Manufacturing and related uses, products, and solar cells of perovskite solar cells

Abstract

To provide solar cells, especially large-scale solar cells, efficiently and cost-effectively. [Solution] In an ink printing operation on the surface of an intermediate product in the manufacture of a perovskite solar cell, the use of a solution as an ink to provide a surface film that can be converted into a functional layer of a perovskite solar cell by drying, The ink printing operation uses a print head having at least 100 nozzles and / or at least 0.3 m of the surface. 2 The ink is deposited over the region, The functional layer is one of an electron transport layer, a perovskite layer, and a hole transport layer. The solution is used to contain the precursor of the functional layer in a polar solvent containing alcohol and / or ether.

Description

[Technical Field]

[0001] This disclosure relates to a perovskite solar cell and the manufacture of the same, wherein the solar cell includes a substrate, the surface of which is provided with electrode wiring, and further comprises a laminate of a plurality of functional layers in the order described, which are an electron transport layer, a perovskite layer, and a hole transport layer on the substrate side. This disclosure also relates to a method for manufacturing a product that can be processed into a perovskite solar cell or is a perovskite solar cell, in particular a method for manufacturing the foregoing, and a printer and print head used in this method. This disclosure also relates to the use of a solution as an ink in an ink printing operation on the surface of an intermediate product in the manufacture of a perovskite solar cell, which provides a surface film that can be converted into a functional layer of a perovskite solar cell by drying. [Background technology]

[0002] Perovskite solar cells (PSCs), formed using a perovskite layer between the functional layer, i.e., the electron transport layer and the hole transport layer, have rapidly developed into one of the most promising photovoltaic technologies in the past decade, achieving power conversion efficiencies (PCE) such as 26%. Known fabrications of perovskite solar cells and such cells based on organic semiconductors include, for example, - Zhang et al., “Ion-modulated radical doping of spiro-OMeTAD for more efficient and stable perovskite solar cells”, Science, 28 July 2022, Vol 377, Issue 6605 pp. 495-501 (DOI: 10.1126 / science.abo2757), and - You et al., “Bifunctional hole-shuttle molecule for improved interfacial energy level alignment and pass defectivation in perovskite solar cells”, Nature Energy, 8, pp. 515-525, 2023 (https: / / doi.org / 10.1038 / s41560-023-01249-0) It is shown here.

[0003] A known product, PEDOT:PSS, is a combination of polymer components, such as poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate, used as a substrate for forming the hole transport layer in perovskite solar cells. This product is available, for example, from Xi'an Polymer Light Technology Corp. in Xi'an, China, or from Heraeus Epurio GmbH (CHEMPARK Leverkusen, 51368 Leverkusen, Germany) under the trade name CLEVIOS. It is thought to provide stability to the hole transport layer in perovskite solar cells, particularly in regularly structured nip-type cells. Other known polymers suitable as substrates for forming such a polymer component are poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) and poly(3-hexylthiophene)(P3HT). These polymer components include conductive polymers such as thiophene-based polymers. The hole transport layer of a perovskite solar cell further contains a spiro compound as a charge transfer agent.

[0004] The solution for forming the functional layer of the PSC is, - DK Lee et al., “Precursor Engineering for a Large-Area Perovskite Solar Cell with >19% Efficiency”, ACS Energy Letters 2019 4 (10), 2393-2401, and - M. Yavari et al., “Greener, Nonhalogenated Solvent Systems for Highly Efficient Perovskite Solar Cells”, Advanced Energy Materials, April 2018 (21):1800177 It has been reported.

[0005] The attempt to enable inkjet printing of the functional layer of PSC is - F. Schackmar et al., “Perovskite Solar Cells with All-Inkjet-Printed Absorber and Charge Transport Layers”, Adv. Mater. Technol. 2021, 6 (2), 2000271, - B. Gao et al., “Flexible CH3NH3PbI3perovskite solar cells with high stability based on all inkjet printing”, Solar Energy, 230, 2021, 598-604, and - A. Gheno et al., “Toward Highly Efficient Inkjet-Printed Perovskite Solar Cells Fully Processed Under Ambient Conditions and at Low Temperature”, Solar RRL, 2018, 2 (11), pp.1800191. It has been reported.

[0006] Known conditioning methods prior to functional layer deposition include cleaning, annealing, plasma treatment, flame or corona treatment, and vacuum annealing. Several conditioning methods are described in AB Djurisic et al., “Surface treatments of indium tin oxide substrates: comprehensive investigation of mechanical, chemical, thermal, and plasma treatments”, Proc. SPIE 4464, Organic Light-Emitting Materials and Devices V, (27 February 2002). J. Liu et al., “Effect of surfactants on the structure and photoelectric properties of ITO films by sol-gel method”, Rare Metals 29, 143-148 (2010) describes surfactant-based conditioning. [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of the present invention is to substantially improve upon the shortcomings of the prior art described above. The object of the present invention is to enable the efficient provision of solar cells, particularly large solar cells, in a cost-effective manner. The object of the present invention is to facilitate the manufacture of solar cells, particularly large solar cells. Avoiding the excessive use of hazardous substances contributes to achieving this objective. [Means for solving the problem]

[0008] In this regard, the present disclosure relates to the use of a solution as an ink in an ink printing operation, in particular an inkjet printing operation, to provide a surface film on a surface, preferably a conditioned plasma-treated surface, in particular the surface of an intermediate product in the manufacture of a perovskite solar cell, preferably a conditioned plasma-treated surface, which can be converted into a functional layer of a perovskite solar cell by drying, wherein the ink printing operation has at least 100, preferably at least 200 nozzles and / or at least 0.3 m of the surface 2 , more preferably at least 0.5m 2 or 1m 2 A printhead is used to deposit ink over a region, preferably with a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, more preferably 3 to 20 pL, wherein the functional layer is an electron transport layer, and the solution contains a precursor of the functional layer in a polar solvent containing alcohol and / or ether. The surface can be the surface of an inorganic material and is plasma-treated with a surfactant, preferably a nonionic surfactant, and conditioning concepts from the prior art mentioned earlier regarding conditioning may be used for this purpose.

[0009] The solvent preferably comprises at least one of alcohols, preferably ethylene glycol, n-propanol, glycerol, isopropoxyethanol, and 2-amino-1-2-methyl-propanol, and the viscosity of the solution is preferably 7 mPa·s to 14 mPa·s, more preferably 9 mPa·s to 12 mPa·s. The solvent more preferably comprises water, ethylene glycol, and glycerol. These viscosities and the viscosities described below are dynamic viscosities measured in particular according to ASTM D7042-2021.

[0010] Drying preferably involves exposing the surface film to a combination of heating and near-infrared irradiation.

[0011] The precursor preferably contains dispersed tin oxide, preferably as particles having a diameter D50 of 0.1 μm to 0.3 μm, and more preferably as particles having a D50 of 0.15 μm to 0.25 μm.

[0012] This disclosure also relates to the use of a solution as an ink in an ink printing operation, particularly an inkjet printing operation, to provide a surface film on a surface (the surface of the electron transport layer of a perovskite solar cell, preferably a conditioned plasma-treated surface), particularly on the surface of an intermediate product in the manufacture of a perovskite solar cell, which can be converted into a functional layer of a perovskite solar cell by drying, wherein the ink printing operation has at least 100, preferably at least 200 nozzles and / or at least 0.3 m of the surface 2 , more preferably at least 0.5m 2 or 1m 2 A printhead is used to deposit ink over a region, preferably with a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, more preferably 3 to 20 pL, wherein the functional layer is a perovskite layer, and the solution contains a precursor of the functional layer in a polar solvent containing alcohol and / or ether. The surface can be the surface of an inorganic material and is plasma-treated with a surfactant, preferably a nonionic surfactant, and conditioning concepts from the prior art mentioned earlier regarding conditioning may be used for this purpose.

[0013] The solvent preferably contains an alcohol group and an ether group, such as 2-methoxyethanol and / or methoxypropanol. For example, the viscosity of the solution is preferably 2.5 mPa·s to 5.5 mPa·s, for example 3 mPa·s to 5 mPa·s, more preferably 3 mPa·s to 4 mPa·s. The solvent preferably does not contain water, and preferably does not contain either DMF or DMSO.

[0014] Drying preferably involves exposing the surface film to a combination of air drying (preferably using compressed air, such as compressed air exceeding 0.2 MPa directed towards the surface) and annealing.

[0015] The precursor typically contains a lead salt containing iodine ions and acetate ions, and may be, for example, a generally known perovskite layer precursor from the prior art mentioned above that exhibits a perovskite layer.

[0016] The present disclosure also relates to the use of a solution as an ink for providing a surface film convertible into a functional layer of a perovskite solar cell by drying on a surface (the surface of the perovskite layer of the perovskite solar cell, preferably a conditioned and plasma-treated surface), particularly the surface of an intermediate product in the manufacture of a perovskite solar cell, where the ink printing operation has at least 100, preferably at least 200 nozzles, and / or deposits ink over an area of at least 0.3 m 2 more preferably at least 0.5 m 2 or 1 m 2 using a print head, preferably a print head adjusted to a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, more preferably 3 to 20 pL. The functional layer is a hole transport layer, and the solution contains a precursor of the functional layer in a polar solvent containing alcohol and / or ether, preferably an aromatic ether, particularly anisole. The viscosity of the solution is preferably 0.5 mPa·s to 1.0 mPa·s.

[0017] The precursor may be one of the prior arts mentioned above that exhibits a hole transport layer, preferably containing spiro-OMeTAD and / or PTAA, and typically contains a lead salt containing iodine ions and acetate ions, and may be, for example, a generally known perovskite layer precursor from the prior art mentioned above that exhibits a perovskite layer.

[0018] Due to the above-described usage characteristics, excellent wettability for forming a high-quality surface film is ensured while suppressing the possibility of clogging of the print head, particularly an industrial print head.

[0019] The above substrate is glass, glass coated with ITO (indium tin oxide), FTO (fluorine-doped tin oxide) or TCO (transparent conductive oxide), PEN (polyethylene naphthalate), or a combination of two or more of these materials, and preferably can withstand temperatures up to at least 120°C.

[0020] For each of the above usages, the solution used may be filled into an industrial print head, or particularly a print head for an ink printing operation for depositing ink at a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL in an area of at least 0.3 m on the surface. 2 The print head has at least 100 nozzles, and in an ink printing operation, the solution is filled as an ink for providing a surface film that can be converted into a functional layer of a perovskite solar cell by drying.

[0021] On an area of at least 0.3 m on the surface 2 An inkjet printer for an ink printing operation for depositing ink at a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL may include a print head.

[0022] For each of the above usages, according to the present invention, a method suitable for the usage is provided. Therefore, the present disclosure also relates to a method for manufacturing a product that can be processed into a perovskite solar cell or is a perovskite solar cell, which includes a substrate, has electrode wiring on the surface of the substrate, and further includes a laminate of a plurality of functional layers, namely an electron transport layer, a perovskite layer, and a hole transport layer, in the described order on the substrate side so as to form a perovskite solar cell. Here, the product At least 0.3 m of the surface obtained from conditioning2 In the region, a surface film convertible to one of the functional layers is deposited using the ink printing operation of the printer described in claim 12, with a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, and The above deposition process includes evaporating the solvent deposited from the printer's print head, thereby converting the surface film into one of the above functional layers. It is manufactured by [company name].

[0023] Conditioning includes at least one operation selected from cleaning, annealing, plasma treatment, flame treatment, or corona treatment, and vacuum annealing at a temperature of 90°C to 180°C for 5 to 45 minutes.

[0024] This method makes it possible to provide a method for manufacturing a product which is a perovskite solar cell comprising a substrate, having electrode wiring on the surface of the substrate, and further comprising a laminate of multiple functional layers in the described order, the substrate side being an electron transport layer, a perovskite layer, and a hole transport layer, the method comprising repeating the above method with conditioning as a further operation before deposition in order to form each of the functional layers. This method makes it possible to efficiently obtain a perovskite solar cell, in particular a large-area perovskite solar cell, comprising a substrate, having electrode wiring on the surface of the substrate, and further comprising a laminate of multiple functional layers in the described order, the substrate side being an electron transport layer, a perovskite layer, and a hole transport layer.

[0025] Preferably, the disclosed printhead, and the printheads referred to above in relation to the disclosed use, method and printer, have more than 1,000 nozzles.

[0026] Ink printing (drop deposition) is preferably performed on the substrate, i.e., the intermediate product on which the ink is printed, at the following temperatures. [Table 1]

[0027] The features, advantages, and technical and industrial significance of exemplary embodiments of the present invention are described below with reference to the accompanying drawings. In the drawings, the same reference numerals indicate the same elements. [Brief explanation of the drawing]

[0028] [Figure 1A] Figure 1A is a schematic diagram of the formation of a surface film that can be converted into an electron transport layer according to the present invention. [Figure 1B] Figure 1B shows the ink droplets deposited during the formation of a surface film convertible to the electron transport layer shown in Figure 1A. [Figure 2A] Figure 2A is a schematic diagram of the formation of a surface film convertible to a perovskite layer according to the present invention. [Figure 2B] Figure 2B is a schematic diagram of the air drying process in the formation of the surface film convertible to the perovskite layer shown in Figure 2A according to the present invention. [Figure 3] Figure 3 is a schematic diagram of the formation of the hole transport layer according to the present invention. [Figure 4] Figure 4 shows the product obtained from the formation of the hole transport layer shown in Figure 3. [Modes for carrying out the invention]

[0029] method The methods shown in Figures 1A, 2A, and 3 may be combined as a series of methods for forming functional layers 3, 4, and 5. The conditions and materials used before and after each ink printing operation (droplet deposition) in these methods may be those from known perovskite solar cell manufacturing processes, but surface pretreatment and ink printing with the industrial printhead P will be described in detail below.

[0030] For the method shown in Figure 1A, which is performed in a cleanroom, the scribed substrate (i.e., the wiring surface with electrodes) is cleaned by immersion in a cleaning solution. Figure 1A shows, from left to right, the subsequent operations: plasma treatment, ink printing by a print head P that deposits droplets shown as dots in Figures 1A and 1B, and near-infrared (NIR) drying.

[0031] In the method shown in Figure 2A, the product produced by the method shown in Figure 1A is subjected to ink printing using printhead P, depositing droplets shown as dots in Figure 2A. Subsequently, the product is subjected to air drying as shown in Figure 2B for solvent evaporation to reduce the thickness of the deposited surface film, and then perovskite annealing is performed in a cleanroom (not shown in Figure 2A).

[0032] In the method shown in Figure 3, which is performed in a cleanroom, the product obtained from perovskite annealing is subjected to ink printing using a printhead P, depositing droplets shown as dots in Figure 3. Subsequently, the thickness of the deposited surface film is reduced by dropping and evaporating a solvent. The product obtained by the method shown in Figure 3 may also be subjected to electrode layer deposition (vapor deposition).

[0033] The resulting solar cells Following the protocol described below, solar cells were manufactured using the sequence of these methods shown in Figures 1A, 2A, and 3, and verified to have a high PCE of 10.75%. This solar cell is shown in Figure 4.

[0034] Formation of the electron transport layer Materials and equipment The materials and equipment used in the layer formation described below are as follows: [Table 2]

[0035] A commercially available substrate, ITO PEN with a diamond coating, was used. P1 scribes were made on the substrate for the contact electrodes. Other suitable substrates include different types of TCO-coated glass or transparent plastic (e.g., FTO, ITO glass, different ITO PEN, etc.), metal-coated glass, or plastic. The substrate must be able to withstand temperatures up to 120°C.

[0036] The substrate was wet-cleaned: ultrasonic bath in 2% Hellmanex in deionized water for 15 minutes, followed by two 10-minute ultrasonic baths in deionized water, and then dried with compressed air.

[0037] Prior to plasma treatment, the substrate was treated by blowing a stream of compressed air onto it to remove particles. Immediately before printing the surface film to obtain the electron transport layer (ETL), the substrate was plasma-treated in a cleanroom using a plasma torch (compressed air plasma, inocon MicroColdPlasmaMCP501 plasma torch) at a distance of 5-10 mm and an x-speed of 400 mm / s-800 mm / s, in 3 mm steps between treatment lines (2-pass plasma treatment). Plasma treatment, when combined with the ETL ink described below, enables good wetting with a low total cost of ownership (TCO). Other suitable pretreatments to achieve good wetting behavior include flame treatment, corona treatment, and various plasma treatments.

[0038] Ethylene glycol (ROTH), n-propanol (TCI), AMP (C4H 11 ETL inks were prepared using a SnO2 nanoparticle solution (15% in H2O, Alfa Aesar) prepared by mixing NO (Alfa Aesar), glycerol (ACROS), and 2-isopropoxyethanol in a volume ratio of 9.99:51.31:25.65:0.45:4.5:8.1. This ETL ink composition prevents nozzle clogging and allows for good wetting of the substrate after pretreatment.

[0039] The ETL ink was filtered through a 0.2 μm particle size filter. The viscosity of the ink was 10.5 mPa·s. This ETL ink was printed in a cleanroom using a Ricoh MH5421 printhead at a resolution of 600 dpi × 600 dpi with droplets of an average volume of 10.3 pL.

[0040] The printing speed was 50 mm / s and the printing distance was 2-3 mm. The substrate temperature was 90°C. 15.45 seconds after printing (heating of the lamp), the printed ETL substrate was passed five times under an adphos NIR lamp (NIR96-250-E (752928), nominal input power 30 W / cm) at an intensity of 30%, a speed of 140 mm / s, and a distance of 55 mm between the lamp and the substrate. The resulting product was plasma-treated in a cleanroom.

[0041] Perovskite layer formation The ETL (End-to-Line Transport) substrates, supported by the cleanroom described above, were processed using a plasma torch (compressed air plasma, inocon) at a distance of 8 mm and an x-speed of 600 mm / s, in 3 mm steps between processing lines (1-pass plasma processing).

[0042] Before plasma treatment, compressed air was blown onto the substrate to remove particles.

[0043] Perovskite precursor inks were prepared by dissolving PbI2 (0.6M, TCI), PbAc2 (0.4M, TCI), and MAI (1.8M, Dyesol) in 2-methoxyethanol (2-ME) solvent. The powders were mixed with the solvent approximately one hour before printing. The inks were stirred at 50°C for 20 minutes, and then cooled for 40 minutes while stirring.

[0044] The perovskite ink composition enables high-quality perovskite without damaging industrial printheads.

[0045] The perovskite ink was filtered through a 0.2 μm particle size filter. The viscosity of the ink was 3 mPa·s. This perovskite ink was printed onto a heated substrate using a Ricoh MH5420 printhead with 18 pL droplets at a resolution of 450 dpi × 600 dpi. The relative humidity was reduced to 5% by introducing dry air to the platform before printing, and then slowly increased. The printing speed was 50 mm / s, and the printing distance was 2-3 mm. The substrate temperature was 40°C. After printing, the perovskite ink was dried for 8.3 seconds with a flow of dry air at a speed of 10 mm / s (air dryer pressure 10 mm of water column). The distance between the substrate and the air dryer was 5.7 mm, and the slot width of the air dryer was 1 mm. Next, the surface film was annealed in a vacuum oven at a pressure of 400 mmHg at 120°C for 20 minutes.

[0046] For storage, the obtained products were stored in a plastic box that was vacuum-sealed inside a plastic bag containing silica beads.

[0047] Hole transport layer formation The spiro-OMeTAD / PTAA / P3HT (1.5g) ink for obtaining the hole transport layer (HTL) was prepared by dissolving 4-tert-butylpyridine (525μL), Li-TFSI (325μL) at 520mg / mL in acetonitrile, and Co[t-BuPyPz]3[TFSI]3 (FK209, Dyesol) (350μL) at 380mg / mL in acetonitrile in anisole (50mL). This recipe allows for the printing of functional HTLs without clogging or attacking the printhead.

[0048] The HTL ink was filtered through a 0.2 μm particle size filter. The viscosity of the ink was 0.7 mPa·s. This HTL ink was printed onto the heated product from the perovskite layer formation described above using a Ricoh MH5420 printhead with droplets of approximately 10 pL at a resolution of 600 dpi × 600 dpi, and allowed to dry on the surface. The printing speed was 50 mm / s, and the printing distance was 2-3 mm. The substrate temperature was 60°C.

[0049] For transportation, the obtained product (PSC) was stored in a plastic box and vacuum-sealed inside a plastic bag containing silica beads.

[0050] Formation of counter electrodes Finally, a 70 nm thick gold electrode was placed on the hole transport layer formed as described above by thermal evaporation to serve as a counter electrode, completing the device fabrication.

[0051] Preparing the print head In each of the above-described formations of the ETL, perovskite layer, and HTL, the Ricoh MH5420 / MH5421 printhead was adapted as follows.

[0052] ETL printhead: When not in use, this printhead was filled with Siegwerk Sicura Jet flashing solution and capped. To fill with ETL ink, the first step was to purge the Siegwerk flashing solution and fill the empty printhead with isopropanol, the second step was to purge the isopropanol and fill the empty printhead with ethylene glycol, and finally, the third step was to purge the ethylene glycol and fill with ETL ink. After printing, the ETL printhead was cleaned as follows: the first step was to purge the ETL ink and fill the printhead with ethylene glycol, the second step was to purge the ethylene glycol and fill the printhead with isopropanol, and finally, the third step was to purge the isopropanol, and the printhead was filled with Siegwerk flashing solution and capped for "storage".

[0053] Perovskite layer printhead: When not in use, this printhead was filled with Siegwerk flash fluid and capped. To fill with perovskite ink, the first step was to purge the Siegwerk flash, fill the empty printhead with isopropanol, the second step was to purge the isopropanol, fill the empty printhead with 2-methoxyethanol, and finally, the third step was to purge the 2-methoxyethanol and fill with perovskite ink. After printing, the perovskite printhead was cleaned as follows: the first step was to purge the perovskite ink, fill the printhead with 2-methoxyethanol, the second step was to purge the 2-methoxyethanol, fill the printhead with isopropanol, and finally, the third step was to purge the isopropanol, and for "storage" the printhead was filled with Siegwerk flash fluid and capped.

[0054] HTL printhead: When not in use, this printhead was filled with Siegwerk flash fluid and capped. To fill with HTL ink, the first step was to purge the Siegwerk flash, fill the empty printhead with isopropanol, the second step was to purge the isopropanol, fill the empty printhead with anisole, and finally, the third step was to purge the anisole and fill with HTL ink. After printing, the HTL printhead was cleaned as follows: the first step was to purge the HTL ink, fill the printhead with anisole, the second step was to purge the anisole, fill the printhead with isopropanol, and finally, the third step was to purge the isopropanol, fill the printhead with Siegwerk flash fluid for "storage", and cap it.

[0055] Alternative perovskite precursor inks In the above example of a specific perovskite layer formation, the perovskite precursor ink preparation was replaced with the following: PbI2 (0.4M, TCI), PbAc2 (0.4M, TCI), and MAI (0.4M, Dyesol) were dissolved in (2-ME) solvent. The powders were mixed with the solvent approximately 1 hour before printing. The ink was stirred at 50°C for 20 minutes, then cooled for 40 minutes while stirring.

[0056] While this disclosure refers to certain exemplary embodiments, modifications to these embodiments may be made without departing from the general scope of the invention as defined in the claims. In particular, in further embodiments, the individual characteristics of the various embodiments described / referenced may be combined. Accordingly, the detailed description and drawings of the invention should be interpreted as illustrative rather than restrictive. [Explanation of Symbols]

[0057] 1 circuit board 2. Contact layer (wiring) 3 Electron transport layer 4 Perovskite layer 5. Hole transport layer 3A, 4A, 5A surface film 4b Dried surface film 6. Plasma Torch 7 Near-infrared (NIR) dryer 8. Compressed air dryer P Printhead

Claims

1. In the ink printing operation on the surface of an intermediate product in the manufacture of a perovskite solar cell, the use of a solution as an ink to provide a surface film that can be converted into a functional layer of the perovskite solar cell by drying, The ink printing operation uses a print head having at least 100 nozzles and / or at least 0.3 m of the surface. ２ The ink is deposited over the region, The functional layer is one of an electron transport layer, a perovskite layer, and a hole transport layer. The solution is used to contain the precursor of the functional layer in a polar solvent containing alcohol and / or ether.

2. The functional layer is an electron transport layer or a perovskite layer. The aforementioned surface is a plasma-treated surface. The use described in claim 1.

3. The use according to claim 2, wherein the surface is a surface of an inorganic material and is a surface that has been plasma-treated with a surfactant.

4. The aforementioned functional layer is an electron transport layer, The solvent includes an alcohol. The viscosity of the aforementioned solution is 7 mPa·s to 14 mPa·s. The use described in claim 2 or 3.

5. The use according to claim 4, wherein the drying includes exposing the surface film to a combination of heating and near-infrared irradiation.

6. The alcohol is at least one of ethylene glycol, n-propanol, glycerol, isopropoxyethanol, and 2-amino-2-methyl-propanol. The precursor comprises dispersed tin oxide. The use described in claim 4.

7. The aforementioned functional layer is a hole transport layer, The solvent includes Ether, The viscosity of the aforementioned solution is 0.5 mPa·s to 1.0 mPa·s. The use described in claim 1.

8. The aforementioned surface is the surface of the electron transport layer of the perovskite solar cell. The aforementioned functional layer is a perovskite layer, The precursor comprises a lead salt containing iodide ions and acetate ions. The solvent includes Ether, The viscosity of the aforementioned solution is 2.5 mPa·s to 5.5 mPa·s. The use described in claim 1, 2, or 3.

9. The print head has at least 200 nozzles, and / or the area is at least 0.5 m of the surface. ２ The use according to claim 1, 2, or 3.

10. The use according to claim 1, 2, or 3, wherein the ink printing operation is adjusted to a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL.

11. at least 0.3 m of the surface ２ A print head for ink printing operations to deposit ink in a region with a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, The print head has at least 100 nozzles, and the print head is filled with a solution as ink for providing a surface film that can be converted into a functional layer of a perovskite solar cell by drying during the ink printing operation. The functional layer is one of an electron transport layer, a perovskite layer, and a hole transport layer. The solution is a print head comprising a precursor of the layer in a polar solvent containing alcohol and / or ether.

12. The print head according to claim 11, with a surface of at least 0.3 m ２ An inkjet printer for ink printing operations that deposits ink in a region with a resolution of 100 dpi x 100 dpi to 2400 dpi x 2400 dpi and a droplet size of 1 pL to 225 pL.

13. A method for manufacturing a product which includes a substrate, has electrode wiring on the surface of the substrate to form a perovskite solar cell, and further comprises a laminate of multiple functional layers in the order described, the substrate side being an electron transport layer, a perovskite layer, and a hole transport layer, which can be processed into a perovskite solar cell, or a product which is a perovskite solar cell, The aforementioned product is At least 0.3 m of the surface obtained from conditioning ２ In the region, a surface film convertible to one of the plurality of functional layers is deposited using the ink printing operation of the printer described in claim 12, with a resolution of 100 dpi × 100 dpi to 2400 dpi × 2400 dpi and a droplet size of 1 pL to 225 pL, and The deposition process includes evaporating the solvent deposited from the print head of the printer, thereby converting the surface film into one of the plurality of functional layers. Manufactured by The conditioning method comprises at least one operation selected from cleaning, annealing, plasma treatment, flame treatment or corona treatment, and vacuum annealing at a temperature of 90°C to 180°C for 5 to 45 minutes.

14. A method for manufacturing a product which is a perovskite solar cell, comprising a substrate, having electrode wiring on the surface of the substrate, and further comprising a laminate of a plurality of functional layers in the order described, wherein the plurality of functional layers are an electron transport layer, a perovskite layer, and a hole transport layer on the substrate side, the method comprising repeatedly performing the method of claim 13 with conditioning as a further operation before deposition in order to form each of the plurality of functional layers.

15. A perovskite solar cell comprising a substrate, having electrode wiring on the surface of the substrate, and further comprising a laminate of a plurality of functional layers in the order described, wherein the substrate-side electron transport layer, perovskite layer, and hole transport layer, the perovskite solar cell is obtained according to the method of claim 14, and at least 0.3 m ２ A perovskite solar cell having a surface area of ​​[specified area].

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