Method for forming film layer, organic solar cell and preparation method of organic solar cell

Abstract

The invention belongs to the field of solar cells. The invention provides a method for forming a film layer, an organic solar cell and a preparation method thereof. The method for forming the film layer comprises the following steps: providing a support body; enabling one side surface of the supporting body to be in contact with the substrate, and covering the supporting body with a film layer precursor solution to form a film layer; wherein the temperature difference between the temperature T1 of the substrate and the temperature T2 of the film layer precursor solution is controlled to be not greater than a target temperature, the target temperature is used for regulating and controlling the formation of a flow pattern of the film layer precursor solution, and the target temperature is 0-20 DEG C. According to the method, the uniform film layer can be obtained, the process is simple, and the large-area film layer can be obtained without an additional technological operation process.

Description

Technical Field

[0001] The present application relates to the technical field of solar cells, and in particular to a method for forming a film layer, an organic solar cell and a preparation method thereof. Background Art

[0002] Organic / polymer solar cells have great market potential in portable energy, indoor photovoltaics, building photovoltaic integration and other application scenarios due to their inherent advantages of light weight, flexibility, non-toxicity, roll-to-roll high-throughput preparation and other advantages. At present, the energy conversion efficiency of single-junction organic solar cells has exceeded 20%, initially reaching the threshold for commercialization, and has become an important branch of the current development of the solar cell field. At present, high-efficiency devices are based on small-area active layers prepared by spin coating, but for spin coating, a large amount of solution is thrown away during film formation, which will cause material waste; and due to the different centrifugal forces of the inner and outer parts when the substrate rotates at high speed, when the film size is expanded to a certain extent, the thickness will be uneven, so it is not suitable for the preparation of large-area films. When scraping, the scraper can spread the solution evenly on the substrate without causing loss or waste of the solution, and the solution is evenly stressed, so that the film thickness will not change significantly due to changes in size, which is more suitable for the preparation of large-area films.

[0003] However, the large-area active layers currently prepared by processes such as scraping and slit coating still have problems with poor film quality (such as uneven thickness). The efficiency of large-area components is still far behind that of small-area devices, which restricts the commercial development of organic solar cells.

[0004] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the invention

[0005] The embodiments of the present application provide a method for forming a film layer, an organic solar cell and a method for preparing the same, so as to solve or alleviate the above-mentioned problem that the film layer quality is still poor (such as uneven thickness) when a large-area active layer is prepared by processes such as scraping and slit coating.

[0006] In a first aspect of an embodiment of the present application, a method for forming a film layer is provided, the method comprising: providing a support body; making one side of the support body contact with a substrate, and covering a film layer precursor solution on a side of the support body away from the substrate to form a film layer; wherein the temperature T of the substrate is controlled 1 and the film precursor solution temperature T 2 The temperature difference between them is not greater than the target temperature, and the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution, and the target temperature is 0-20°C.

[0007] By controlling the temperature between the substrate temperature and the film precursor solution temperature to be no greater than the target temperature, the target temperature is used to regulate the formation of the flow pattern of the film precursor solution, and the target temperature range is 0-20°C. This lower temperature difference can effectively control the formation of the flow pattern of the film precursor solution, that is, control the strength and direction of the Marangoni flow, achieve the dynamic balance of the Marangoni flow and the capillary flow, and then regulate the fluid mechanics of the film precursor solution during the volatilization and drying process, so that the film precursor solution can be uniformly deposited, thereby improving the uniformity of the formed film layer. This method has a simple process and strong adaptability, and does not require additional process operation procedures, and can obtain a large-area film layer.

[0008] According to an embodiment of the present application, the support body includes a transparent conductive electrode and a functional layer, and the functional layer is located on one side surface of the transparent conductive electrode.

[0009] According to an embodiment of the present application, the functional layer includes a hole transport layer or an electron transport layer.

[0010] According to an embodiment of the present application, the functional layer is a hole transport layer, and the hole transport layer is located on a side of the transparent conductive electrode away from the substrate.

[0011] According to the embodiment of the present application, T 1 20-80℃.

[0012] According to the embodiment of the present application, T 2 20-90℃.

[0013] According to an embodiment of the present application, the membrane layer precursor solution includes an active layer precursor solution.

[0014] According to an embodiment of the present application, the active layer precursor solution includes a solid additive, an electron donor, an electron acceptor and a solvent.

[0015] According to an embodiment of the present application, the concentration of the electron donor in the active layer precursor solution is 3-15 mg / mL.

[0016] According to an embodiment of the present application, the concentration of the electron acceptor in the active layer precursor solution is 5-20 mg / mL.

[0017] According to an embodiment of the present application, the ratio of the mass of the solid additive to the mass of the electron acceptor is (0.15-1.5):1.

[0018] According to an embodiment of the present application, the electron donor includes , , At least one of .

[0019] According to an embodiment of the present application, the electron acceptor comprises , , , , At least one of .

[0020] According to an embodiment of the present application, the solid additive includes a halogen substitute of benzene.

[0021] According to an embodiment of the present application, the solvent is at least one of chloroform, chlorobenzene, toluene, o-xylene, m-xylene, p-xylene, and tetrahydrofuran.

[0022] According to an embodiment of the present application, after covering the active layer precursor solution and before forming the active layer, it further includes: annealing treatment, the annealing treatment temperature is 80-110° C., and the time is 3-10 min.

[0023] In a second aspect of the embodiment of the present application, a method for preparing an organic solar cell is provided, comprising: providing a support body, the support body comprising a transparent conductive electrode and a functional layer stacked in layers, making the transparent conductive electrode contact with a substrate, and covering a film layer precursor solution on a side of the functional layer away from the transparent conductive electrode to form a film layer; wherein the temperature T of the substrate is controlled 1 and the film precursor solution temperature T 2 The temperature difference between them is not greater than the target temperature, and the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution. The target temperature is 0-20°C, the functional layer includes a hole transport layer or an electron transport layer, the film layer includes an active layer, and the film layer precursor solution includes an active layer precursor solution.

[0024] The method for preparing the organic solar cell of the embodiment of the present application is simple to operate, and a large-area active layer can be obtained without additional process operation procedures. In addition, the obtained active layer has a more uniform film thickness, a smaller surface roughness, and a higher crystallinity, so that the carrier transport in the active layer is faster and the charge recombination is reduced, which is beneficial to improving the photoelectric performance of the organic solar cell.

[0025] In a third aspect of the embodiments of the present application, an organic solar cell is provided, which comprises a transparent conductive electrode, a hole transport layer, an active layer, an electron transport layer and a top electrode arranged in a stacked manner, wherein the active layer is prepared by the method described in the first aspect.

[0026] The organic solar cell of the present application has a high photoelectric efficiency. This is because the active layer is obtained by the method described in the first aspect, so that the film thickness of the active layer is more uniform, the surface roughness is smaller, and the crystallinity is higher, so that the carrier transmission in the active layer is faster and the charge recombination is reduced, which is beneficial to improving the photoelectric performance of the organic solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the multiple drawings represent the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings only depict some embodiments disclosed in the present application and should not be regarded as limiting the scope of the present application.

[0028] Figure 1 is a schematic structural diagram of an organic solar cell according to some embodiments; Figure 2 Schematic diagrams of structures of organic solar cells in other embodiments.

[0029] Reference numerals: 1: top electrode; 2: electron transport layer; 3: active layer; 4: hole transport layer; 5: transparent conductive electrode; 6: third scribe; 7: second scribe; 8: first scribe. DETAILED DESCRIPTION

[0030] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. In the accompanying drawings, for clarity, the sizes of layers, regions, elements and their relative sizes may be exaggerated. Wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be understood as limitations on the present application. It should be noted that, in the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0031] It should be understood that when an element or layer is referred to as "on ...", "adjacent to ...", "connected to" or "coupled to" other elements or layers, it can be directly on, adjacent to, connected to or coupled to other elements or layers, or there can be intervening elements or layers. On the contrary, when an element is referred to as "directly on ...", "directly adjacent to ...", "directly connected to" or "directly coupled to" other elements or layers, there is no intervening element or layer. It should be understood that although the terms first, second, third, etc. can be used to describe various elements, components, regions, layers and / or parts, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teachings of the present application, the first element, component, region, layer or part discussed below can be represented as the second element, component, region, layer or part. When the second element, component, region, layer or part is discussed, it does not indicate that the present application necessarily has the first element, component, region, layer or part.

[0032] In this application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0033] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein, for example. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0034] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for broadly including quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0035] There are still many major problems in the large-area active layer currently prepared by processes such as blade coating and slit coating. Large-area thin films still have problems such as low film uniformity, difficult morphology control, severe donor-acceptor phase separation, and poor molecular crystallinity, which in turn lead to severe carrier recombination inside the device. The efficiency of large-area components is still far behind that of small-area devices.

[0036] In a first aspect of an embodiment of the present application, a method for forming a film layer is provided, the method comprising: providing a support body; making one side of the support body contact with a substrate, and covering a film layer precursor solution on a side of the support body away from the substrate to form a film layer; wherein the temperature T of the substrate is controlled 1 and the film precursor solution temperature T 2 The temperature difference between them is not greater than the target temperature, and the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution, and the target temperature is 0-20°C.

[0037] By controlling the temperature between the substrate temperature and the film precursor solution temperature to be no greater than the target temperature, the target temperature is used to regulate the formation of the flow pattern of the film precursor solution, and the target temperature range is 0-20°C. This lower temperature difference can effectively control the formation of the flow pattern of the film precursor solution, that is, control the strength and direction of the Marangoni flow, achieve the dynamic balance of the Marangoni flow and the capillary flow, and then regulate the fluid mechanics of the film precursor solution during the volatilization and drying process, so that the film precursor solution can be uniformly deposited, thereby improving the uniformity of the formed film layer. This method has a simple process and strong adaptability, and does not require additional process operation procedures, and can obtain a large-area film layer.

[0038] Furthermore, the target temperature is 5-10° C. This is beneficial to the crystallization of the film layer and obtains a film layer with uniform thickness.

[0039] In some embodiments, the support includes a transparent conductive electrode and a functional layer, and the functional layer is located on one side of the transparent conductive electrode. In this way, the support composed of the transparent conductive electrode and the functional layer can be covered with a film precursor solution on the functional layer to obtain a film layer.

[0040] Furthermore, the functional layer includes a hole transport layer or an electron transport layer.

[0041] As some examples, the functional layer is a hole transport layer, the hole transport layer is located on one side of the transparent conductive electrode, and the hole transport layer is far away from the substrate, so that a film layer can be prepared on the hole transport layer.

[0042] As some other examples, the functional layer is an electron transport layer, the electron transport layer is located on one side of the transparent conductive electrode, and the electron transport layer is far away from the substrate, so that a film layer can be prepared on the electron transport layer.

[0043] Generally, the temperature of the substrate and the temperature of the film precursor solution are selected based on the following principle: the temperature difference between the substrate and the film precursor solution is not greater than the target temperature, so that the film precursor solution can achieve a dynamic balance between Marangoni flow and capillary flow during the drying process. In addition, the target temperature is adapted to the volatilization rate of the appropriate solution, so that the solution applied from the tool head of the equipment will not dry too early (the liquid film will dry and solidify as soon as it contacts the substrate) or too late (the liquid film will not evaporate and dry for more than 10 seconds after application).

[0044] Optionally, T 1 It is 20-80°C, for example, 20°C, 40°C, 60°C, 80°C, etc.

[0045] Optionally, T 2 It is 20-90°C, for example, 20°C, 50°C, 70°C, 90°C, etc.

[0046] Generally, the film layer precursor solution can be selected according to the film layer to be formed. For example, the film layer precursor solution includes an organic active layer solution, a metal oxide precursor solution and a perovskite precursor solution.

[0047] In some embodiments, the film layer precursor solution is an active layer precursor solution. The active layer precursor solution is used to form an active layer. The function of the active layer is to form a heterojunction morphology, generate excitons after absorbing sunlight, and split into free electrons and holes at the donor-acceptor interface, and then the free electrons and holes are respectively transmitted to the electrodes at the two ends using the acceptor phase and the donor phase as transmission channels to form a current.

[0048] In some embodiments, the active layer precursor solution includes a solid additive, an electron donor, an electron acceptor, and a solvent. The molecular interaction between the solid additive and the acceptor optimizes the phase separation size of the electron donor and the electron acceptor, enhances the π-π stacking of the electron acceptor and the crystallinity of the active layer, and is beneficial to improving the quality of the photoactive layer film.

[0049] Optionally, in the active layer precursor solution, the ratio of the mass of the solid additive to the mass of the electron acceptor is (0.15-1.5) : 1. In this way, the aggregation of the electron acceptor can be reduced, and an acceptor phase of suitable size can be obtained. In addition, the π-π stacking of the electron acceptor and the crystallinity of the active layer are improved, and the internal charge of the active layer is reduced, the charge mobility is improved, and the efficiency of charge transfer is improved.

[0050] Furthermore, the ratio of the mass of the solid additive to the mass of the electron acceptor is (0.8-1.1):1.

[0051] Optionally, based on the active layer precursor solution, the concentration of the electron donor in the active layer precursor solution is 3-15 mg / mL.

[0052] Optionally, based on the active precursor solution, the concentration of the electron acceptor in the active layer precursor solution is 5-20 mg / mL.

[0053] Optionally, the mass ratio between the electron donor and the electron acceptor in the active layer is (2:1)-(1:5).

[0054] It can be understood that the masses of the electron donor, the electron acceptor and the solid additive, as well as the mass ratio of the electron donor, the electron acceptor and the solid additive can be changed and adjusted to a certain extent according to the different materials of the electron donor, the electron acceptor and the solid additive, as well as the thickness of the active layer to be prepared, the type of active layer to be prepared (selective control of the light absorption band, such as a semi-transparent active layer film, etc.), etc.

[0055] Optionally, the electron donor comprises (PM6), (D18), At least one of (D18-Cl).

[0056] Generally, the above n is a positive integer.

[0057] Optionally, the electron acceptor comprises (ITIC), (Y6), (BTP-eC9), (L8-BO), At least one of (N3).

[0058] Optionally, the solid additive includes a halogen substitute of benzene. The halogen substitute of benzene is used as a solid additive and added to the active layer composed of the donor and the acceptor, thereby improving the overall quality of the photoactive layer film (obtaining a more suitable phase separation scale of the donor phase and the acceptor phase, the acceptor molecules are more densely packed, and the crystallinity of the film is improved).

[0059] Furthermore, the solid additive includes at least one of 1,3-dibromo-5-chlorobenzene, 3,5-dichloro-1-bromobenzene, 1,4-diiodobenzene, 1,3,5-triiodobenzene, 1,3,5-tribromobenzene and the like.

[0060] Optionally, the solvent is at least one of chloroform, chlorobenzene, toluene, o-xylene, m-xylene, p-xylene and tetrahydrofuran.

[0061] As an example, the film layer is an active layer. The covering method of the active layer includes coating. During coating, the resultant of the stacked transparent conductive electrode and the hole transport layer is used as a support, and the transparent conductive electrode is brought close to the substrate, and then the active layer precursor solution is covered on the hole transport layer to obtain an active layer. The active layer precursor solution includes solid additives, electron donors, electron acceptors and solvents. At the same time, by dual regulation of the substrate temperature and the solution temperature, the active layer precursor solution achieves a dynamic balance between Marangoni flow and capillary flow during the drying process, improves the uniform deposition of the solute during the solution drying process, and is conducive to the preparation of an active layer with uniform film thickness. In addition, this method can also prepare a large-sized active layer, that is, the size of the active layer is not limited. The halogen substituent of benzene is used as a solid additive and added to the active layer composed of the donor and the acceptor, which improves the overall quality of the photoactive layer film (obtaining a more suitable phase separation scale of the donor phase and the acceptor phase, the acceptor molecules are more tightly stacked, and the crystallinity of the film is improved). When the component is used in a solar cell, it is beneficial to improve the photoelectric performance of the component.

[0062] In some embodiments, the covering comprises coating.

[0063] Optionally, the coating comprises knife coating.

[0064] As another example, the film layer is an active layer. The active layer is covered by coating. During coating, the transparent conductive electrode and the electron transport layer are stacked as a support, and the transparent conductive electrode is placed close to the substrate, and then the active layer precursor solution is covered on the hole transport layer to obtain the active layer.

[0065] In some embodiments, when coating the active layer precursor solution, the coating speed during scraping is 5-100 mm / s, the scraper height is 30-300 μm, the temperature of the active layer precursor solution is 20-90° C., and the substrate temperature is 20-80° C.

[0066] In some embodiments, after the covering film precursor solution and before the film formation, the method further includes: annealing treatment. Annealing treatment can make the formed film crystallize more uniformly and improve the film quality.

[0067] As some examples, after covering the active layer precursor solution and before forming the active layer, the process further includes: annealing, wherein the annealing temperature is 80-110° C. and the time is 3-10 min.

[0068] In some embodiments, the thickness of the active layer is selected according to actual application requirements and production requirements. Optionally, the thickness of the active layer is 90-500 nm.

[0069] In some embodiments, the mass ratio between the electron donor and the electron acceptor in the active layer is (2:1)-(1:5).

[0070] In a second aspect of the embodiment of the present application, a method for preparing an organic solar cell is provided, comprising: providing a support body, the support body comprising a stacked transparent conductive electrode and a functional layer, making the transparent conductive electrode contact the substrate, and covering a film layer precursor solution on a side of the functional layer away from the transparent conductive electrode to form a film layer; wherein the temperature T of the substrate is controlled 1 and the film precursor solution temperature T 2 The temperature difference between them is not greater than the target temperature, the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution, the target temperature is 0-20°C, the functional layer includes a hole transport layer or an electron transport layer, the film layer includes an active layer, and the film layer precursor solution includes an active layer precursor solution.

[0071] The method controls the temperature between the temperature of the substrate and the temperature of the film layer precursor solution to be no greater than the target temperature, and the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution, and the target temperature is 0-20°C. This relatively low temperature difference can effectively control the strength and direction of the Marangoni flow, achieve a dynamic balance between the Marangoni flow and the capillary flow, and then regulate the fluid mechanics of the active layer precursor solution during the volatilization and drying process, so that the thickness of the formed film layer is uniform. And the process of this method is simple, and a large-area active layer can be obtained without additional process operation procedures. In addition, the film thickness of the obtained active layer is more uniform, the surface roughness is smaller, and the crystallinity is higher, so that the carrier transmission in the active layer is faster and the charge recombination is reduced, which is beneficial to improve the photoelectric performance of organic solar cells.

[0072] In some embodiments, the active layer precursor solution includes a solid additive, an electron donor, an electron acceptor, and a solvent. The molecular interaction between the solid additive and the acceptor optimizes the phase separation size of the electron donor and the electron acceptor, enhances the π-π stacking of the electron acceptor and the crystallinity of the active layer, and is beneficial to improving the quality of the photoactive layer film.

[0073] As an example, the covering method of the active layer includes coating. During coating, the resultant of the stacked transparent conductive electrode and the hole transport layer is used as a support, and the transparent conductive electrode is brought close to the substrate, and then the active layer precursor solution is covered on the hole transport layer to obtain an active layer. The active layer precursor solution includes solid additives, electron donors, electron acceptors and solvents. In this way, by dual regulation of the substrate temperature and the solution temperature, the dynamic balance of Marangoni flow and capillary flow is achieved, which promotes the uniform deposition of solutes during the drying process of the solution, is conducive to the preparation of an active layer with uniform film thickness, and the size of the active layer is not limited. The halogen substituent of benzene is used as a solid additive and added to the active layer composed of the donor and the acceptor, which improves the overall quality of the photoactive layer film (obtaining a more suitable phase separation scale of the donor phase and the acceptor phase, the acceptor molecules are more tightly packed, and the crystallinity of the film is improved). When the component is used in a solar cell, it is beneficial to improve the photoelectric performance of the component.

[0074] As another example, the active layer is covered by coating. During coating, a transparent conductive electrode and an electron transport layer are stacked as a support, and the transparent conductive electrode is placed close to the substrate, and then an active layer precursor solution is covered on the hole transport layer to obtain an active layer.

[0075] Optionally, when coating the active layer precursor solution, the coating speed during scraping is 5-100 mm / s, the scraper height is 30-300 μm, the temperature of the active layer precursor solution is 20-90° C., and the substrate temperature is 20-80° C.

[0076] In some embodiments, after the covering film precursor solution and before the film formation, an annealing process is further included. The annealing process can remove residual volatile solid additives, so that the formed film has higher crystallinity and better film quality.

[0077] In some embodiments, a method for preparing a solar cell in a continuous operation: S1: dissolving an electron donor, an electron acceptor and a solid additive in a solvent, stirring and mixing them uniformly to obtain an active layer of the organic solar cell; S2: P1 scribing (first scribing) of the transparent conductive electrode (ITO) glass substrate is cut into multiple independent areas by laser etching, and ultrasonic cleaning is performed with a cleaning solution, deionized water and isopropyl alcohol respectively, and then dried with nitrogen gas after cleaning; S3: The nitrogen-dried substrate is placed in an ultraviolet ozone machine (UVO) for treatment for 10-40 minutes, a hole transport layer material is scraped on the substrate in air, and then the hole transport layer is thermally annealed at 110-180° C. for 10-20 minutes in air, wherein the substrate includes a transparent conductive electrode.

[0078] S4: placing the substrate with the hole transport layer on a substrate at a certain temperature in air, and scraping the active layer precursor solution at a certain temperature, and then performing a thermal annealing treatment at 80° C.-110° C. for 3-10 min on the scraped product to obtain an active layer; S5: In a glove box filled with nitrogen, 9-12 nm of C 60 and 3-8nm BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) to form an electron transport layer; S6: Use laser to perform P2 pattern cutting (second scribing) on ​​the film, and cut the hole transport layer, active layer and electron transport layer into multiple independent parts by laser etching and cutting; S7: In a glove box filled with nitrogen, a metal electrode with a thickness of 100-300 nm is evaporated on the electron transport layer, and then P3 pattern cutting (third scribing) is performed by laser to obtain the organic solar cell.

[0079] In some embodiments, the material of the hole transport layer includes one or more of Spiro-OMeTAD (2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), P3HT (poly(3-hexylthiophene-2,5-diyl)), PEDOT:PSS (poly(ethylenedioxythiophene-poly(styrenesulfonate)), NiOx (nickel oxide), CuSCN (cuprous thiocyanate) and PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]).

[0080] According to a third aspect of the present application, an organic solar cell is provided. Figure 1 The battery comprises a transparent conductive electrode 5, a hole transport layer 4, an active layer 3, an electron transport layer 2 and a top electrode 1 which are stacked, wherein the active layer 3 is prepared by the method described in the first aspect.

[0081] The organic solar cell of the present application has a high photoelectric efficiency. This is because the active layer is obtained by the method described in the first aspect, so that the film thickness of the active layer is more uniform, the surface roughness is smaller, and the crystallinity is higher, so that the carrier transmission in the active layer is faster and the charge recombination is reduced, which is beneficial to improving the photoelectric performance of the organic solar cell.

[0082] In some embodiments, reference Figure 2 The battery comprises a transparent conductive electrode 5, a hole transport layer 4, an active layer 3, an electron transport layer 2 and a top electrode 1 arranged in a stacked manner, wherein the active layer 3 is prepared by the method described in the first aspect. The transparent conductive electrodes 5 are arranged in intervals, and the intervals are marked with a groove formed by a first mark 8, in which an electron transport layer is arranged; the second mark 7 divides the hole transport layer 4, the active layer 3 and the electron transport layer 2 into non-conductive parts, and the top electrode 1 is arranged in the groove formed by the second mark 7; the third mark 6 marks the top electrode 1 into current non-conductive parts, thereby completing the series connection of the perovskite battery.

[0083] Hereinafter, exemplary embodiments according to the present application will be described in more detail with reference to the accompanying drawings. It should be noted that these exemplary embodiments can be implemented in many different forms and should not be construed as being limited to the embodiments described herein.

[0084] Example 1 (1) The ITO conductive glass substrate after P1 patterning was etched and treated with UVO for 20 minutes; (2) A layer of PEDOT:PSS was scraped onto the ITO substrate and then annealed at 150°C for 15 min. (3) Electron donors PM6 and D18, electron acceptor BTP-eC9 and solid additive DIB (1,4-diiodobenzene) were weighed and mixed in a sample bottle at a mass ratio of PM6: D18: BTP-eC9: DIB = 0.8: 0.2: 1.2: 1.2, dissolved in chloroform solvent to a PM6 concentration of 5.44 mg / mL, and heated and stirred at 50 °C for 4.5 h.

[0085] (4) In an air environment, at a substrate temperature of 40°C, a 50°C active layer precursor solution was scraped onto the hole transport layer film at a scraper height of 200 μm and a scraping speed of 17 mm / s, and then annealed at 85°C for 5 min; (5) Deposit 10 nm of C and 60 and 5 nm of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) to obtain C 60 / BCP electron transport layer; (6) Before evaporating the metal electrode, the film was cut into P2 patterns using a laser (532 nm); (7) Depositing a 150 nm thick Ag electrode on the cut film by thermal evaporation; (8) Use laser to perform P3 patterning cutting on the Ag electrode to separate the top electrode to form a tandem cell to obtain an organic solar cell.

[0086] Example 2 An organic solar cell was prepared in the manner of Example 1, except that in S4, the temperature of the substrate was 80° C., the temperature of the active layer precursor solution was 90° C., and the solvent was o-xylene with a high boiling point.

[0087] Example 3 An organic solar cell was prepared in the manner of Example 1, except that in S4, the temperature of the substrate was 20°C, and the temperature of the active layer precursor solution was 25°C.

[0088] Example 4 An organic solar cell was prepared in the same manner as in Example 1, except that the temperature of the substrate in S4 was 50°C.

[0089] Examples 5 and 6 An organic solar cell was prepared in the manner of Example 1, except that the PM6 concentrations were 3.88 mg / mL and 11.64 mg / mL.

[0090] Examples 7 and 8 An organic solar cell was prepared in the manner of Example 1, except that PM6:D18:BTP-eC9:DIB=0.8:0.2:1.2:0.7 and PM6:D18:BTP-eC9:DIB=0.8:0.2:1.2:2.1.

[0091] Example 9 An organic solar cell was prepared in the same manner as in Example 1, except that the solid additive included 1,3-dibromo-5-chlorobenzene.

[0092] Example 10 An organic solar cell was prepared in the same manner as in Example 1, except that the electron acceptor was Y6.

[0093] Embodiment 11 An organic solar cell was prepared in the same manner as in Example 1, except that the electron donor was D18-Cl.

[0094] Example 12 An organic solar cell was prepared in the same manner as in Example 1, except that no solid additive was added.

[0095] Comparative Example 1-2 An organic solar cell was prepared in the same manner as in Example 1, except that the temperatures of the substrates were 15° C. and 80° C., respectively.

[0096] The above embodiments and test examples were tested by placing an organic solar cell module (effective area: 15.64 cm 2 ) Under standard test conditions (AM1.5G, 100mW / cm 2 ) were tested, and the specific photoelectric parameter results are shown in Table 1.

[0097] Table 1

[0098] It can be seen from Table 1 that in Examples 1 to 12, the photoelectric performance of the organic solar cells prepared by the method of the present application is better than the photoelectric performance of the solar cell modules of Comparative Examples 1 to 2. It can be seen that the method of the present application can effectively optimize the coating quality of the photoactive layer of the organic solar cell, thereby improving the performance of the cell device.

[0099] Compared with Comparative Examples 1-2, when the difference between the temperature of the substrate and the temperature of the active layer precursor solution is large, the photoelectric performance of the obtained solar cell module is poor. This is because during the film formation process of the active layer, there will be a large temperature difference between the substrate temperature and the ambient temperature, which will cause a large temperature difference between the interior of the solution (close to the substrate) and the surface (close to the atmospheric environment), thereby generating a large surface tension gradient difference in the solution and a large Marangoni flow, which makes the solute flow distribution uneven during the volatilization of the solution, resulting in uneven thickness of the final deposited film.

[0100] It should be noted that the "some embodiments", "other embodiments", "embodiments", etc. mentioned in this application refer to the specific features, structures or characteristics described in conjunction with the embodiment included in at least one embodiment generally described in this application. The same expression appearing in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure or characteristic is described in conjunction with any embodiment, it is claimed that the realization of such feature, structure or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0101] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0102] It should also be noted that the above are only preferred embodiments of the present application, and the patent protection scope of the present application is not limited thereto. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for forming a film layer, characterized in that: include: Providing a support body; Making one side of the support body contact with the substrate, and covering the side of the support body away from the substrate with a film precursor solution to form a film layer; The temperature difference between the substrate temperature T1 and the film precursor solution temperature T2 is controlled to be not greater than a target temperature, and the target temperature is used to regulate the formation of the flow pattern of the film precursor solution, and the target temperature is 0-20°C.

2. The method according to claim 1, characterized in that The support body comprises a transparent conductive electrode and a functional layer, wherein the functional layer is located on one side surface of the transparent conductive electrode.

3. The method according to claim 2, characterized in that The functional layer includes a hole transport layer or an electron transport layer.

4. The method according to claim 3, characterized in that The functional layer is a hole transport layer, and the hole transport layer is located on a side of the transparent conductive electrode away from the substrate.

5. The method according to claim 1, characterized in that T1 is 20-80℃; And / or, T2 is 20-90°C.

6. The method according to claim 5, characterized in that The membrane layer precursor solution includes an active layer precursor solution.

7. The method according to claim 6, characterized in that The active layer precursor solution comprises a solid additive, an electron donor, an electron acceptor and a solvent.

8. The method according to claim 7, characterized in that The concentration of the electron donor in the active layer precursor solution is 3-15 mg / mL; The concentration of the electron acceptor in the active layer precursor solution is 5-20 mg / mL; The ratio of the mass of the solid additive to the mass of the electron acceptor is (0.15-1.5):

1.

9. The method according to claim 8, characterized in that The electron donor includes , , At least one of; And / or, the electron acceptor comprises , , , , At least one of; and / or, the solid additive comprises a halogen substituted benzene; And / or, the solvent is at least one of chloroform, chlorobenzene, toluene, o-xylene, m-xylene, p-xylene and tetrahydrofuran.

10. The method according to any one of claims 1 to 9, characterized in that: After covering the active layer precursor solution and before forming the active layer, the process further includes: annealing treatment, The annealing treatment is performed at a temperature of 80-110° C. and for a time of 3-10 minutes.

11. A method for preparing an organic solar cell, characterized in that: include: providing a support body, the support body comprising a transparent conductive electrode and a functional layer stacked in layers, The transparent conductive electrode is brought into contact with a substrate, and a film precursor solution is covered on a side of the functional layer away from the transparent conductive electrode to form a film layer; Among them, the temperature difference between the temperature T1 of the substrate and the temperature T2 of the film layer precursor solution is controlled to be no greater than the target temperature, the target temperature is used to regulate the formation of the flow pattern of the film layer precursor solution, the target temperature is 0-20°C, the functional layer includes a hole transport layer or an electron transport layer, the film layer includes an active layer, and the film layer precursor solution includes an active layer precursor solution.

12. An organic solar cell, characterized in that: The invention comprises a transparent conductive electrode, a hole transport layer, an active layer, an electron transport layer and a top electrode which are stacked, wherein the active layer is prepared by the method according to claims 1 to 10.

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