the width direction, the direction of extension or arrangement being inclined relative to the width direction such that the ends of both sides are further downstream than the center in the relative movement direction.

[0151] Therefore, the deviation in liquid contact time in the width direction of the object can be reduced by the shape of the air knife with an air nozzle.

[0152] (Form 4)

[0153] In the antisolvent removal mechanism 15 described in form 1 or 2, the air knife 100 has a slit-shaped or a plurality of open-shaped air nozzles extending in the width direction, and is composed of a pair of air knife 100 components, each half of the width direction from the center to the ends of both sides of the total width of the antisolvent. The pair of air knife 100 components are configured such that the ends of the central side overlap each other in the relative movement direction, and the direction of extension or arrangement is inclined relative to the width direction, such that the ends of the end sides are further downstream in the relative movement direction than the ends of the central side.

[0154] This enables the miniaturization of the air knife used here.

[0155] (Form 5)

[0156] In the antisolvent removal mechanism 15 according to any one of the forms 1 to 4, the substrate 18 is a continuous sheet supplied from a supply section that is in the form of a roll.

[0157] Therefore, compared with sliced ​​objects, the production efficiency of the liquid film removal mechanism can be improved.

[0158] (Form 6)

[0159] In the antisolvent removal mechanism 15 described in aspect 5, a support device is provided to support the continuous sheet-like substrate 18 at the part blown by air from the air knife 100.

[0160] This allows for the stable removal of the liquid film.

[0161] (Form 7)

[0162] A perovskite film forming apparatus for forming a perovskite film on a substrate includes: a perovskite precursor coating unit 11 for applying a perovskite precursor solution to the substrate; an antisolvent coating unit 13 for applying a precipitation liquid to the substrate on which the precursor solution has been applied, for causing perovskite crystals to precipitate onto the substrate; and an antisolvent removal unit 15 for removing the antisolvent from the substrate after the precipitation liquid has been applied by the antisolvent coating unit 13. The antisolvent removal unit 15 is one of any of embodiments 1 to 6. The precipitation liquid is preferably an antisolvent for perovskite.

[0163] This allows for the formation of a uniform perovskite film.

[0164] (Form 8)

[0165] A liquid film removal method removes antisolvent adhering to a plane of a substrate 18 by blowing air from an air knife 100, wherein air is blown in a width direction perpendicular to the relative movement direction of the substrate 18 and the air knife 100 in such a way as to flush away the liquid antisolvent from the center toward the ends of both sides respectively.

[0166] This reduces the deviation in liquid contact time along the width of the object.

[0167] (Form 9)

[0168] A method for forming a perovskite film on a substrate includes: a precursor solution application step, in which a perovskite precursor solution is applied to the substrate; a precipitation liquid application step, in which a precipitation liquid for precipitating perovskite crystals onto the substrate having the precursor solution applied is applied; and a liquid film removal step, in which the antisolvent on the substrate is removed after the precipitation liquid application step has been applied. As the liquid film removal step, the liquid film removal method described in aspect 8 is used.

[0169] This allows for the formation of a uniform perovskite film.

[0170] (Form 10)

[0171] In the method for manufacturing a perovskite solar cell, which includes a perovskite film formation step, the perovskite film formation method described in Form 9 is used in the perovskite film formation step.

[0172] This enables the provision of solar cells with uniform perovskite layers and excellent performance.

[0173] (Form 11)

[0174] The perovskite solar cell is manufactured by the perovskite solar cell manufacturing method described in Form 10.

[0175] Therefore, having a uniform perovskite layer allows it to perform well as a solar cell.

[0176] <Firing Mechanism>

[0177] A sintering apparatus is used to sinter the perovskite precursor film after the antisolvent has been removed. There are no particular limitations on the sintering apparatus as long as it can sinter the perovskite precursor film; it can be appropriately selected according to the purpose. For example, a heating apparatus can be used to heat the film to the sintering temperature. Examples of heating apparatuses include hot air heaters and infrared heaters.

[0178] The embodiments of the present invention have been described in detail above. The above embodiments illustrate specific examples of implementing the present invention. The technical scope of the present invention includes, but is not limited to, the illustrated embodiments. Without departing from the scope of the invention as defined in the claims, various design changes can be made, such as alterations, additions, and deletions of constituent elements. New embodiments with design changes combine the effects of combined embodiments with the individual effects of the changes. In the described embodiments, the content enabling such design changes is emphasized by expressions such as "in this embodiment" or "in this embodiment," but design changes are permitted even without such expressions. Any combination of the above constituent elements is also valid as a form of the present invention.

[0179] [Example]

[0180] The present invention will now be described in more detail based on embodiments, but the present invention includes, but is not limited to, the following embodiments.

[0181] (Example 1)

[0182] <Preparation of Electron Transport Layer Ink>

[0183] The tin oxide colloidal solution (S-8 manufactured by Tamaki Chemical Co., Ltd.) was diluted with an equal volume of ultrapure water. 0.1 wt% of Triton X (manufactured by Sigma-Aldrich) was added as a surfactant.

[0184] <Preparation of Perovskite Precursor Ink>

[0185] In a glove box under a nitrogen atmosphere, 1.3 g, 16.0 g, 48.38 g, 0.75 g, 0.21 g, and 1.01 g of cesium iodide, formamidinium iodide (compounds containing one or more monovalent cations), lead iodide, lead bromide (compounds containing one or more divalent metal cations), methylammonium bromide, and methylammonium chloride (compounds containing one or more halide anions) were weighed out, respectively. Then, 16.7 g and 80.7 g of dimethyl sulfoxide and N,N-dimethylacrylamide were added, respectively, at 20°C under atmospheric conditions. A clear perovskite precursor liquid composition was then prepared by stirring.

[0186] <Preparation of Hole Transport Layer Ink>

[0187] Measure 3g of PTAA (Sigma-Aldrich, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) and dissolve it in 100g of o-dichlorobenzene.

[0188] <Fabrication of Photoelectric Conversion Components>

[0189] use Figure 2 The apparatus shown is used to fabricate photoelectric conversion elements. A substrate is placed on a strip conveyor, and films are formed layer by layer, starting with the electron transport layer. Laser processing is then performed as needed to create patterns.

[0190] A UV / O3 cleaning process was performed on a 300 mm² square ITO substrate with a strength of 10 Ω / sq. An electron transport layer ink was then applied using an electron transport layer coating apparatus (die coating machine), and the solvent in the ink was dried at 170°C for 30 seconds using a drying apparatus. The resulting electron transport layer had a thickness of 45 nm. Then, for multi-unit processing, the ITO was cut using a laser processing machine.

[0191] Next, a precursor ink is coated onto the substrate using a perovskite precursor coating machine (die coating machine). The solvent in the precursor ink is dried using a drying device. Then, an antisolvent coating machine (slit nozzle method) is used to coat the precursor ink with an antisolvent (chlorobenzene) film. Figure 9 The shown antisolvent removal mechanism removes excess solvent, and the final crystallization is carried out at 170°C for 30 seconds using a sintering mechanism. The resulting perovskite layer has a thickness of 450 nm. Furthermore, for the antisolvent coating mechanism and the antisolvent removal mechanism, [the following is used]... Figure 5 The structure shown.

[0192] Next, a hole transport layer ink was applied using a hole transport layer coating machine (die coating machine), and the solvent of the hole transport layer ink was dried at 170°C for 30 seconds using a drying device. The resulting hole transport layer had a film thickness of 60 nm. Then, a laser processing machine was used to expose the ITO at the junctions between the cells.

[0193] Next, a 100nm gold film is formed by vacuum deposition using a vacuum deposition mask.

[0194] Finally, the sealing film and UV barrier film are bonded together using a hot press laminator. Through these operations, the photoelectric conversion element module is obtained.

[0195] <Evaluation of photoelectric conversion characteristics>

[0196] For the obtained photoelectric conversion element module, a solar energy simulation device (AM1.5, 100 mW / cm²) was used. 2 The photoelectric conversion characteristics (initial characteristics) were evaluated using a DC voltage-current device (KEYSGIHT B2910BL) controlled by System House Sunrise's solar cell IV measurement software while being exposed to light. The photoelectric conversion module consisted of 15 units connected in series, enabling evaluation of each individual cell. The results are shown in Table 1.

[0197] <Example 2>

[0198] Except for changing the coating method in the coating apparatus (electron transport layer coating mechanism, perovskite precursor coating mechanism, hole transport layer coating mechanism) of Example 1 from a die-coating machine to an inkjet coating method, a series of evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0199] <Example 3>

[0200] The substrate in Example 2 was changed to a 300mm wide ITO film roll, and... Figure 3The apparatus shown was used to fabricate photoelectric conversion elements in a roll-to-roll manner (with the substrate being horizontally conveyed). Otherwise, a series of evaluations were performed in the same manner as in Example 2. Furthermore, the photoelectric conversion element module was cut into 300mm square dimensions, the same as in Example 2, by dividing the film roll into 300mm wide units. The results are shown in Table 1.

[0201] <Example 4>

[0202] In addition to removing the removal mechanism used in Example 1, Figure 9 The organization shown has been changed to Figure 10 Apart from the apparatus shown, a series of evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0203] <Comparative Example 1>

[0204] Except for changing the antisolvent coating mechanism in Example 1 to a spray type, a series of evaluations were performed in the same manner as in Example 1. Furthermore, a total of five nozzles were evenly arranged with a width of 300 mm, and the gap between the substrate and the nozzle surface was 10 cm. The results are shown in Table 1.

[0205] [Table 1]

[0206]

[0207] Furthermore, it has been found that by coating each layer of the photoelectric conversion element using inkjet printing (Example 2), compared to coating using a die-coating machine (Example 1), the standard deviation is smaller and the deviation between units is smaller. Moreover, by employing a roll-to-roll method (horizontal substrate transport) (Example 3), the effect becomes even more significant.

[0208] In addition, as a removal mechanism, due to the change to Figure 10 The mechanism shown thus suppresses the deviation in time from the application of the antisolvent to its removal, thereby improving both the average value and standard deviation compared to Example 1 (Example 4).

[0209] Examples of various embodiments of the present invention are as follows:

[0210] <1>

[0211] An apparatus for manufacturing a perovskite solar cell, characterized in that it comprises:

[0212] The perovskite precursor coating mechanism coats a substrate with perovskite precursor ink to form a perovskite precursor film;

[0213] The drying unit dries the perovskite precursor film;

[0214] The antisolvent coating mechanism coats the dried perovskite precursor film with an antisolvent from a slit nozzle in a direction perpendicular to the substrate, without contacting the perovskite precursor film.

[0215] A conveying mechanism horizontally conveys the substrate coated with the antisolvent;

[0216] The antisolvent is removed from the perovskite precursor membrane transported horizontally; and

[0217] The sintering mechanism sinters the perovskite precursor film from which the antisolvent has been removed.

[0218] <2>

[0219] The perovskite solar cell manufacturing apparatus according to <1> above is characterized in that the perovskite precursor coating mechanism is an inkjet nozzle.

[0220] <3>

[0221] The manufacturing apparatus for perovskite solar cells according to <1> or <2> above is characterized in that the conveying mechanism is a roll-to-roll method.

[0222] <4>

[0223] The perovskite solar cell manufacturing apparatus according to <3> above is characterized in that the antisolvent coating mechanism coats the antisolvent in the width direction of the substrate in the roll-to-roll manner.

[0224] <5>

[0225] The apparatus for manufacturing perovskite solar cells according to any one of <1> to <4> above is characterized in that the removal mechanism is an air knife that blows air from the center of the liquid film toward both ends in the width direction of the substrate, toward the ends, in a direction inclined relative to the relative movement direction.

[0226] <6>

[0227] According to the manufacturing apparatus for a perovskite solar cell described in <5> above, the center is defined as the range of the center 1 / 7 after dividing the total width of the liquid film in the width direction into seven equal parts.

[0228] <7>

[0229] The apparatus for manufacturing perovskite solar cells according to <5> above is characterized in that:

[0230] The air knife has slit-shaped or multiple opening-shaped air nozzles extending in the width direction.

[0231] The direction of extension or arrangement is inclined relative to the width direction, such that the ends of both sides become the downstream side of the center in the relative movement direction.

[0232] <8>

[0233] A method for manufacturing a perovskite solar cell, characterized by comprising the following steps:

[0234] The perovskite precursor ink coating process involves coating a perovskite precursor ink onto a substrate to form a perovskite precursor film;

[0235] The drying process involves drying the perovskite precursor film.

[0236] The antisolvent coating process, having a slit nozzle shape, coats the dried perovskite precursor film with antisolvent in a direction perpendicular to the substrate without contacting the substrate.

[0237] In the conveying process, the substrate coated with the aforementioned anti-solvent is conveyed horizontally;

[0238] The removal process involves removing the antisolvent from the perovskite precursor film coated with the antisolvent; and

[0239] The firing process involves firing the perovskite precursor film after the antisolvent has been removed.

[0240] <9>

[0241] The method for manufacturing a perovskite solar cell according to <8> above is characterized in that, in the conveying process, the substrate is conveyed horizontally.

[0242] <10>

[0243] The method for manufacturing a perovskite solar cell according to <8> or <9> above is characterized by further comprising:

[0244] The first carrier transport layer precursor ink coating process involves coating a first carrier transport layer precursor ink onto a substrate to form a first carrier transport layer; and

[0245] The second carrier transport layer precursor ink coating process involves coating the substrate with the second carrier transport layer precursor ink to form the second carrier transport layer.

Claims

1. An apparatus for manufacturing perovskite solar cells, characterized in that, include: The perovskite precursor coating mechanism coats a substrate with perovskite precursor ink to form a perovskite precursor film; The drying unit dries the perovskite precursor film; The antisolvent coating mechanism coats the dried perovskite precursor film with an antisolvent from a slit nozzle in a direction perpendicular to the substrate, without contacting the perovskite precursor film. A conveying mechanism horizontally conveys the substrate coated with the antisolvent; The antisolvent is removed from the perovskite precursor membrane transported horizontally; and The sintering mechanism sinters the perovskite precursor film from which the antisolvent has been removed.

2. The apparatus for manufacturing perovskite solar cells according to claim 1, characterized in that, The perovskite precursor coating mechanism is an inkjet nozzle.

3. The apparatus for manufacturing perovskite solar cells according to claim 1 or 2, characterized in that, The conveying mechanism is a roll-to-roll type.

4. The apparatus for manufacturing perovskite solar cells according to claim 3, characterized in that, The antisolvent coating mechanism applies the antisolvent in the width direction of the substrate in the roll-to-roll configuration.

5. The apparatus for manufacturing perovskite solar cells according to claim 1 or 2, characterized in that, The removal mechanism is an air knife that blows air from the center of the liquid film toward both ends in the width direction of the substrate, toward the ends, in a direction inclined relative to the relative movement direction.

6. The apparatus for manufacturing perovskite solar cells according to claim 5, characterized in that, The center is the area within the central 1 / 7 of the total width of the liquid film in the width direction after dividing it into seven equal parts.

7. The apparatus for manufacturing perovskite solar cells according to claim 5, characterized in that... : The air knife has slit-shaped or multiple opening-shaped air nozzles extending in the width direction. The direction of extension or arrangement is inclined relative to the width direction, such that the ends of both sides become the downstream side of the center in the relative movement direction.

8. A method for manufacturing a perovskite solar cell, characterized in that, The process includes the following steps: The perovskite precursor ink coating process involves coating a perovskite precursor ink onto a substrate to form a perovskite precursor film; The drying process involves drying the perovskite precursor film. The antisolvent coating process, having a slit nozzle shape, coats the dried perovskite precursor film with antisolvent in a direction perpendicular to the substrate without contacting the substrate. In the conveying process, the substrate coated with the antisolvent is conveyed horizontally; The removal process involves removing the antisolvent from the perovskite precursor film coated with the antisolvent; and The firing process involves firing the perovskite precursor film after the antisolvent has been removed.

9. The method for manufacturing a perovskite solar cell according to claim 8, characterized in that, In the conveying process, the substrate is conveyed horizontally.

10. The method for manufacturing a perovskite solar cell according to claim 8 or 9, characterized in that... Further including: The first carrier transport layer precursor ink coating process involves coating a first carrier transport layer precursor ink onto a substrate to form a first carrier transport layer; and The second carrier transport layer precursor ink coating process involves coating the substrate with the second carrier transport layer precursor ink to form the second carrier transport layer.

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