Perovskite thin film and preparation method thereof, perovskite precursor solution, photoelectric device and electric device

Abstract

The invention relates to the technical field of photoelectric devices, in particular to a perovskite thin film and a preparation method thereof, a perovskite precursor solution, a photoelectric device and an electric device. According to the perovskite thin film provided by the invention, the perovskite thin film comprises an ABX3 type perovskite material and a cross-linked polymer, and the cross-linked polymer is a polymer obtained by cross-linking an ether-containing amide monomer. The cross-linked polymer contained in the perovskite thin film provided by the invention can effectively passivate surface defects of the perovskite thin film so as to improve thermal stability and photoelectric properties of the perovskite thin film.

Description

Technical Field

[0001] The present application relates to the technical field of optoelectronic devices, and in particular to a perovskite film and a preparation method thereof, a perovskite precursor solution, an optoelectronic device, and an electrical device. Background Art

[0002] In recent years, due to the advantages of perovskite materials such as high absorption coefficient, long carrier lifetime, low exciton binding energy and low cost, they have been widely used in optoelectronic devices such as solar cells, light-emitting diodes, and field-effect transistors.

[0003] Research has found that the crystallization quality of perovskite films in optoelectronic devices plays an important role in ensuring their optoelectronic properties. The main reasons for the poor crystallization quality of perovskite films include surface defect enrichment and morphological inhomogeneity. The defects of perovskite materials will lead to increased scattering on the carrier transmission path, hinder the effective migration of carriers, etc., which in turn affects its optoelectronic properties. In addition, the defects of perovskite materials are also attack points for external factors such as temperature and light, as well as water and oxygen environmental conditions, which destroys the perovskite crystal structure and easily leads to the decomposition of perovskite, affecting the performance of optoelectronic devices at high temperatures. Therefore, chemical passivation treatment of perovskite surface defects has become a hot topic of current research. Summary of the invention

[0004] Based on this, the present application provides a perovskite film and a preparation method thereof, a perovskite precursor solution, an optoelectronic device, and an electrical device. The cross-linked polymer contained in the perovskite film provided in the present application can effectively passivate the surface defects of the perovskite film to improve the thermal stability and optoelectronic performance of the perovskite film.

[0005] In a first aspect of the present application, a perovskite film is provided, wherein the perovskite film comprises an ABX3 type perovskite material and a cross-linked polymer.

[0006] Wherein, the monomers for preparing the cross-linked polymer include ether-containing amide monomers.

[0007] In one embodiment, the ether group-containing amide monomer includes one or more compounds represented by formula (I-1):

[0008] ,

[0009] Among them, R 11 and R 12 Each is independently a substituted or unsubstituted C2~C6 alkenyl, or a substituted or unsubstituted C2~C6 alkynyl; n1 is an integer between 1 and 30.

[0010] In one embodiment, R 11 and R 12Each is independently vinyl, allyl, ethynyl or propargyl; n1 is an integer between 0 and 20.

[0011] In one embodiment, the ether group-containing amide monomer includes one or more of the compounds represented by formula (II-1) to formula (II-3):

[0012] , or ; n2~n4 are each independently an integer between 1 and 20.

[0013] In one embodiment, the number average molecular weight of the polyethylene glycol diacrylamide is 400-4000.

[0014] In one of the embodiments, in the perovskite film, the mass ratio of the ABX3 type perovskite material and the cross-linked polymer is (0.7~2): (0.0005~0.003).

[0015] The second aspect of the present application provides a perovskite precursor solution, which includes an ABX3 precursor material, an ether-containing amide monomer and a solvent; the ether-containing amide monomer is the ether-containing amide monomer in the perovskite film described in any embodiment of the first aspect of the present application.

[0016] In one embodiment, in the perovskite precursor solution, the concentration of the ether-containing amide monomer is 0.3 mg / mL to 3 mg / mL.

[0017] In one embodiment, in the perovskite precursor solution, the concentration of the ABX3 precursor material is 0.7 g / mL~2 g / mL.

[0018] In a third aspect of the present application, a method for preparing a perovskite film is provided, comprising the following steps:

[0019] Mixing an ABX3 precursor material, an ether-containing amide monomer, and a solvent to prepare a perovskite precursor solution;

[0020] coating the perovskite precursor solution on a substrate;

[0021] Annealing is performed on the substrate coated with the perovskite precursor solution to crosslink the ether group-containing amide monomers to obtain a crosslinked polymer; and the perovskite film is prepared.

[0022] In a fourth aspect of the present application, a photoelectric device is provided, comprising the perovskite film described in any one of the embodiments of the first aspect of the present application or the perovskite film prepared by the preparation method described in the third aspect of the present application.

[0023] In one embodiment, the optoelectronic device includes a stacked hole transport layer, a perovskite film, a passivation layer, and an electron transport layer;

[0024] Wherein, the hole transport layer comprises one or more of formula (III-1) and formula (III-2): ;

[0025] R 31 , R 32 , R 33 , R 34 , R 35 and R 36 Each is independently hydrogen, halogen, cyano, amino, substituted or unsubstituted C1~C6 alkyl, C1~C6 alkoxy; m1 and m2 are each independently an integer between 0 and 9.

[0026] In one embodiment, the hole transport layer comprises , , and One or more of .

[0027] In one embodiment, the passivation layer comprises ; wherein m3 is an integer between 1 and 6, and R4 is a halogen.

[0028] In one embodiment, the passivation layer includes propylenediamine hydroiodide.

[0029] A fifth aspect of the present application provides an electrical device comprising the optoelectronic device described in any one of the embodiments of the fourth aspect of the present application.

[0030] The present application selects a polymer obtained by cross-linking ether-containing amide monomers as an additive for the perovskite film, wherein the flexibility of the ether bond can reduce the system hardness of the perovskite material to fill the grain boundaries in the perovskite body, thereby effectively isolating the external environment from the perovskite film, enhancing the thermal temperature resistance or environmental stability of the device, and extending its service life.

[0031] In addition, the cross-linked polymer of the present application can solve the problems of high activity, volatility and fragility of small molecule monomers. Moreover, ether-containing amide monomers can be cross-linked and polymerized at room temperature or annealing temperature to form polymers, and their cross-linked network structure can effectively control the disordered movement during the formation of perovskite films, thereby improving the stability of perovskite films and reducing the defect enrichment of perovskite films. At the same time, the oxygen atoms and nitrogen atoms in the amide can respectively react with the B in the perovskite. 2+ and X -interaction to further suppress the formation of multiple intermediate phases and promote the directional crystallization of perovskite films.

[0032] Therefore, the cross-linked polymer contained in the perovskite film provided in the present application can effectively passivate the surface defects of the perovskite film and improve the crystallization quality of the perovskite film to ensure the thermal stability and photoelectric performance of the optoelectronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 A schematic diagram of the structure of an optoelectronic device provided in one embodiment of the present application; wherein, the optoelectronic device-10, the transparent conductive layer-101, the hole transport layer-102, the perovskite film-103, the passivation layer-104, the electron transport layer-105, the electrode-106;

[0035] Figure 2 JV curves of perovskite solar cells prepared in the examples and comparative examples of the present application;

[0036] Figure 3 This is a thermal stability curve diagram of the perovskite solar cells prepared in the examples and comparative examples of the present application. DETAILED DESCRIPTION

[0037] The following is a further complete and clear description of the perovskite film and its preparation method, perovskite precursor solution, optoelectronic device, and electrical device of the present application in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0038] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0039] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: C1~C5 alkyl, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NQQ', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, nitro or halogen, and the above groups may also be further substituted by substituents acceptable in the art; it is understood that Q and Q' in -NQQ' are each independently substituted by a group acceptable in the art, including but not limited to H, C1~C5 alkyl, halogen, hydroxyl, nitro or amino.

[0040] In the present application, "alkenyl" refers to a group containing at least one unsaturated site, i.e., a carbon-carbon sp 2 A hydrocarbon of a positive carbon atom, a secondary carbon atom, a tertiary carbon atom or a ring carbon atom of a double bond. A phrase comprising the term, for example, "C2~C6 alkenyl" refers to an alkenyl group comprising 2 to 6 carbon atoms, and each occurrence may be independently of each other C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl. Suitable examples include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7) and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0041] "Alkynyl" refers to a hydrocarbon containing a positive carbon atom, a secondary carbon atom, a tertiary carbon atom or a ring carbon atom having at least one unsaturated site, i.e., a carbon-carbon sp triple bond. Phrases containing this term, for example, "C2~C6 alkynyl" refers to an alkynyl containing 2 to 6 carbon atoms, each occurrence of which can be independently C2 alkynyl, C3 alkynyl, C4 alkynyl, C5 alkynyl, C6 alkynyl. Suitable examples include, but are not limited to, ethynyl (-C≡CH) and propargyl (-CH2C≡CH).

[0042] In the present application, "alkyl" can represent straight chain, branched and / or cyclic alkyl. The phrase comprising the term, for example, "C1~C6 alkyl" refers to an alkyl containing 1~6 carbon atoms, and each occurrence can be independently of each other C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl. The non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 4-methyl-2-pentyl, n-hexyl or cyclohexyl.

[0043] "Alkoxy" refers to a group with -O-alkyl, i.e., an alkyl group as defined above is connected to a parent core structure via an oxygen atom. Phrases containing this term, for example, "C1~C6 alkoxy" refers to an alkyl moiety containing 1 to 6 carbon atoms, each occurrence of which can be independently C1 alkoxy, C4 alkoxy, C5 alkoxy, C6 alkoxy. Suitable examples include, but are not limited to, methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt) and tert-butoxy (-OC(CH3)3 or -OtBu).

[0044] In a first aspect of the present application, a perovskite film is provided, wherein the perovskite film comprises an ABX3 type perovskite material and a cross-linked polymer.

[0045] Wherein, the monomers for preparing the cross-linked polymer include ether-containing amide monomers.

[0046] The present application selects a polymer obtained by cross-linking ether-containing amide monomers as an additive for the perovskite film, wherein the flexibility of the ether bond can reduce the system hardness of the perovskite material to fill the grain boundaries in the perovskite body, thereby effectively isolating the external environment from the perovskite film, enhancing the thermal temperature resistance or environmental stability of the device, and extending its service life.

[0047] In addition, the cross-linked polymer of the present application can solve the problems of high activity, volatility and fragility of small molecule monomers. Moreover, ether-containing amide monomers can be cross-linked and polymerized at room temperature or annealing temperature to form polymers, and their cross-linked network structure can effectively control the disordered movement during the formation of perovskite films, thereby improving the stability of perovskite films and reducing the defect enrichment of perovskite films. At the same time, the oxygen atoms and nitrogen atoms in the amide can respectively react with the B in the perovskite. 2+ and X - interaction to further suppress the formation of multiple intermediate phases and promote the directional crystallization of perovskite films.

[0048] Therefore, the cross-linked polymer included in the perovskite film provided in the present application can effectively passivate the surface defects of the perovskite film and improve the crystallization quality of the perovskite film to ensure the thermal stability and photoelectric performance of the optoelectronic device.

[0049] In one example, the cross-linked polymer is a polymer obtained by cross-linking ether-containing amide monomers.

[0050] The traditional method to reduce defects in perovskite films is mainly to add crosslinkers to the perovskite films. At present, the widely used crosslinkers are mainly triacrylate crosslinkers and their derivatives, siloxane crosslinkers and their derivatives; the crosslinking temperature required for the above crosslinking monomers is too high, usually above 150°C. Therefore, in the preparation process of perovskite films, they are usually heated again after annealing. Continuous high-temperature annealing will damage the perovskite film, causing its structure to reorganize or decompose, thereby affecting the efficiency and stability of optoelectronic devices.

[0051] Based on this, in one example, the ether group-containing amide monomer includes one or more of the compounds represented by formula (I-1):

[0052] ,

[0053] Among them, R 11 and R 12 Each is independently a substituted or unsubstituted C2-C6 alkenyl or a substituted or unsubstituted C2-C6 alkynyl; n1 is an integer between 1 and 30. Specifically, n1 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[0054] The ether group-containing amide monomer provided above can be polymerized to form a network structure at room temperature or in an annealing step without an additional heating step, thereby effectively avoiding structural damage to the perovskite film caused by high temperature conditions; at the same time, the flexible ether bond of the cross-linking monomer can effectively fill the grain boundary of the perovskite body, and the C=O functional group and the NH functional group can respectively bind to the B in the perovskite film. 2+ and X - interact with each other to passivate the surface defects of the perovskite film and improve the crystallization quality of the perovskite film.

[0055] In one example, R 11 and R 12 Each is independently vinyl, allyl, ethynyl or propargyl; n1 is an integer between 0 and 20.

[0056] In one example, the ether group-containing amide monomer includes one or more of the compounds represented by formula (II-1) to formula (II-3):

[0057] , or ; n2~n4 are each independently an integer between 1 and 20.

[0058] n2, n3 and n4 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0059] In one specific example, the structural formula of the ether group-containing amide monomer is In a more specific example, the number average molecular weight of the ether group-containing amide monomer is 400-4000. On the one hand, the polyethylene glycol diacrylamide can be polymerized to form a network structure at room temperature or during the annealing process of the perovskite film preparation, and the flexible structure of the ether bond main chain can fill the perovskite grain boundary; the amide group can be respectively combined with the active ingredient B of the perovskite 2+ , X - Such interactions promote the directional crystallization of perovskite films and improve device efficiency.

[0060] Specifically, the number average molecular weight of the ether-containing amide monomer includes but is not limited to 400, 600, 800, 1000, 1200, 1500, 1800, 2000, 2400, 2800, 3000, 3200, 3500, 3600, 3700, 3800, 3900 or 4000.

[0061] In one example, in the perovskite film, the mass ratio of the ABX3 perovskite material and the cross-linked polymer is (0.7~2): (0.0005~0.003) mg. Limiting the mass ratio of the ABX3 perovskite material and the cross-linked polymer can effectively cover the defects of the perovskite material with the cross-linked polymer; in addition, ensuring a high content of the ABX3 perovskite material can also provide more active areas, which helps to increase the generation and transmission of carriers, reduce losses in the transmission path, and improve the open circuit voltage and short circuit current of the battery. Specifically, the mass ratio of the ABX3 type perovskite material and the cross-linked polymer includes but is not limited to 0.96:0.0005, 0.96:0.0006, 0.96:0.0007, 0.96:0.0008, 0.96g:0.0009, 0.96:0.001, 0.96:0.0011, 0.96:0.0012, 0.96:0.0013, 0.96:0.0014, 0.96:0.0015, 0.96:0.0016, 0.96: 0.0018, 0.96: 0.002, 0.96: 0.0025, 0.96: 0.003, 1: 0.0005, 1: 0.0006, 1: 0.0007, 1: 0.0008, 1: 0.001, 1.1: 0.0005, 1.13: 0.0005, 1.15: 0.0005, 1.15: 0.0006, 1.15: 0.0007, 1.15: 0.0008, 1.15: 0.0009, 1.15 : 0.001, 1.15: 0.0012mg, 1.15: 0.0014, 1.15: 0.0015mg, 1.2: 0.005, 1.2: 0.0006, 1.2: 0.0007, 1.2g: 0.00 08, 1.2: 0.0009, 1.2: 0.001, 1.2: 0.0012, 1.2: 0.0014, 1.2: 0.0015, 1.3: 0.0005mg, 1.3: 0.0006, 1.3: 0.0 007, 1.3: 0.0008, 1.3g: 0.0009, 1.3: 0.001, 1.3: 0.0012, 1.3: 0.0014, 1.3: 0.0015, 1.5: 0.0005, 1.5: 0.0 006, 1.5: 0.0007, 1.5: 0.0008, 1.5: 0.0009, 1.5: 0.001, 1.5: 0.0012, 1.5: 0.0014, 1.5: 0.0015, 2: 0.0005.

[0062] In one example, A includes FA + 、MA + , Cs + , Rb + and K+ One or more of. B includes Pb 2+ and Sn 2+ One or more of. X includes Cl - Br - and I - One or more of .

[0063] In a second aspect of the present application, a perovskite precursor solution is provided, the perovskite precursor solution comprising an ABX3 precursor material, an ether-containing amide monomer and a solvent. The ether-containing amide monomer is the ether-containing amide monomer in the perovskite film described in any example of the first aspect of the present application.

[0064] In one example, the ABX3 precursor material A includes FA + 、MA + , Cs + , Rb + and K + One or more of. B includes Pb 2+ and Sn 2+ One or more of. X includes Cl - Br - and I - One or more of .

[0065] It can be understood that the types of the ether group-containing amide monomers are the same as the types of the ether group-containing amide monomers described in the first aspect of the present application, so they are not described here in detail.

[0066] In one example, the solvent includes one or more of N,N-dimethylformamide, N-methylpyrrolidone, acetonitrile, dimethyl sulfoxide, ethanol and acetone.

[0067] The concentration of the ether-containing amide monomer in the perovskite precursor solution plays an important role in promoting the orderly growth of perovskite crystals, reducing crystal defects, and improving crystal quality. In one example, the concentration of the ether-containing amide monomer in the perovskite precursor solution is 0.3 mg / mL to 3 mg / mL. Specifically, in the perovskite precursor solution, the concentration of the ether-containing amide monomer includes but is not limited to 0.3 mg / mL, 0.35 mg / mL, 0.45 mg / mL, 0.48 mg / mL, 0.5 mg / mL, 0.52 mg / mL, 0.55 mg / mL, 0.6 mg / mL, 0.65 mg / mL, 0.7 mg / mL, 0.75 mg / mL, 0.8mg / mL, 0.9 mg / mL, 1 mg / mL, 1.1 mg / mL, 1.2 mg / mL, 1.3 mg / mL, 1.4 mg / mL, 1.5 mg / mL, 1.6 mg / mL, 1.7 mg / mL, 1.8 mg / mL, 1.9 mg / mL, 2 mg / mL, 2.1 mg / mL, 2.2 mg / mL, 2.3 mg / mL, 2.4 mg / mL, 2.5 mg / mL, 2.6 mg / mL, 2.7 mg / mL, 2.8 mg / mL, 2.9 mg / mL or 3 mg / mL.

[0068] The appropriate concentration of ABX3 helps to promote the formation of large perovskite grains and reduce the number of grain boundaries. At the same time, it is also possible to avoid premature crystallization and precipitation caused by excessive concentration of ABX3 precursor materials, thereby affecting the temperature and storage time of the solution. In one example, in the perovskite precursor solution, the concentration of the ABX3 precursor material is 0.7g / mL~2g / mL. Specifically, in the perovskite precursor solution, the concentration of the ABX3 precursor material includes but is not limited to 0.7g / mL, 0.8 g / mL, 0.9 g / mL, 1 g / mL, 1.15 g / mL, 1.17 g / mL, 1.19 g / mL, 1.2 g / mL, 1.3 g / mL, 1.4 g / mL, 1.5 g / mL, 1.6 g / mL, 1.7 g / mL, 1.8 g / mL, 1.9 g / mL or 2 g / mL.

[0069] In another example, in the perovskite precursor solution, the concentration of the ABX3 precursor material is 0.8 mol / L to 2 mol / L. Specifically, in the perovskite precursor solution, the concentration of the ABX3 precursor material is 0.9 mol / L, 1 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L or 2 mol / L.

[0070] In one example, the ABX3 precursor material A includes FA + 、MA + , Cs + , Rb + and K + One or more of. B includes Pb 2+ and Sn 2+ One or more of. X is 1 - . At this time, the perovskite precursor solution also includes an additive. Specifically, the types of additives include one or more of MACl, PbCl2, MABr, ammonium chloride and ammonium bromide. In the perovskite precursor solution, the mass ratio of the additive to the ABX3 precursor material is (0.05~0.2):1. Specifically, in the perovskite precursor solution, the mass ratio of the additive to the ABX3 precursor material includes but is not limited to 0.05:1, 0.06:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.15:1, 0.17:1, 0.19:1 or 0.2:1.

[0071] In one example, the perovskite precursor solution further includes a hole transport layer material. The hole transport layer material includes one or more of formula (III-1) and formula (III-2): ; R 31 , R 32 , R 33 , R 34 , R 35 and R 36 Each is independently hydrogen, halogen, cyano, amino, substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy; m1 and m2 are each independently an integer between 0 and 9. m1 and m2 include but are not limited to 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0072] The perovskite precursor solution includes a hole transport layer material, and the perovskite film and the hole transport layer can be prepared by a one-step method. For example, the perovskite precursor solution also includes a hole transport layer material. The ether-containing amide monomer can simultaneously passivate the interface between the hole transport layer and the perovskite layer and the interface on the perovskite layer, simplifying the preparation process. In addition, by adding ether-containing amide monomers to the perovskite precursor solution, the polymer skeleton formed by cross-linking the monomers can ensure the uniformity of thermal diffusion during the annealing process, thereby effectively inhibiting the formation of coffee rings.

[0073] Specifically, the hole transport layer material includes , , and One or more of .

[0074] More specifically, the hole transport layer material includes .

[0075] In one example, in the precursor solution, the mass ratio of the hole transport layer material to the ABX3 precursor material is (0.0003-0.002): (0.7-2). Specifically, the mass ratio of the hole transport layer material to the ABX3 precursor material includes but is not limited to 0.0003:1, 0.0005:1, 0.001:1, 0.0012:1, 0.0013:1, 0.0014:1, 0.0015:1, 0.0015:1.1, 0.0015:1.2, 0.0015:1.3, 0.0015:1.4, 0.0015:1 .5, 0.0015:1.6, 0.0015:1.7, 0.0015:1.8, 0.0015mg:1.9, 0.0015:2, 0.0016:1, 0.0017:1, 0.0018:1, 0.0019:1, 0.002:1, 0.002:1.2, 0.002:1.4, 0.002:1.6, 0.002:1.8 or 0.002:2.

[0076] In another example, in the precursor solution, the concentration of the hole transport layer material is 0.3 mg / mL to 2.5 mg / mL. Specifically, the concentration of the hole transport layer material includes but is not limited to 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.1 mg / mL, 1.2 mg / mL, 1.3 mg / mL, 1.4 mg / mL, 1.5 mg / mL, 1.6 mg / mL, 1.7 mg / mL, 1.8 mg / mL, 1.9 mg / mL, 2 mg / mL, 2.2 mg / mL or 2.5 mg / mL.

[0077] In a third aspect of the present application, a method for preparing a perovskite film is provided, comprising the following steps:

[0078] a1. Mixing ABX3 precursor material, ether-containing amide monomer and solvent to prepare a perovskite precursor solution;

[0079] a2, coating the perovskite precursor solution on a substrate;

[0080] a3. Annealing the substrate coated with the perovskite precursor solution to cross-link the ether-containing amide monomers to obtain a cross-linked polymer; and preparing the perovskite film.

[0081] In one example, in step a2, the perovskite precursor solution may be coated on the substrate by spin coating, spray coating, slit coating or doctor blade coating.

[0082] In one example, in step a3, the temperature of the annealing treatment is 90° C. to 110° C. Specifically, the temperature of the annealing treatment includes but is not limited to 92° C., 95° C., 98° C., 100° C., 102° C., 105° C., 108° C. or 110° C.

[0083] In the preparation process of the above-mentioned perovskite film, the terminal unsaturated hydrocarbon group of the ether-containing amide monomer can be cleaved by heat at room temperature or annealing temperature to form free radicals, and the free radicals undergo polymerization reaction, so that the monomers are connected to each other to form a polymer with a cross-linked structure.

[0084] In the fourth aspect of the present application, a photoelectric device is provided, comprising the perovskite film described in any example of the first aspect of the present application or the perovskite film prepared by the preparation method described in the third aspect of the present application. The photoelectric devices mentioned in the present application include but are not limited to perovskite solar cells, two-terminal stacked perovskite solar cells with a bottom cell of silicon / CdTe / CIGS, and four-terminal stacked cells with a bottom cell of silicon / CdTe / CIGS.

[0085] In one example, the optoelectronic device 10 includes a hole transport layer 102 , a perovskite film 103 , a passivation layer 104 , and an electron transport layer 105 that are stacked.

[0086] In one example, the optoelectronic device 10 further includes a transparent conductive layer 101 and an electrode 106. Specifically, the optoelectronic device includes a transparent conductive layer 101, a hole transport layer 102, a perovskite film 103, a passivation layer 104, an electron transport layer 105 and an electrode 106 stacked in sequence.

[0087] In one example, the material of the transparent conductive layer 101 includes one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped tungsten oxide (IWO), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyimide (PI) and polydimethylsiloxane (PDMS).

[0088] In one example, the thickness of the transparent conductive layer 101 is 10 nm to 1000 nm. Specifically, the thickness of the transparent conductive layer 101 includes but is not limited to 20 nm, 30 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or 1000 nm.

[0089] In one example, the hole transport layer 102 includes one or more of formula (III-1) and formula (III-2): ;

[0090] R 31 , R 32 , R 33 , R 34 , R 35 and R 36 Each is independently hydrogen, halogen, cyano, amino, substituted or unsubstituted C1~C6 alkyl, C1~C6 alkoxy; m1 and m2 are each independently an integer between 0 and 9.

[0091] In one example, the hole transport layer 102 includes , , and One or more of .

[0092] In a more specific example, the hole transport layer 102 includes .

[0093] In one example, the thickness of the hole transport layer 102 is 10 nm to 200 nm. Specifically, the thickness of the hole transport layer includes but is not limited to 20 nm, 30 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm or 200 nm.

[0094] In one example, the thickness of the perovskite film 103 is 200 nm to 1000 nm. Specifically, the thickness of the perovskite film includes but is not limited to 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 330 nm, 400 nm, 450 nm, 500 nm, 700 nm, 900 nm or 1000 nm.

[0095] In one example, the passivation layer 104 includes ; wherein m3 is an integer between 1 and 6, and R4 is a halogen. m3 is 1, 2, 3, 4, 5, or 6. The addition of the above passivation layer can further reduce or eliminate the surface defects of the perovskite film, which are often the centers of electron and hole recombination, resulting in the loss of charge carriers. By introducing the passivation layer, the collection efficiency of carriers can be effectively increased, thereby improving the overall photoelectric conversion efficiency of the battery.

[0096] In one example, the passivation layer 104 includes propylene diamine hydroiodide.

[0097] In one example, the steps of preparing the passivation layer 104 include:

[0098] b1. Mixing with an organic solvent to prepare a passivation solution;

[0099] b2, coating the passivation solution on the perovskite film;

[0100] b3. Annealing the perovskite film coated with the passivation solution to prepare the passivation layer.

[0101] In one example, in step b1, the organic solvent is isopropanol.

[0102] In one example, the passivation solution contains: The concentration of is 0.1 mg / mL~5 mg / mL. Specifically, in the passivation solution, The concentration of includes but is not limited to 0.2 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL, 1 mg / mL, 1.2 mg / mL, 1.5 mg / mL, 1.8 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL.

[0103] In one example, in step b2, the passivation solution may be coated on the perovskite film by spin coating, spray coating, slit coating or scraping.

[0104] In one example, in step b3, the temperature for annealing is 90° C. to 110° C. Specifically, the temperature for annealing includes but is not limited to 92° C., 95° C., 98° C., 100° C., 102° C., 105° C., 108° C. or 110° C.

[0105] In one example, the thickness of the passivation layer 104 is 0.5 nm to 3 nm. Specifically, the thickness of the passivation layer includes but is not limited to 0.5 nm, 0.8 nm, 1 nm, 1.2 nm, 1.5 nm, 1.8 nm, 2 nm, 2.2 nm, 2.4 nm, 2.6 nm, 2.8 nm or 3 nm.

[0106] In one example, the material of the electron transport layer 105 includes one or more of titanium dioxide (TiO2), tin dioxide (SnO2), indium oxide (In2O3), zinc oxide (ZnO), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), fullerene derivatives, graphene, and graphene derivatives. For example, fullerene derivatives include but are not limited to PCBM and C60.

[0107] In one example, the thickness of the electron transport layer 105 is 10 nm to 200 nm. Specifically, the thickness of the electron transport layer includes but is not limited to 20 nm, 30 nm, 35 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 180 nm or 200 nm.

[0108] In one example, the material of the electrode 106 includes one or more of gold (Au), silver (Ag), copper (Cu), aluminum (Al), titanium (Ti), nickel (Ni), and molybdenum (Mo).

[0109] In one example, the thickness of the electrode 106 is 10 nm to 5000 nm. Specifically, the thickness of the electrode 105 includes but is not limited to 20 nm, 50 nm, 100 nm, 500 nm, 800 nm, 1000 nm, 1500 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm or 5000 nm.

[0110] In a fifth aspect of the present application, there is provided an electrical device comprising the optoelectronic device described in any example of the fourth aspect of the present application.

[0111] The following further specific examples are provided to explain the present application in detail. It should also be understood that the following examples are only used to further explain the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application belong to the scope of protection of the present application. The specific process parameters of the following embodiments are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not necessarily limited to the specific values ​​of the embodiments below.

[0112] [raw material]

[0113] Polyethylene glycol diacrylamide PEGDA, purchased from Sigma-Aldrich; model: 725676; Mn: 3700; containing ≤1500 ppm HQ as an inhibitor;

[0114] Ether-containing amide monomer P1: : Prepared with reference to the preparation method of US20090220607A1.

[0115] 4-(2,7-Dibromo-9,9-dimethylacridin-10(9H)-yl)butyl)phosphonic acid ): Prepared by referring to the preparation method of CN116056531A.

[0116] [2-(3,6-Dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid was purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.

[0117] Propylene diamine hydroiodide was purchased from Aladdin Reagent Co., Ltd.

[0118] Preparation Example 1

[0119] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 0.5mg of polyethylene glycol diacrylamide PEGDA (containing ether amide monomer) was added as a crosslinker and 1.5mg of 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid was added as a hole transport material, and stirred to dissolve to obtain a perovskite precursor solution. In the perovskite precursor solution, FA 0.85 MA 0.05 Cs 0.1 The molar concentration of PbI3 is 1.5 mol / L.

[0120] The preparation steps of the hole transport layer and the perovskite film include:

[0121] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0122] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 60 μL of perovskite precursor solution was spin-coated on the surface of the ITO substrate at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 40 min to complete annealing. Polyethylene glycol diacrylamide PEGDA was cross-linked to form a cross-linked polymer, forming a 10 nm hole transport layer and a 300 nm perovskite film respectively; in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:0.5mg.

[0123] Preparation Example 2

[0124] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 1mg of polyethylene glycol diacrylamide PEGDA (containing ether amide monomer) was added as a crosslinker and 1.5mg of 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid was added as a hole transport material, and stirred to dissolve to obtain a perovskite precursor solution. In the perovskite precursor solution, FA 0.85 MA 0.05 Cs 0.1 The molar concentration of PbI3 is 1.5 mol / L.

[0125] The preparation steps of the hole transport layer and the perovskite film include:

[0126] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0127] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 60 μL of perovskite precursor solution was spin-coated on the surface of the ITO substrate at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 40 min to complete annealing. Polyethylene glycol diacrylamide PEGDA was cross-linked to form a cross-linked polymer, forming a 10 nm hole transport layer and a 300 nm perovskite film respectively; in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:1mg.

[0128] Preparation Example 3

[0129] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 1.5mg of polyethylene glycol diacrylamide PEGDA (containing ether amide monomer) was added as a crosslinker and 1.5mg of 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid was added as a hole transport material, and stirred to dissolve to obtain a perovskite precursor solution. In the perovskite precursor solution, FA 0.85 MA 0.05 Cs 0.1 The molar concentration of PbI3 is 1.5 mol / L.

[0130] The preparation steps of the hole transport layer and the perovskite film include:

[0131] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0132] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 60 μL of perovskite precursor solution was spin-coated on the surface of the ITO substrate at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 40 min to complete annealing. Polyethylene glycol diacrylamide PEGDA was cross-linked to form a cross-linked polymer, forming a 10 nm hole transport layer and a 300 nm perovskite film respectively; in the perovskite film, the perovskite material FA 0.85MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:1.5mg.

[0133] Preparation Example 4

[0134] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 2mg of polyethylene glycol diacrylamide PEGDA (containing ether amide monomer) was added as a crosslinker and 1.5mg of 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid was added as a hole transport material, and stirred to dissolve to obtain a perovskite precursor solution. In the perovskite precursor solution, FA 0.85 MA 0.05 Cs 0.1 The molar concentration of PbI3 is 1.5 mol / L.

[0135] The preparation steps of the hole transport layer and the perovskite film include:

[0136] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0137] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 60 μL of perovskite precursor solution was spin-coated on the surface of the ITO substrate at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 40 min to complete annealing. Polyethylene glycol diacrylamide PEGDA was cross-linked to form a cross-linked polymer, forming a 10 nm hole transport layer and a 300 nm perovskite film respectively; in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:2mg.

[0138] Preparation Example 5

[0139] Preparation Example 5 is basically the same as Preparation Example 1, with the main difference being that in Preparation Example 5, the ether-containing amide monomer P1 is used to replace the polyethylene glycol diacrylamide PEGDA in Preparation Example 1.

[0140] Preparation Example 6

[0141] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 1.5mg of 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid was used as a hole transport material, and stirred and dissolved to obtain a perovskite precursor solution. In the perovskite precursor solution, FA 0.85 MA 0.05 Cs 0.1 The molar concentration of PbI3 is 1.5 mol / L.

[0142] The preparation steps of the hole transport layer and the perovskite film include:

[0143] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0144] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 60 μL of perovskite precursor solution was spin-coated on the surface of the ITO substrate at a speed of 5000 rpm / min and an acceleration of 1000 rpm / s for 50 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 40 min to complete annealing, forming a 10 nm hole transport layer and a 300 nm perovskite film respectively; in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:0mg.

[0145] Preparation Example 7

[0146] Perovskite precursor solution: 0.96 g FA 0.85 MA 0.05 Cs 0.1 PbI3 and 0.006g of additive MACl were dissolved in 1mL of solvent with a volume ratio of DMF:NMP=4:1, and 0.5mg of polyethylene glycol diacrylamide PEGDA (containing ether amide monomer) was added as a crosslinker, and stirred to dissolve to obtain a perovskite precursor solution. 0.85 MA 0.05 Cs 0.1The molar concentration of PbI3 is 1.5 mol / L.

[0147] Hole transport precursor solution: 0.5 mg of hole transport material [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was dissolved in 1 mL of ethanol solvent, and the mixture was stirred to dissolve to obtain a hole transport precursor solution with a concentration of 0.5 mg / mL.

[0148] The preparation steps of the hole transport layer and the perovskite film include:

[0149] (1) Transparent conductive layer: 100 nm thick ITO conductive glass was ultrasonically cleaned with glass cleaning solution, deionized water, and ethanol for 20 min respectively, and finally dried in a drying oven at 75°C for later use; the dried ITO glass substrate was treated in a UV ozone machine for 20 min to remove organic impurities on its surface and optimize its surface wettability;

[0150] (2) Hole transport layer and perovskite film: In a nitrogen glove box, 80 μL of hole transport precursor solution was spin coated on the surface of the ITO substrate at a speed of 4000 rpm / min and an acceleration of 1000 rpm / s for 20 s. After completion, it was transferred to an annealing hot plate and heated at 100°C for 15 min to complete annealing, forming a 10 nm hole transport layer. In a nitrogen glove box, 80 μL of perovskite precursor solution was first spin-coated at a speed of 1000 rpm / min and an acceleration of 1000 rpm / s for 10 seconds, and then at a speed of 5000 rpm / min and an acceleration of 5000 rpm / s for 30 seconds. At the 32nd second of the total time, 150 μL of chlorobenzene was added as an anti-solvent to coat the surface of the hole transport layer. After completion, it was transferred to an annealing hot stage and heated at 100°C for 40 minutes to complete annealing. Polyethylene glycol diacrylamide PEGDA was cross-linked to form a cross-linked polymer to form a 300 nm perovskite film. Among them, in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 The mass ratio of PbI3 and the cross-linked polymer is 0.96g:0.5mg.

[0151] Example 1

[0152] The preparation steps of perovskite solar cells include:

[0153] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 1 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min, thereby forming a passivation layer of 2 nm;

[0154] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0155] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0156] Example 2

[0157] The preparation steps of perovskite solar cells include:

[0158] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 2 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min to form a passivation layer of 2 nm;

[0159] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0160] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0161] Example 3

[0162] The preparation steps of perovskite solar cells include:

[0163] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 3 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min, thereby forming a passivation layer of 2 nm;

[0164] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0165] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0166] Example 4

[0167] The preparation steps of perovskite solar cells include:

[0168] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 4 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min, thereby forming a passivation layer of 2 nm;

[0169] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0170] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0171] Example 5

[0172] The preparation steps of perovskite solar cells include:

[0173] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 5 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min to form a passivation layer of 2 nm;

[0174] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0175] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0176] Comparative Example 1

[0177] The preparation steps of perovskite solar cells include:

[0178] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 6 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min to form a passivation layer of 2 nm;

[0179] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0180] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0181] Comparative Example 2

[0182] The preparation steps of perovskite solar cells include:

[0183] (1) Passivation layer: Propylene diamine hydroiodide was dissolved in an isopropanol solution at a concentration of 0.8 mg / mL, and coated on the surface of the perovskite film of Preparation Example 7 by spin coating at a speed of 5000 rpm / min and an acceleration of 3000 rpm / s for 30 s, and annealed on a hot stage at 100° C. for 15 min to form a passivation layer of 2 nm;

[0184] (2) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the passivation layer as an electron transport layer;

[0185] (3) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0186] Comparative Example 3

[0187] (1) 20 nm of C60 and 15 nm of BCP were sequentially deposited on the surface of the perovskite film of Preparation Example 1 as an electron transport layer;

[0188] (2) 150 nm of Ag was evaporated on the surface of the electron transport layer as an electrode layer to prepare a perovskite solar cell.

[0189] The above-mentioned perovskite solar cell is subjected to a performance test, and the test method includes:

[0190] (1) When the light intensity is 100 mW cm -2 Under the simulated sunlight AM1.5G irradiation condition, the JV curves of the perovskite solar cells of the above embodiments and comparative examples were tested; the corresponding test results are shown in FIG. Figure 2 At the same time, under this condition, the open circuit voltage (VOC), short circuit current (JSC), fill factor (FF), and photoelectric conversion efficiency (PCE) of the perovskite solar cell were measured, and the corresponding test results are shown in Table 1.

[0191] (2) The perovskite solar cells of the above-mentioned embodiment and comparative example were heated at a constant temperature of 100° C. and 25% RH to test the thermal stability curve of the perovskite solar cells. The corresponding test results are shown in FIG. Figure 3 shown.

[0192] Table 1

[0193]

[0194] From Table 1 and Figure 2As shown, Examples 1 to 5 respectively use the perovskite films including cross-linked polymers in Preparation Examples 1 to 5. Compared with Comparative Example 1 which uses the perovskite film without cross-linked polymers in Preparation Example 6, the PCEs of Examples 1 to 5 are higher. In Examples 1 to 5, Example 3 uses the perovskite material FA 0.85 MA 0.05 Cs 0.1 In Preparation Example 3, the mass ratio of PbI3 to cross-linked polymer is 0.96g:1.5mg. At this time, the PCE of the perovskite solar cell is the highest, which can reach 24.68%, and its photoelectric performance is the best. In Comparative Example 2, the amount of cross-linked polymer added to the perovskite film is the same as that in Example 1, but when assembling the solar cell, the hole transport material selected in Comparative Example 2 is [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), which is different from 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid in Example 1, resulting in a lower PCE. In Comparative Example 3, the perovskite film of Preparation Example 1 is selected, but when assembling the solar cell, Comparative Example 3 does not include a passivation layer, which also results in a lower PCE.

[0195] Depend on Figure 3 As shown, in Example 2, in the perovskite precursor solution, the concentration of polyethylene glycol diacrylamide PEGDA is 1 mg / mL; in the perovskite film, the perovskite material FA 0.85 MA 0.05 Cs 0.1 When the mass ratio of PbI3 and cross-linked polymer is 0.96g:1mg, the PCE decay of the perovskite solar cell after 100h of heating aging at 100°C is the lowest, followed by Example 3.

[0196] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0197] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A perovskite film, characterized in that: The perovskite film comprises an ABX3 type perovskite material and a cross-linked polymer, Wherein, the monomers for preparing the cross-linked polymer include ether-containing amide monomers.

2. The perovskite film according to claim 1, characterized in that The ether group-containing amide monomers include one or more of the compounds represented by formula (I-1): ， Among them, R 11 and R 12 Each is independently a substituted or unsubstituted C2~C6 alkenyl, or a substituted or unsubstituted C2~C6 alkynyl; n1 is an integer between 1 and 30.

3. The perovskite film according to claim 2, characterized in that: R 11 and R 12 Each is independently vinyl, allyl, ethynyl or propargyl; n1 is an integer between 0 and 20.

4. The perovskite film according to claim 2, characterized in that: The ether group-containing amide monomers include one or more of the compounds represented by formula (II-1) to formula (II-3): , or ; n2~n4 are each independently an integer between 1 and 20.

5. The perovskite film according to claim 2, characterized in that: The number average molecular weight of the polyethylene glycol diacrylamide is 400-4000.

6. The perovskite thin film according to any one of claims 1 to 5, characterized in that: In the perovskite film, the mass ratio of the ABX3 type perovskite material to the cross-linked polymer is (0.7~2):(0.0005~0.003).

7. A perovskite precursor solution, characterized in that: The perovskite precursor solution comprises an ABX3 precursor material, an ether-containing amide monomer and a solvent; the ether-containing amide monomer is the ether-containing amide monomer in the perovskite film according to any one of claims 1 to 6.

8. The perovskite precursor solution according to claim 7, characterized in that The perovskite precursor solution has one or more of the following characteristics: (1) In the perovskite precursor solution, the concentration of the ether-containing amide monomer is 0.3 mg / mL to 3 mg / mL; (2) In the perovskite precursor solution, the concentration of the ABX3 precursor material is 0.7 g / mL~2 g / mL.

9. A method for preparing a perovskite film, characterized in that: The following steps are involved: Mixing an ABX3 precursor material, an ether-containing amide monomer, and a solvent to prepare a perovskite precursor solution; coating the perovskite precursor solution on a substrate; Annealing the substrate coated with the perovskite precursor solution to cross-link the ether-containing amide monomer to obtain a cross-linked polymer; The perovskite film is prepared.

10. A photoelectric device, characterized in that: A perovskite film comprising the perovskite film according to any one of claims 1 to 6 or a perovskite film prepared by the preparation method according to claim 9.

11. The optoelectronic device according to claim 10, characterized in that: The photoelectric device comprises a hole transport layer, a perovskite film, a passivation layer and an electron transport layer which are stacked; Wherein, the hole transport layer comprises one or more of the compounds represented by formula (III-1) and formula (III-2): ； R 31 , R 32 , R 33 , R 34 , R 35 and R 36 Each is independently hydrogen, halogen, cyano, amino, substituted or unsubstituted C1~C6 alkyl, C1~C6 alkoxy; m1 and m2 are each independently an integer between 0 and 9.

12. The optoelectronic device according to claim 11, characterized in that: The hole transport layer includes , , and One or more of .

13. The optoelectronic device according to claim 11 or 12, characterized in that: The passivation layer includes ; wherein m3 is an integer between 1 and 6, and R4 is a halogen.

14. The optoelectronic device according to claim 13, characterized in that: The passivation layer includes propylenediamine hydroiodide.

15. An electrical device, characterized in that: The optoelectronic device comprises the optoelectronic device according to any one of claims 10 to 14.

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