Solar cell, manufacturing method thereof, compound and energy storage system

Abstract

The invention relates to the field of power, and particularly provides a solar cell, a manufacturing method thereof, a compound and an energy storage system. The solar cell comprises a substrate, a first electrode layer, a hole transport layer, a photoelectric layer, an electron transport layer and a second electrode layer which are sequentially arranged in a stacked mode. The hole transport layer is a polymer layer, molecules of the polymer layer comprise functional groups, polymeric groups and anchoring groups, and at least part of the anchoring groups are chemically connected with the first electrode layer; the functional group is arranged towards one side of the photoelectric layer, and the polymeric group is connected with the functional group and the anchoring group. The hole transport layer and the modification layer in the solar cell have better stability, and the stability of the solar cell is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electric power, in particular to a solar cell, a manufacturing method thereof, a compound and an energy storage system. BACKGROUND

[0002] Perovskite solar cells are the third generation of solar cells with the most promising commercialization, which have the advantages of high theoretical conversion efficiency, low preparation cost, and highly adjustable band gap. The mainstream commercial perovskite structure includes planar formal structure, planar reverse structure and mesoporous structure. The planar reverse structure can avoid the use of an organic hole transport layer requiring ion dopant, has the characteristics of natural high stability and high efficiency, and is widely accepted by the industry.

[0003] The hole transport layer in the reverse structure is of great significance to the performance of the perovskite solar cell, which plays a role in transporting holes and blocking electrons, and therefore needs to have good compactness and band matching. At present, nickel oxide, self-assembled monolayers (SAM), or a composite layer of nickel oxide and SAM are often used as the hole transport layer in the reverse structure. The SAM layer is formed by depositing a monomolecular compound to improve the ability of the hole transport layer surface to transport holes and block electrons. Using nickel oxide as the hole transport layer has the advantages of simple preparation method and can be prepared by vacuum method, but since nickel oxide has multiple valence states, it is easy to cause redox reaction and decompose the perovskite film during operation, resulting in a decrease in the stability of the perovskite. The preparation method of SAM or a composite layer of nickel oxide and SAM is simple and can be prepared by solution method or vacuum method. The SAM can be used as a hole transport layer or a modification layer to passivate defects of the perovskite, so it has the characteristics of high conversion efficiency, and therefore has been widely used in recent years.

[0004] However, when the hole transport layer in the reverse structure uses a self-assembled layer or a composite layer of nickel oxide and SAM, a large number of small molecules in the SAM are connected to the electrode layer in a physical adsorption manner, and the self-assembled molecules are extremely easy to desorb, which causes the performance of the perovskite photovoltaic cell to decrease rapidly and deteriorate the stability of the perovskite solar cell. SUMMARY

[0005] The present application provides a solar cell, a manufacturing method thereof, a compound and an energy storage system to improve the stability of the solar cell.

[0006] In a first aspect, the present application provides a solar cell, which comprises a substrate, a first electrode layer, a hole transport layer, a photoelectric layer, an electron transport layer and a second electrode layer arranged in sequence and stacked.

[0007] The hole transport layer is a polymer layer, the molecules of the polymer layer include functional groups, polymer groups and anchor groups, and at least part of the anchor groups are chemically connected to the first electrode layer; the functional groups are arranged towards the side of the photoelectric layer, and the polymer groups connect the functional groups and the anchor groups.

[0008] The solar cell of the present application is a reverse structure solar cell. The hole transport layer is located between the substrate and the photoelectric layer and is formed by a polymer. In the molecules of the polymer forming the hole transport layer, the functional groups are used to realize the transport of holes, and the anchor groups are used to realize chemical connection and physical adsorption connection with the first electrode layer. The polymer groups are used to connect the functional groups and the anchor groups to obtain a macromolecular polymer. Compared with the traditional monomolecular SAM, the SAM in the present application is a polymer layer. Since the energy required for the migration of the polymer is high, the difficulty of the movement of the molecules in the device can be effectively increased, and in the working process of the solar cell, the molecules in the SAM can be prevented from falling off and moving to the photoelectric layer, thereby preventing the decrease of the photoelectric conversion efficiency of the photoelectric layer. Therefore, the stability of the solar cell can be improved.

[0009] In an optional implementation, the polymer layer is a monomolecular layer in the thickness direction. The polymer layer adopts a single-layer non-stacked structure, which can avoid the decrease of the connection strength between the polymer layer and the substrate caused by the stacked arrangement of multiple molecular layers.

[0010] In an optional implementation, the functional groups include the following groups:

[0011]

[0012] In formula (1-1), R 21 and R 22 are each independently selected from an aryl group of 6-30 carbon atoms;

[0013] A and B are each independently present or not present, and when A and B are present, A and B are each independently selected from an aryl group of 6-30 carbon atoms;

[0014] The hydrogen in formula (1-1) and formula (1-2) can be substituted by an alkyl group of 1-20 carbon atoms, an alkoxy group of 1-20 carbon atoms, or halogen;

[0015] * is a site connected to the polymer group.

[0016] The above groups can help improve the hole transport efficiency.

[0017] In an optional implementation, the repeating units in the polymer group can be selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms;

[0018] In formula (1-1), the hydrogen in the polymer group can be substituted by halogen.

[0019] The polymeric group can be selected from the above structural groups to serve as a stable linkage.

[0020] In an alternative implementation, the anchoring group is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group.

[0021] The anchoring group is selected from the above structural groups to form a covalent bond with the active group in the first electrode layer to achieve a covalent linkage.

[0022] In an alternative implementation, the hole transport layer includes repeating units of formula (A) or formula (B):

[0023]

[0024] wherein R is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R can be substituted with a halogen;

[0025] R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group;

[0026] m is an integer greater than or equal to 1;

[0027] n is an integer greater than or equal to 2.

[0028] The hole transport layer is a polymer having the above repeating units, which can help to improve the stability of the polymer and to achieve fast hole conduction and to hinder electron transport.

[0029] In an alternative implementation, the hole transport layer is formed by polymerization of a compound of formula (Al) or formula (B l),

[0030]

[0031] R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R' can be substituted with a halogen, and R' contains at least two polymerizable groups;

[0032] R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group;

[0033] m is an integer greater than or equal to 1.

[0034] The compound of the above structure, the polymerizable groups in R' can achieve polymerization between compounds, the N-containing group can achieve hole transport, and the number of anchoring groups R0 can be multiple. The compound of the above structure, after polymerization, can form a macromolecular polymer to increase the volume of the molecules in the SAM and to reduce the movement of the SAM to the photoelectric layer.

[0035] In an alternative implementation, the polymerizable group comprises at least one of a carbonyl group, an aldehyde group, an alkenyl group, or an amine group.

[0036] In a second aspect, the present application provides a solar cell, which comprises a substrate, a first electrode layer, a hole transport layer, a modification layer, a photoelectric layer, an electron transport layer and a second electrode layer arranged in sequence and in a stack;

[0037] The hole transport layer is an inorganic oxide layer, and the modification layer is a polymer layer. The molecules of the polymer layer comprise a functional group, a polymerizable group and an anchor group. At least part of the anchor groups are chemically connected to the hole transport layer. The functional group is arranged on one side of the photoelectric layer, and the polymerizable group connects the functional group and the anchor group.

[0038] The solar cell of the present application is a reverse structure solar cell. The hole transport layer is arranged between the substrate and the photoelectric layer, and the surface of the hole transport layer is provided with the modification layer. The modification layer is used to improve the stability of the hole transport layer. The modification layer is formed by a polymer. In the molecules of the polymer, the functional group is used to realize the transmission of holes, and the anchor group is used to realize the chemical connection and the physical adsorption connection with the hole transport layer. The polymerizable group is used to connect the functional group and the anchor group to obtain a macromolecular polymer. Compared with the traditional single molecule SAM, the SAM in the present application is a polymer layer. Since the migration energy of the polymer is high, the difficulty of the movement of the molecules in the device can be effectively increased. During the working process of the solar cell, the molecules in the SAM can be prevented from falling off and moving to the photoelectric layer, thereby preventing the decrease of the photoelectric conversion efficiency of the photoelectric layer. Therefore, the stability of the solar cell can be improved.

[0039] In the solar cell of the second aspect of the present application, the polymer forming the modification layer is the same as the polymer forming the hole transport layer in the first aspect of the present application. Herein, no repeated description is given.

[0040] In a third aspect, the present application provides a manufacturing method of a solar cell, which comprises:

[0041] forming a first electrode layer on the surface of the substrate;

[0042] forming a polymerizable single molecule compound layer on the surface of the first electrode layer, the polymerizable single molecule compound being a compound as shown in formula (A1) or formula (B1), and the polymerizable single molecule compound forming the hole transport layer through a polymerization reaction;

[0043]

[0044] forming a photoelectric layer on the surface of the hole transport layer;

[0045] forming an electron transport layer on the surface of the photoelectric layer;

[0046] forming a second electrode layer on a surface of the electron transport layer;

[0047] In formula (A1) and formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups; R0 is selected from at least one of hydroxyl, siloxyl, and phosphonic acid group; and m is an integer greater than or equal to 1.

[0048] In a fourth aspect, the present application provides a method for manufacturing a solar cell, the method comprising:

[0049] forming a first electrode layer on a surface of the substrate;

[0050] forming a hole transport layer on a surface of the first electrode layer, the hole transport layer being an inorganic oxide layer;

[0051] forming a polymerizable monomolecular compound layer on a surface of the hole transport layer, the polymerizable monomolecular compound being a compound as shown in formula (A1) or formula (B1), and the polymerizable monomolecular compound forming a modification layer after polymerization;

[0052]

[0053] forming a photoelectric layer on a surface of the modification layer;

[0054] forming an electron transport layer on a surface of the photoelectric layer;

[0055] forming a second electrode layer on a surface of the electron transport layer;

[0056] In formula (A1) and formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups; R0 is selected from at least one of hydroxyl, siloxyl, and phosphonic acid group; and m is an integer greater than or equal to 1.

[0057] In a fifth aspect, the present application provides a compound for manufacturing a solar cell, the compound being as shown in formula (A1) or formula (B1),

[0058]

[0059] R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups;

[0060] R0 is selected from at least one of hydroxyl, siloxyl, and phosphonic acid group;

[0061] m is an integer greater than or equal to 1.

[0062] In a sixth aspect, the present application provides an energy storage system, which comprises a power converter and the solar cell of the present application, and the power converter is used to transform the voltage and current generated by the solar cell into input to an electrical device or an energy storage battery.

[0063] The technical effects achieved by the third to sixth aspects described above can refer to the corresponding effect descriptions in the first aspect, which will not be repeated here. BRIEF DESCRIPTION OF DRAWINGS

[0064] Figure 1 Structure diagram of a solar cell according to an embodiment;

[0065] Figure 2 Flowchart of a manufacturing method of a solar cell according to an embodiment;

[0066] Figure 3 Structure diagram of a connection of a polymer layer according to an embodiment;

[0067] Figure 4 Structure diagram of a solar cell according to another embodiment of the present application;

[0068] Figure 5 Flowchart of a manufacturing process of a polymer layer according to an embodiment;

[0069] Figure 6 Flowchart of a manufacturing process of a polymer layer according to another embodiment.

[0070] REFERENCE NUMERALS:

[0071] 11 - substrate; 12 - first electrode layer; 13 - hole transport layer; 14 - modification layer; 15 - photoelectric layer; 16 - electron transport layer; 17 - second electrode layer; 21 - functional group; 22 - polymer group; 23 - anchoring group. DETAILED DESCRIPTION

[0072] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings.

[0073] The terms used in the following examples are only for the purpose of describing specific embodiments and are not intended to be limiting of the present application. As used in the specification and the appended claims, the singular forms "a," "an" and "the" are intended to include both singular and plural forms, unless the context clearly indicates otherwise.

[0074] Reference in the specification to "one embodiment" or "some embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. The appearances of the phrase "in one embodiment" or "in some embodiments" in various places in the specification are not necessarily all referring to the same embodiment, although it can. The terms "including," "comprising," "having" and variations thereof are meant to encompass the items listed thereafter and equivalents thereof as well as additional items. The terms "coupled" and "connected," along with variations thereof, are used broadly and encompass both direct and indirect couplings or connections.

[0075] Perovskite solar cells need to solve the problems of high-efficiency large-area preparation, high conversion efficiency, high stability, etc. to realize commercial application, among which the stability problem is widely considered as the biggest obstacle to hinder the commercialization of perovskite, especially the ion movement and molecular movement problem inside the device is serious, which aggravates the difficulty of improving stability. The mainstream commercial perovskite structure includes planar formal structure, planar reverse structure and mesoporous structure. Among them, the planar reverse structure can avoid the use of ion-doped organic hole transport layer, has the characteristics of natural high stability and high efficiency, and is widely accepted by the industry. In the solar cell of reverse structure, the hole transport layer plays the role of transporting holes and blocking electrons, and needs to have good denseness and band matching. At present, nickel oxide, SAM, or nickel oxide and SAM composite layer are often used as hole transport layer in reverse structure. Using nickel oxide as hole transport layer has the advantages of simple preparation method and can be prepared by vacuum method, but because nickel oxide itself has multiple valence states, it is easy to cause redox reaction and decompose perovskite film during operation, resulting in the decrease of perovskite stability. Using SAM or nickel oxide and SAM composite layer as hole transport layer has the advantages of simple preparation method and can be prepared by solution method or vacuum method. Among them, SAM can be used as a hole transport layer or a modification layer of the hole transport layer, and the passivation of nickel oxide is realized by using SAM to prevent the decomposition of perovskite film. Although SAM can physically isolate the contact between perovskite and nickel oxide or avoid the use of nickel oxide, the introduction of a single molecular layer leads to the emergence of other problems. For example, due to the physical adsorption connection of part of the single molecules to the substrate, the physical adsorption connection has poor stability and is easy to desorb under the action of high temperature and electric field, and the single molecules are small in size and easy to move from the substrate to the inside of the cell over time, which can cause the decrease of the power generation efficiency of the cell and reduce the stability of the solar cell.

[0076] Figure 1 FIG. 1 is a schematic diagram of a structure of a solar cell. As shown in FIG. 1, the solar cell includes a substrate 1, a hole transport layer 2, a perovskite layer 3, an electron transport layer 4 and a back electrode 5. Figure 1As shown, the solar cell is a solar cell in a reverse structure. The solar cell comprises, in sequence and in a stacked manner, a substrate 11, a first electrode layer 12, a hole transport layer 13, a photoelectric layer 15, an electron transport layer 16, and a second electrode layer 17.

[0077] The photoelectric layer 15 is a light absorption conversion layer, and is used to realize photoelectric conversion. After the perovskite thin film absorbs light, electron-hole pairs are generated, and the electrons and holes move to the electron transport layer 16 and the hole transport layer 13, respectively, under the action of the built-in electric field, and finally reach the electrode to generate a photovoltaic effect. The photoelectric layer 15 can be a perovskite thin film. The material of the perovskite thin film has a chemical formula of ABX3, where A + includes but is not limited to CH3NH3 + (MA + ), NH2CH=NH2 + (FA + ), Cs + , or Rb + , etc. 2+ includes but is not limited to Pb 2+ , or Sn 2+ , etc. - X includes halogen ions such as Cl-, Br - , or I-. Among them, the perovskite thin film can be, for example, MAPbI3. By adjusting the material composition in ABX3, the band gap of the perovskite battery can be adjusted, for example, the band gap can be controlled between 1.2 eV and 2.5 eV.

[0078] The hole transport layer 13 is used to transport holes. The holes generated by the photoelectric layer 15 move to the hole transport layer 13 and are transported to the first electrode layer 12 through the hole transport layer 13.

[0079] The first electrode layer 12 can be a positive electrode, and is used to connect the hole transport layer 13. The first electrode layer 12 can be a transparent conductive oxide (TCO) such as an indium tin oxide layer.

[0080] The electron transport layer 16 is used to transport electrons. The electrons generated by the photoelectric layer 15 move to the electron transport layer 16 and are transported to the second electrode layer 17 through the electron transport layer 16.

[0081] The second electrode layer 17 can be a negative electrode, and is used to connect the electron transport layer 16. The second electrode layer 17 can be a metal conductive layer such as a silver electrode layer, an aluminum electrode layer, etc. When an external resistance is connected between the first electrode layer 12 and the second electrode layer 17, the electrons flow from the second electrode layer 17 to the first electrode layer 12. The current direction of the external circuit is from the first electrode layer 12 to the second electrode layer 17.

[0082] The substrate 11 is a transparent cover plate, which can be a glass plate or a PET film. The substrate 11 serves as a carrier for the first electrode layer 12 and as an encapsulation for the photoelectric layer 15. During photoelectric conversion, light penetrates the substrate 11, the first electrode layer 12 and the hole transport layer 13, and is incident on the photoelectric layer 15, which absorbs and converts the light to form electron-hole pairs, thereby generating an electric current.

[0083] The hole transport layer 13 is in contact with the photoelectric layer 15. The stability of the hole transport layer 13 directly affects the stability of the photoelectric layer 15. In the embodiments of the present application, the hole transport layer 13 is a polymer layer. The molecules of the polymer layer include functional groups, polymer groups and anchoring groups, at least part of the anchoring groups are chemically adsorbed and connected to the first electrode layer 12; the functional groups are arranged on the side facing the photoelectric layer 15 for hole transport, and the polymer groups connect the functional groups and the anchoring groups.

[0084] Figure 2 FIG. 1 shows a schematic diagram of the connection structure of the polymer layer according to an embodiment. As shown in FIG. 1, the anchoring groups 23 are connected to the first electrode layer 12 on the side of the substrate 11. The functional groups 21 are on the side facing the photoelectric layer, which are mainly used for transporting holes. The polymer groups 22 are located between the functional groups 21 and the anchoring groups 23, and realize polymer connection. Figure 2

[0085] The functional groups include the following groups:

[0086]

[0087] wherein * is a site connected to the polymer group.

[0088] In formula (1-1), R 21 and R 22 are each independently selected from an aryl group or a nitrogen-containing heterocyclic group having 6-30 carbon atoms. R 21 and R 22 may be the same or different.

[0089] For example, the aryl group having 6-30 carbon atoms can be at least one of a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluoranthene group, a triphenylene group, a fluorenyl group, a spirofluorenyl group, a pyrenyl group, a benzanthracene group, a benzofluorene group, a naphthanthracene group, a naphthofluorene group, a dibenzanthracene group, a dibenzofluorene group, a hydrobenzanthracene group, an indenofluorene group, a benzindenofluorene group, and the like.

[0090] The nitrogen-containing heterocyclic group can be, for example, at least one of a carbazolyl group, a benzocarbazolyl group, an indolocarbazolyl group or an indenocarbazolyl group, a pyridyl group, a pyrimidyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, an imidazolyl group, a benzimidazolyl group, a thiazolyl group, a benzothiazolyl group, an oxazolyl group, a benzoxazolyl group, a pyrazolyl group, or a purinyl group.

[0091] ​In formula (1-2), A, B are each independently present or absent, and when A, B are present, A, B are each independently selected from an aryl group of 6 to 30 carbon atoms. The connecting position of A, B in formula (1-2) can be connected to different carbon atoms on the benzene ring of carbazole, and is not limited to the position shown in formula (1-2). Illustratively, the aryl group of 6 to 30 carbon atoms can be at least one of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, fluoranthene, triphenylene, fluorenyl, spirofluorenyl, pyrenyl, benzanthracene, benzofluorene, naphthanthracene, naphthofluorene, dibenzanthracene, dibenzofluorene, hydrogenated benzanthracene, indenofluorene, benzindenofluorene, and the like.

[0092] The hydrogen in formula (1-1) and formula (1-2) can be substituted by an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or halogen. Among them, the alkyl group of 1 to 20 carbon atoms can be a chain alkyl group, such as a straight chain alkyl group or a branched chain alkyl group, or a cyclic alkyl group, and the hydrogen on the ring of the cyclic alkyl group can be substituted by a chain alkyl group. Among them, the lower limit of the number of carbon atoms in the alkyl group can be 1, 2, 3, 4, 5, 6, 7, etc., and the upper limit can be 8, 10, 12, 15, 18, or 20, etc. In some embodiments, the carbon atoms in the alkoxy group can be 1 to 15, 1 to 10, 1 to 8, or 1 to 6, or 1 to 4. Illustratively, the alkyl group of 1 to 20 carbon atoms can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, hexyl, 2-methyl-pentyl, 3-methyl-pentyl, 1,1,2-trimethyl-propyl, 3,3,-dimethyl-butyl, heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, isoheptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, and isomers thereof.

[0093] The alkoxy group of 1 to 20 carbon atoms can be a chain alkoxy group, such as a straight chain alkoxy group or a branched chain alkoxy group, or a cyclic alkoxy group, and the hydrogen on the ring of the cyclic alkyl group can be substituted by a chain alkoxy group. Among them, the lower limit of the number of carbon atoms in the alkoxy group can be 1, 2, 3, 4, 5, 6, 7, etc., and the upper limit can be 8, 10, 12, 15, 18, or 20, etc. In some embodiments, the carbon atoms in the alkoxy group can be 1 to 15, 1 to 10, 1 to 8, or 1 to 6, or 1 to 4. Illustratively, the alkoxy group of 1 to 20 carbon atoms can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, n-octoxy, n-nonoxy, n-decoxy, and isomers of the above alkoxy groups, which are not listed one by one here.

[0094] Halogen can be, for example, F, Cl, Br, I, and the like. Illustratively, when hydrogen in formula (1-1) and formula (1-2) is replaced by halogen, it can be replaced by F.

[0095] The above functional group is a free group in the hole transport layer, which is only connected to the polymerization group, and there is no chemical connection between the functional group and the photoelectric layer.

[0096] Referring to Figure 2 The anchoring group 23 is used to connect with the active group of the first electrode layer 12. The density of the active group on the surface of the first electrode layer 12 for chemical adsorption with the anchoring group 23 is crucial for the deposition of the SAM film. The active group on the surface of the first electrode layer 12 is mainly a hydroxyl group. The oxide layer such as indium tin oxide (ITO) layer obtained by atomic layer deposition (ALD) deposition can increase the density of hydroxyl on the surface of the substrate 11. Correspondingly, the anchoring group 23 in the polymer layer can be selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group. The anchoring group 23 adopts the above groups, which can more easily form a chemical connection such as chemical adsorption connection or form a chemical bond connection with the active group of the first electrode layer 12, effectively increasing the difficulty of molecular movement, thereby effectively improving the stability of the perovskite photovoltaic device.

[0097] Illustratively, the siloxyl group can be trimethoxysilane or triethoxysilane. When the anchoring group 23 is a siloxyl group, the Si atom is connected to the polymerization group 22. When the anchoring group 23 is a phosphonic acid group, the P atom is connected to the polymerization group 22. When the anchoring group 23 is a hydroxyl group, the oxygen in the hydroxyl group can be connected to the polymerization group 22.

[0098] Continuing to refer to Figure 2 The polymerization group 22 is used to connect the anchoring group 23 and the functional group 21. The polymerization group 22 is a macromolecular group, and its structure includes at least two repeating units. The polymerization group 22 can be composed of multiple repeating units. The repeating units in the polymerization group 22 can be selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms. The aryl group of 6-30 carbon atoms, the alkyl group of 1-20 carbon atoms, or the alkoxy group of 1-20 carbon atoms in the polymerization group 22 can be explained and described in the same way as the aryl group of 6-30 carbon atoms, the alkyl group of 1-20 carbon atoms, or the alkoxy group of 1-20 carbon atoms involved in the functional group 21. The hydrogen in the polymerization group 22 can be replaced by halogen, such as F, Cl, Br, I, and the like.

[0099] In one embodiment, the polymer forming the hole transport layer can include repeating units shown in formula (A) or formula (B):

[0100]

[0101] R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups to form a multi-molecular polymerization linkage. The polymerizable groups in R' include, but are not limited to, a carbonyl group, an aldehyde group, an alkenyl group, or an amine group, etc. The R' after polymerization through the polymerizable groups can form a polymerization group of the polymer.

[0102] R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group. R0 can form an anchoring group of the polymer.

[0103] m is an integer greater than or equal to 1, such as 1, 2, 3, 4, 5, 6, or a larger natural number, which is not listed one by one here.

[0104] n is an integer greater than or equal to 2, such as 2, 4, 5, 7, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, or a larger natural number, etc., which is not listed one by one here.

[0105] wherein the polymer layer can be formed by polymerization of a compound represented by formula (A1) or formula (B1),

[0106]

[0107] R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups to form a multi-molecular polymerization linkage. The polymerizable groups in R' include, but are not limited to, a carbonyl group, an aldehyde group, an alkenyl group, or an amine group, etc. The R' after polymerization through the polymerizable groups can form a polymerization group of the polymer.

[0108] R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group. R0 can form an anchoring group of the polymer.

[0109] After polymerization of the above compound, the groups other than R' and R0 can form functional groups of the polymer.

[0110] m is an integer greater than or equal to 1, such as 1, 2, 3, 4, 5, 6, or a larger natural number, which is not listed one by one here.

[0111] Figure 3 A flowchart of a method for manufacturing a solar cell is shown. As shown in FIG. 1, the manufacturing can include the following steps: Figure 3

[0112] S11, forming a first electrode layer 12 on a surface of a substrate; ​

[0113] S12, forming a layer of polymerizable monomolecular compound on the surface of the first electrode layer 12, the polymerizable monomolecular compound being a compound as shown in formula (A1) or formula (B1), the compound as shown in formula (A1) or formula (B1) forming a hole transport layer 13 through a polymerization reaction;

[0114]

[0115] S13, forming a photoelectric layer 15 on the surface of the hole transport layer 13;

[0116] S14, forming an electron transport layer 16 on the surface of the photoelectric layer 15;

[0117] S15, forming a second electrode layer 17 on the surface of the electron transport layer 16.

[0118] When the solar cell of the embodiments of the present application is a battery assembly, a process of laser scribing can be added between steps S11 and S12, between steps S14 and S15, and after step S15, to cut the first electrode layer 12, the hole transport layer 13, the photoelectric layer 15, the electron transport layer 16, and the second electrode layer 17, to form a battery assembly composed of a plurality of thin film cells connected in series and in parallel.

[0119] In formula (A1) and formula (B1), R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R' can be substituted by a halogen, and R' contains at least two polymerizable groups. The number of polymerizable groups in R' is at least two, to form a multi-molecular polymerization connection. The polymerizable groups in R' include, but are not limited to, a carbonyl group, an aldehyde group, an alkenyl group, or an amine group, etc.

[0120] R0 is selected from at least one of a hydroxyl group, a siloxyl group, and a phosphonic acid group. m is an integer greater than or equal to 1.

[0121] In step S11, the first electrode layer 12 can be formed by coating or deposition, for example, a transparent electrode layer can be formed by depositing indium tin oxide on the surface of a substrate. After the first electrode layer 12 is formed, a surface activation treatment can be performed on the first electrode layer 12, to form active groups on the surface of the first electrode layer 12, for example, hydroxyl groups can be formed on the surface of the first electrode layer 12.

[0122] In step S12, the polymerizable monomolecular compound layer is formed on the surface of the first electrode layer 12. The formation can be achieved by one of the following methods: spin coating, blade coating, slot coating, or immersion. The polymerizable monomolecular compound can be the same compound or different compounds. The polymerizable monomolecular compound, such as the compound shown in formula (A1) or formula (B1), is chemically or physically adsorbed to the first electrode layer 12 by self-assembly. For example, the anchor group 23 in the compound shown in formula (A1) or formula (B1) can form a chemical bond with the active group in the first electrode layer 12, or the anchor group 23 can form a physical adsorption with the first electrode layer 12. After the monomolecular layer is formed, the compound that is not chemically or physically adsorbed to the first electrode layer 12 can be removed by cleaning, such as immersion or flushing, leaving a dense monomolecular compound layer. This ensures that in the compound shown in formula (A1) or formula (B1) deposited on the first electrode layer 12, the anchor group 23 is connected to the first electrode layer 12, and the functional group 21 faces the photoelectric layer 15.

[0123] After the excess monomolecular compound is removed, a polymerization reaction is performed. This ensures that in the polymer formed, the anchor group 23 is connected to the first electrode layer 12, and the functional group 21 faces the photoelectric layer 15. In the polymerization reaction, the organic condensation reaction of the intermolecular linking group R' can be achieved by heating or solution immersion. The monomolecules form chemical bonds, and multiple monomolecules form a macromolecule through the linking group R'.

[0124] Referring to Figure 2 and Figure 3 together, after the polymerization of the monomolecular compound, the monomolecular compounds are polymerized together to form a macromolecular polymer. In one molecule of the polymer, the number of anchor groups 23 increases compared to the monomolecular compound. If the molecule of the polymer moves, more energy is required. This increases the difficulty of molecular movement and improves the stability of the hole transport layer 13. The polymerization reaction of the monomolecular compound can be performed under catalytic conditions, or a bridging molecule can be added to achieve the polymerization reaction between different monomolecular compounds. The specific polymerization reaction conditions can be selected according to the type of the polymerizable group, which is not limited here.

[0125] It can be understood that the same polymer layer can be formed by self-polymerization of a single monomolecular compound or copolymerization of multiple monomolecular compounds with different structures. In the thickness direction of the polymer layer, the polymer layer is a monomolecular layer, i.e., the polymer layer is a single layer without stacking at the molecular level. The monomolecular layer structure can ensure the ordered arrangement of each group in the polymer layer and avoid the stacking of multiple molecular layers, which can cause misalignment of the functional groups and reduce the connection strength between the polymer layer and the substrate. In the polymer layer, the length direction of the molecular chain segment of the polymer can be parallel to the substrate to form a monomolecular layer structure.

[0126] The photoelectric layer, electron transport layer and second electrode layer can be formed according to existing preparation methods, such as deposition method, coating method, etc. This application does not make specific limitations on the formation method of the photoelectric layer, electron transport layer and second electrode layer.

[0127] Based on the same technical objective, embodiments of this application also provide another type of solar cell.

[0128] Figure 4 This is a schematic diagram of the structure of a solar cell according to another embodiment of this application. Figure 4 As shown, the solar cell includes a substrate 11, a first electrode layer 12, a hole transport layer 13, a modification layer 14, a photoelectric layer 15, an electron transport layer 16, and a second electrode layer 17, which are sequentially and stacked. The hole transport layer 13 is an inorganic oxide layer, and the modification layer 14 is a polymer layer. The polymer layer contains functional groups, polymeric groups, and anchoring groups in its molecules, and at least some of the anchoring groups are chemically connected to the hole transport layer. The functional groups are located on one side of the photoelectric layer and are mainly used to realize hole transport. The polymeric groups connect the functional groups and the anchoring groups.

[0129] In the solar cell of this embodiment, the hole transport layer 13 is an oxide, such as nickel oxide. To prevent the nickel oxide from decomposing, a modification layer 14, which is a polymer layer, is disposed on the surface of the hole transport layer 13. The polymer layer, acting as a SAM layer, stabilizes and blocks the hole transport layer 13. In addition to the hole transport layer 13 and... Figure 1 Except for the hole transport layer 13 shown, the other structures, such as the substrate 11, the first electrode layer 12, the photoelectric layer 15, the electron transport layer 16, and the second electrode layer 17, are all the same. Figure 1 The same explanation applies. I will not repeat it here.

[0130] Figure 4 The method for fabricating the solar cell structure shown may include the following steps:

[0131] S21. A first electrode layer 12 is formed on the surface of the substrate;

[0132] S22. A hole transport layer 13 is formed on the surface of the first electrode layer 12; the hole transport layer 13 may be an inorganic oxide layer, such as a nickel oxide layer.

[0133] S23. A polymerizable monomolecular compound layer is formed on the surface of the hole transport layer 13. The polymerizable monomolecular compound is a compound as shown in formula (A1) or formula (B1). The compound shown in formula (A1) or formula (B1) is polymerized to form a modification layer 14.

[0134]

[0135] S24, forming a photoelectric layer 15 on the surface of the modification layer 14;

[0136] S25, forming an electron transport layer 16 on the surface of the photoelectric layer 15;

[0137] S26, forming a second electrode layer 17 on the surface of the electron transport layer 16.

[0138] In formula (A1) and formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; the hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups. The number of polymerizable groups in R' is at least two to form a multi-molecular polymerization connection. The polymerizable groups in R' include but are not limited to carbonyl, aldehyde, alkenyl, or amine, etc.

[0139] R0 is selected from at least one of hydroxyl, siloxyl, phosphonic acid group; m is an integer greater than or equal to 1.

[0140] The first electrode layer 12, the hole transport layer 13, the photoelectric layer 15, the electron transport layer 16 and the second electrode layer 17 of the embodiments of the present application can be prepared according to the existing preparation method, such as deposition method, coating method, etc. The forming method of the first electrode layer 12, the hole transport layer 13, the photoelectric layer 15, the electron transport layer 16 and the second electrode layer 17 is not specifically limited in the present application.

[0141] The preparation of the polymer layer as the modification layer 14 can refer to the preparation method of the polymer layer as the hole transport layer 13 in the above embodiments.

[0142] Specifically as follows:

[0143] In step S23, the polymerizable monomolecular compound layer is formed on the surface of the hole transport layer 13, which can be realized by one of the following methods: such as spin coating, blade coating, slot coating, or soaking method. The polymerizable monomolecular compound can be the same compound, or different compounds. The polymerizable monomolecular compound, such as the compound shown in formula (A1) or formula (B1), realizes chemical adsorption connection or physical adsorption connection with the hole transport layer 13 through self-assembly characteristics. For example, part of the anchor groups in the compound shown in formula (A1) or formula (B1) can form chemical bonds with active groups in the hole transport layer 13, and part of the anchor groups can form physical adsorption connection with the hole transport layer 13. After the monomolecular layer is formed, the compound which is not chemically or physically adsorbed to the hole transport layer 13 can be removed by cleaning, such as soaking or flushing, leaving a dense monomolecular compound layer, so that in the compound shown in formula (A1) or formula (B1) deposited on the hole transport layer 13, the anchor group R0 is connected with the hole transport layer 13, and the functional group is directed to the photoelectric layer 15.

[0144] After the removal of the excess monomolecular compound, the polymerization reaction is performed, so that the anchor groups in the formed polymer are all connected with the hole transport layer, and the functional groups are oriented towards the photoelectric layer. The polymerization reaction of the monomolecular compound can be performed under catalytic conditions, and a bridging molecule can be externally added to achieve the polymerization reaction between different monomolecular compounds. The specific polymerization reaction conditions can be selected according to the type of the specific polymerizable group, and are not specifically limited here.

[0145] It can be understood that the same polymer layer can be formed by self-polymerization of a single monomolecular compound, or can be formed by copolymerization of monomolecular compounds with different structures.

[0146] In the manufacturing method of the present application, the self-assembled monomolecular layer is formed by introducing a polymerizable monomolecular compound. The polymerizable monomolecular compound first forms a monomolecular layer, and then the monomolecular layer is converted into a large-molecular polymer layer in which a plurality of monomoleculars are chemically bonded to each other by using polymerization means (such as heating, soaking in an acidic solution, adding a reaction small molecule, etc.). The thickness of the large-molecular polymer layer is the same as that of the monomolecular layer. The connection sites between the large-molecular polymer and the first electrode layer or the hole transport layer are more, and the volume is larger. The movement of the monomoleculars bonded to each other is hindered, and the energy required for migration is high, which is conducive to reducing the stability problem caused by the movement of the monomoleculars.

[0147] As described above, the polymer layer in the present application can be used as a hole transport layer or a modification layer.

[0148] The present application provides a compound for preparing a solar cell, which is shown in formula (A1) or formula (B1),

[0149]

[0150] wherein the N-containing group is a functional group for transporting holes. R' is a linking group for realizing the polymerization connection between molecules, and connecting the functional group and the anchor group in the monomolecular. R0 is an anchor group for realizing the chemical connection and physical adsorption connection between the monomolecular and the substrate assembly.

[0151] R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; the hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups.

[0152] R0 is selected from at least one of a hydroxyl group, a siloxyl group, and a phosphonic acid group.

[0153] m is an integer greater than or equal to 1.

[0154] In each of the embodiments of the present application, the aryl group of 6-30 carbon atoms can be exemplarily at least one of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, fluoranthene, triphenylene, fluorenyl, spirofluorenyl, pyrenyl, benzanthryl, benzofluorenyl, naphthanthryl, naphthofluorenyl, dibenzanthryl, dibenzofluorenyl, hydrogenated benzanthryl, indenofluorenyl, benzindenofluorenyl, and the like.

[0155] The alkyl group of 1-20 carbon atoms can be a chain alkyl group such as a straight chain alkyl group or a branched chain alkyl group, or a cyclic alkyl group, and the hydrogen on the ring of the cyclic alkyl group can be substituted with a chain alkyl group. Exemplarily, the alkyl group of 1-20 carbon atoms can be a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, an i-pentyl group, a neopentyl group, a hexyl group, a 2-methyl-pentyl group, a 3-methyl-pentyl group, a 1,1,2-trimethyl-propyl group, a 3,3,-dimethyl-butyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, an isoheptyl group, an octyl group, a nonyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, or a cyclodecyl group, and isomers thereof.

[0156] The alkoxy group of 1-20 carbon atoms can be a chain alkoxy group such as a straight chain alkoxy group or a branched chain alkoxy group, or a cyclic alkoxy group, and the hydrogen on the ring of the cyclic alkyl group can be substituted with a chain alkoxy group. Exemplarily, the alkoxy group of 1-20 carbon atoms can be a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a n-butoxy group, an i-butoxy group, a t-butoxy group, a n-pentoxy group, an i-pentoxy group, a neopentoxy group, a n-hexoxy group, a n-octoxy group, a n-nonoxy group, a n-decoxy group, and isomers of the above alkoxy groups, which are not listed one by one here.

[0157] As an exemplary illustration, the compound used for preparing a solar cell can be selected from at least one of the following structures:

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] The compounds 70-126 are respectively compounds 7-63 in which the carbonyl group is replaced with an aldehyde group.

[0166]

[0167] Compounds 133-189 are obtained by replacing the carbonyl group in compounds 64-126 with an amino group, respectively.

[0168] It is understood that all allotropes of the above compounds should be understood to be within the scope of this application.

[0169] Using compounds 6 and 67 as examples, the process of polymer formation is explained.

[0170] Figure 5 This is a schematic diagram illustrating the preparation process of a polymer layer according to one embodiment. Figure 5 As shown, taking compound 6 as an example, compared to conventional self-assembled monomolecule materials, it has two long alkane chains with carbonyl groups at the ends on the benzene ring of the connecting group. These long alkane chains with carbonyl groups at the ends are the connecting groups of the molecule. Obtaining a self-assembled layer with the thickness of a macromolecular polymer layer mainly involves the following steps: First, the monomolecule with the structure shown in compound 6 is deposited on the surface of the first electrode layer, such as transparent indium tin oxide. Due to the self-assembly characteristics of the monomolecule shown in compound 1, the anchoring group shown in silane reacts with the hydroxyl groups on the surface of transparent indium tin oxide to form chemical bonds, constituting chemisorption. Some materials will form physical adsorption, while some compounds will not contact transparent indium tin oxide and float on the surface of other monomolecule compounds. Solvent rinsing can leave behind molecules that have formed chemisorption and physical adsorption, leaving a monolayer that can completely cover the first electrode layer. Then, the sample is immersed in an acidic solution. In the acidic solution, the intermolecular connecting groups of adjacent compounds undergo a condensation reaction to form covalent bonds, thereby obtaining a macromolecular polymer layer.

[0171] Figure 6 This is a schematic diagram illustrating the preparation process of the polymer layer according to another embodiment. Figure 6As shown, compound 67 is an example, which has two short alkanes with aldehyde groups at the end on the benzene ring of the linker, and the alkanes with aldehyde groups at the end are the linker of the molecule. The self-assembled layer with the thickness of the macromolecular polymer layer mainly includes the following steps: first, the compound 67 molecules are deposited on the surface of the transparent indium tin oxide, and the compound molecules are chemically adsorbed by the self-assembly characteristics, the anchor group of the silane reacts with the hydroxyl group on the surface of the transparent indium tin oxide to form a chemical bond, part of the material forms physical adsorption, and another part of the compound is not in contact with the transparent indium tin oxide and floats on the surface of the other monomolecular compound. The solvent flushing can leave the molecules forming chemical adsorption and physical adsorption, and the single-layer molecule layer left can completely cover the first electrode layer. Then the sample is immersed in a solution containing a bridging molecule, such as H2N-(CH2)n-NH2, n can be 1, 2, 3, 4, 5, 6, 7 or 8, etc. The bridging molecule enters between adjacent compound 67 molecules, and the linker of the molecule and the bridging molecule condense to form a covalent bond, thereby obtaining a macromolecular polymer layer.

[0172] The structure of the bridging molecule of one embodiment is as follows:

[0173]

[0174] Through the above analysis, it can be known that the solar cell of the embodiment of the present application adopts self-assembly monomolecular deposition and then polymerization to form a large polymer layer, to form a hole transport layer or a modification layer of a trans-structured perovskite cell. Compared with directly depositing a polymer thin film, the thickness of the hole transport layer or the modification layer can be ensured, and the charge transport is prevented from being blocked due to being too thick. At the same time, the surface group of the hole transport layer is more consistent by using the post-polymerization method. In addition, the polymer molecules formed have a larger binding energy with the substrate than the single assembled molecules, and are less likely to separate from the substrate. At the same time, the polymer molecules are larger in size and have more obvious steric hindrance effects, and are less likely to move. The above are all conducive to the stability of the hole transport layer.

[0175] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed in the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A solar cell, characterized by, The substrate, the first electrode layer, the hole transport layer, the photoelectric layer, the electron transport layer and the second electrode layer are sequentially and laminatedly arranged. The hole transport layer is a polymer layer, molecules of the polymer layer include a functional group, a polymerization group and an anchor group, at least part of the anchor groups are chemically connected with the first electrode layer; the functional group is arranged on a side of the photoelectric layer, and the polymerization group connects the functional group and the anchor group.

2. The solar cell according to claim 1, characterized in that, The functional group includes the following groups: wherein, in formula (1-1), the R 21 and the R 22 are each independently selected from aryl of 6 to 30 carbon atoms; A and B are each independently present or not present, when A and B are present, A and B are each independently selected from an aryl group of 6-30 carbon atoms; Hydrogen in the formula (1-1) and the formula (1-2) can be substituted by an alkyl group of 1-20 carbon atoms, an alkoxy group of 1-20 carbon atoms, or halogen; * is a site connected with a polymerization group.

3. Solar cell according to any of claims 1-2, characterized in that, The repeating unit in the polymerization group is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; Wherein, hydrogen in the polymerization group can be substituted by halogen.

4. Solar cell according to any of claims 1 to 3, characterized in that The anchor group is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group.

5. Solar cell according to any of claims 1 to 4, characterized in that The hole transport layer includes a repeating unit shown in formula (A) or a repeating unit shown in formula (B): Wherein, the R is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; hydrogen in the R can be substituted by halogen; The R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group; m is an integer greater than or equal to 1; n is an integer greater than or equal to 2.

6. The solar cell according to any one of claims 1 to 5, wherein The hole transport layer is formed by polymerization of a compound shown in formula (A1) or formula (B1), The R' is selected from an aryl group of 6-30 carbon atoms, an alkyl group of 1-20 carbon atoms, or an alkoxy group of 1-20 carbon atoms; hydrogen in the R' can be substituted by halogen, and the R' contains at least two polymerizable groups; The R0 is selected from at least one of a hydroxyl group, a siloxyl group, or a phosphonic acid group; m is an integer greater than or equal to 1.

7. The solar cell according to claim 6, characterized in that, The polymerizable group includes at least one of a carbonyl group, an aldehyde group, an alkenyl group, or an amine group.

8. Solar cell according to any of claims 1 to 7, characterized in that The polymer layer is a monomolecular layer structure in the thickness direction.

9. A solar cell, characterized by, The substrate, the first electrode layer, the hole transport layer, the modification layer, the photoelectric layer, the electron transport layer and the second electrode layer are sequentially and laminatedly arranged; The hole transport layer is an inorganic oxide layer, the modification layer is a polymer layer, molecules of the polymer layer include a functional group, a polymerization group and an anchor group, at least part of the anchor groups are chemically connected with the hole transport layer; the functional group is arranged on a side of the photoelectric layer, and the polymerization group connects the functional group and the anchor group.

10. A method for manufacturing a solar cell, characterized in that, It includes: Forming a first electrode layer on a surface of a substrate; Forming a polymerizable monomolecular compound layer on a surface of the first electrode layer, the polymerizable monomolecular compound is a compound shown in formula (A1) or formula (B1), and the polymerizable monomolecular compound forms a hole transport layer through a self-polymerization reaction; Forming a photoelectric layer on a surface of the hole transport layer; Forming an electron transport layer on a surface of the photoelectric layer; forming a second electrode layer on a surface of the electron transport layer; in formula (A1) and formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups; R0 is selected from at least one of hydroxyl, siloxyl, phosphonic acid group; m is an integer greater than or equal to 1.

11. A method for manufacturing a solar cell, characterized in that, comprising: forming a first electrode layer on a surface of the substrate; forming a hole transport layer on a surface of the first electrode layer, the hole transport layer being an inorganic oxide layer; forming a polymerizable monomolecular compound layer on a surface of the hole transport layer, the polymerizable monomolecular compound being a compound as shown in formula (A1) or formula (B1), the polymerizable monomolecular compound forming a modification layer through a self-polymerization reaction; forming a photoelectric layer on a surface of the modification layer; forming an electron transport layer on a surface of the photoelectric layer; forming a second electrode layer on a surface of the electron transport layer; in formula (A1) and formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups; R0 is selected from at least one of hydroxyl, siloxyl, phosphonic acid group; m is an integer greater than or equal to 1.

12. A compound for use in the preparation of a solar cell as claimed in any one of claims 1 to 9, characterised in that, the compound is as shown in formula (A1) or formula (B1), R' is selected from aryl of 6-30 carbon atoms, alkyl of 1-20 carbon atoms, or alkoxy of 1-20 carbon atoms; hydrogen in R' can be substituted by halogen, and R' contains at least two polymerizable groups; R0 is selected from at least one of hydroxyl, siloxyl, phosphonic acid group; m is an integer greater than or equal to 1.

13. An energy storage system characterized by, a power converter for transforming voltage and current generated by the solar cell into input to an electrical device or an energy storage battery.

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