Inverted perovskite solar cells, preparing method thereof, perovskite film composition, crystal-solvate, electrical device and uses thereof

Abstract

The invention provides a trans-perovskite solar cell, a preparation method of the trans-perovskite solar cell, a perovskite film composition, a crystal solvate, electrical equipment and application of the trans-perovskite solar cell. The method comprises the steps that before a perovskite precursor solution is applied to a substrate, a crystal solvate is used for seed crystal on the substrate; the general formula of the crystal solvate is AxPbX4.yDMSO, A is selected from cations of the following substances: ethylenediamine, butanediamine, heptyl diamine, phenylethylamine, piperazine, N, N '-dimethylethylenediamine, N-methylethylenediamine, N, N, N', N '-tetramethylethylenediamine, N, N, N'-trimethyl lethylenediamine and N, N-dimethylethylenediamine; x is selected from I <->, Br <-> and Cl <->; x is 1-2; and y is 1-3. The PCE of the PSC reaches 26.13%, the FF of the PSC reaches 86.75%, 93% of the initial PCE is maintained after 1000h of maximum power point tracking, and 85% of the initial PCE is maintained after 900h of isothermal heating at 85 DEG C.

Description

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202411905653.4 (22) Application Date 2024.12.23 (71) Applicant Hong Kong University of Science and Technology Address Clearwater Bay, Kowloon, Hong Kong, China Applicant China Merchants Testing & Certification International Limited China Merchants Innovation Technology (Hong Kong) Limited (72) Inventors Zhou Yuanyuan, Pang Shuping, Sun Xiuhong (74) Patent Agency Beijing Tianhao United Intellectual Property Agency Co., Ltd. 11112 Patent Attorney Wang Jing (51) Int.Cl. H10K 71 / 00 (2023.01) H10K 77 / 10 (2023.01) H10K 30 / 88 (2023.01) H10K 30 / 40 (2023.01) H10K 30 / 50 (2023.01) H10K 85 / 50(2023.01) C30B 7 / 14(2006.01) C30B 29 / 12(2006.01) C30B 29 / 54(2006.01) H10K 85 / 60(2023.01) H10K 85 / 10(2023.01) (54) Invention Title: Inverted Perovskite Solar Cell and its Preparation Method, Perovskite Film Composition, Crystallized Solvate, Electrical Device and its Application (57) Abstract: Inverted perovskite solar cells, their preparation methods, perovskite film compositions, crystallized solvates, electrical devices and their applications are provided. The method includes: seeding crystals on the substrate with a crystallization solvate before applying a perovskite precursor solution to the substrate; the general formula of the crystallization solvate is AxPbX4·yDMSO, where A is selected from the cations of the following substances: ethylenediamine, butanediamine, heptamethamine, phenylethylamine, piperazine, N,N'-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N-dimethylethylenediamine; X is selected from I-, Br-, Cl-; x is 1-2; y is 1-3. The PCE of the PSC of this invention reaches 26.13%, FF reaches 86.75%, and after 1000 hours of maximum power point tracking, it maintains 93% of the initial PCE, and after 900 hours of isothermal heating at 85 °C, it maintains 85% of the initial PCE. Claims (3 pages), Description (22 pages), Drawings (15 pages), CN 122270013 A, 2026.06.23, CN 1 22 27 00 13 A. 1. A method for preparing an inverted perovskite solar cell, characterized in that: before applying a perovskite precursor solution to a substrate, a crystallizing solvate is used to seed crystals on the substrate to obtain crystals of the crystallizing solvate formed thereon.The substrate of the bulk layer; wherein the general formula of the crystalline solvate is AxPbX4·yDMSO, wherein A comprises one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation; X is selected from one or more of the group consisting of I-, Br-, and Cl-; x is 1-2; y is 1-3; and DMSO is dimethyl sulfoxide. 2. The method according to claim 1, wherein the substrate is a self-assembled monolayer or a hole transport layer. 3. The method according to claim 1, comprising the following steps: 1) providing a self-assembled monolayer; 2) seeding the self-assembled monolayer with the crystallizing solvate to obtain a self-assembled monolayer having a crystallizing solvate crystal layer thereon; 3) forming a perovskite layer on the self-assembled monolayer having the crystallizing solvate crystal layer thereon. 4. The method according to claim 2 or 3, wherein the self-assembled monolayer comprises one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 2-(3,6-dimethoxycarbazole-9-yl)ethylphosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, (4-(9H-dibenzo[a,c]carbazole-9-yl)butyl)phosphonic acid, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid, (2-(pyrene-1-yl)ethyl)phosphonic acid, and (4-(3,6-diphenyl-9H-carbazole-9-yl)butyl)phosphonic acid. 5. The method of claim 1, wherein the thickness of the crystallized solvate layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystallized solvate layer is 1-20 nm. 6. The method of claim 1, wherein the seed crystal comprises: applying a solution of the crystallized solvate onto the substrate; and annealing; wherein the annealing temperature is from room temperature to 200°C, and the time is 2-30 min. 7. The method of claim 6, wherein the annealing is performed in an inert atmosphere or in ambient air with a humidity not exceeding 80%. 8. The method of claim 6, wherein the concentration of the solution of the crystallized solvate is 1-60 mg / mL, and the solvent of the solution is selected from: dimethyl sulfoxide, N',N-dimethylformamide, and N-methylpyrrolidone. 9. The method of claim 6, wherein the solution of the crystallized solvate is applied to the substrate by spin coating.On a substrate; preferably, the spin coating is performed at 1000-5000 rpm for 10-30 seconds; or the solution of the crystalline solvate is applied to the substrate by slot coating, blade coating, or spraying. 10. The method according to claim 1, wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H12)2+. 11. The method according to claim 1, wherein the crystalline solvate crystal layer has an orthorhombic, monoclinic, or tetragonal crystal structure. 12. The method according to claim 3, wherein step 3) of forming the perovskite layer comprises: applying a perovskite precursor solution to the self-assembled monolayer on which the crystalline solvate crystal layer is formed; adding an antisolvent dropwise to the perovskite precursor solution; preferably, the antisolvent is added dropwise 0-50 seconds after applying the perovskite precursor solution; and annealing; wherein the annealing temperature is from room temperature to 350°C for 5-50 min; preferably, the annealing is performed in an inert atmosphere or in ambient air with a humidity not exceeding 80%. 13. The method according to claim 1 or 12, wherein the concentration of the perovskite precursor solution is 0.5-1.7 mol / L, and the solvent of the solution is selected from: N',N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, ethanol, and water. 14. The method of claim 12, wherein the antisolvent is selected from ethyl acetate, chlorobenzene, diethyl ether, methyl acetate, anisole, and isopropanol; and the perovskite precursor solution is applied to the self-assembled monolayer on which the crystalline solvate crystal layer is formed by spin coating; preferably, the spin coating is performed at 1000-5000 rpm for 10-50 seconds. 15. The method of claim 3, wherein the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and combinations of Cs+ with Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), and methylamine ion (MA+); B is selected from Pb2+, Sn2+, and combinations thereof; X is selected from I-, Br-, Cl-, and combinations thereof; preferably, the thickness of the perovskite layer is 200-1000 nm. 16. A perovskite film composition comprising a perovskite layer and a self-assembled monolayer, wherein a crystalline solvate crystal layer formed of a crystalline solvate is present between the perovskite layer and the self-assembled monolayer, wherein the crystalline solvate has the general formula AxPbX4·yDMSO, wherein A comprises ethylenediamine cations, butanediamine cations, heptamethamine cations, phenylethylamine cations, piperazine cations, N,N'-dimethylethylenediamine cations, N-methylethylenediamine cations, N,N,N',N'-tetramethylethylenediamine cations, etc.One or more of the following groups are selected from the group consisting of diamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation, where X is selected from the group consisting of one or more of I-, Br-, and Cl-, x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide. 17. The perovskite film composition according to claim 16, wherein the thickness of the crystalline solvate crystal layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystalline solvate crystal layer is 1-20 nm. 18. The perovskite film composition according to claim 16, wherein the crystalline solvate crystal layer has an orthorhombic, monoclinic, or tetragonal crystal structure. 19. The perovskite film composition according to claim 16, wherein the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and combinations of Cs+ with one or more of Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), and methylamine ion (MA+); B is selected from Pb2+, Sn2+, and combinations thereof; X is selected from I-, Br-, Cl-, and combinations thereof; preferably, the thickness of the perovskite layer is 200-1000 nm. 20. The use of the perovskite film composition according to any one of claims 16-19 in the preparation of an inverted perovskite solar cell. 21. An inverted perovskite solar cell prepared by the method according to any one of claims 1-15. 22. The inverted perovskite solar cell according to claim 21, comprising a transparent conductive substrate, optionally a hole transport layer, the perovskite film composition according to any one of claims 16-19, optionally a passivation layer, an electron transport layer, a blocking layer, and an electrode layer, sequentially stacked. 23. The inverse perovskite solar cell according to claim 22, wherein the transparent conductive substrate is selected from ITO glass and FTO glass, and the thickness of the transparent conductive substrate is 50-200 nm; the hole transport layer comprises one or more of NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene) (P3HT), and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and the thickness of the hole transport layer is 1-20 nm; the passivation layer comprises piperazine bisiodide or piperazine hydroiodide, and the thickness of the passivation layer is 1-10 nm; the electron transport layer comprises C60 or [6,6]-phenyl-C61-butyrate methyl ester (PCBM), and the thickness of the electron transport layer is 20-50 nm; The barrier layer comprises SnO2, (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) (BCP) or LiF, the barrier...The thickness of the layer is 3-30 nm; the electrode layer comprises one or more of silver, ITO, copper, and gold, and the thickness of the electrode layer is 60-200 nm. 24. An electrical device comprising an inverse perovskite solar cell according to any one of claims 21-23. 25. A crystalline solvate, wherein the general formula of the crystalline solvate is AxPbX4·yDMSO, wherein A comprises one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation, X is selected from one or more of the group consisting of I-, Br-, and Cl-, x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide. 26. The crystalline solvate according to claim 25, wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H12)2+. 27. The application of the crystalline solvate according to claim 25 or 26 in the preparation of inverted perovskite solar cells. Claims 3 / 3 pages 4 CN 122270013 A Inverted perovskite solar cells and their preparation methods, perovskite film compositions, crystalline solvates, electrical devices, and their applications Technical Field

[0001] This invention belongs to the field of solar cells, specifically relating to inverted perovskite solar cells and their preparation methods, perovskite film compositions, crystalline solvates, electrical devices, and their applications. Background Art

[0002] In recent years, the power conversion efficiency (PCE) of inverted p-i-n perovskite solar cells (PSCs) has rapidly increased, showing great commercial potential. These advances are due to effective strategies for adjusting interface defects in inverted PSCs. Although grain boundaries within the perovskite film substrate have been confirmed to be crucial, heterointerfaces on the top (n) and bottom (p) sides of the perovskite film also play a significant role in inverse PSCs. Early research focused primarily on modifying the top (n) side heterointerface to significantly improve the photovoltaic performance and stability of the PSC. Later, increasing attention was paid to the bottom (p) heterointerface, but this is relatively difficult to customize because it is buried beneath the perovskite film substrate.

[0003] Currently, inverse PSCs in the prior art employ so-called self-assembled monolayers (SAMs) as hole transport layers (HTLs), for example, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz). Customizing the intrinsic molecular chemistry of the SAM...Properties can modulate perovskite crystallization and interface formation, thereby improving PSC performance and stability. However, these SAMs remain relatively hydrophobic due to the presence of suspended benzene rings after the formation of SAMs on transparent conductive oxides. This makes diffusion and wetting of the perovskite precursor solution over large areas problematic. The increased interfacial energy due to hydrophobicity also limits interfacial nucleation at the bottom of the film. In this case, perovskite crystallization tends to occur at the top of the precursor film and propagate downwards until it reaches the SAM substrate. As a result, morphological voids are inevitably generated at the bottom of the perovskite film, thereby disrupting the microstructure and electronic integrity at the buried interface.

[0004] Furthermore, due to the ultrathin nature of the SAM layer and its deposition method, it becomes impractical to customize the bottom of the perovskite film in p-i-n devices using the molecular additive pre-buried method commonly used in n-i-p devices. In this regard, during the fabrication of inverse p-i-n devices, it is difficult to access the prominent surface nanogrooves located at the grain boundaries and intracrystalline regions at the bottom of the perovskite film, thus limiting the microstructure design for optimal device performance and stability.

[0005] To address the problems existing in the prior art, the present invention utilizes low-dimensional halide crystallized solvate (CSV) seed crystals to regulate the crystallization and bottom surface structure of the perovskite film. CSV is highly effective in promoting heterogeneous nucleation and accelerating crystallization of perovskite, thereby enabling the acquisition of a dense perovskite film bottom grain microstructure. CSV also improves the wettability of the perovskite precursor solution. During annealing, CSV can also release solvent molecules from the lattice. This unique subprocess eliminates interfacial voids and flattens the bottom grain boundary trenches. The low-dimensional halide from CSV retained at the bottom of the perovskite film can not only act as a passivator to suppress electronic defects, thereby mitigating nonradiative carrier recombination, but also reconstruct a surface energy arrangement highly favorable for hole extraction.

[0006] Specifically, the present invention provides:

[0007] (1) A method for preparing an inverted perovskite solar cell, characterized in that: before applying a perovskite pre-propagating agent solution to the substrate, a crystallizing solvate is used to seed crystals on the substrate to obtain a substrate on which a crystallizing solvate crystal layer is formed; wherein the general formula of the crystallizing solvate is AxPbX4·yDMSO, wherein A includes one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation and N,N-dimethylethylenediamine cation; X is selected from the group consisting of I-, Br- and Cl-.Or multiple; x is 1-2; y is 1-3, DMSO is dimethyl sulfoxide.

[0008] (2) According to the method of (1), wherein the substrate is a self-assembled monolayer or a hole transport layer.

[0009] (3) According to the method of (1), comprising the following steps:

[0010] 1) providing a self-assembled monolayer;

[0011] 2) seeding the self-assembled monolayer with the crystallizing solvate to obtain a self-assembled monolayer on which a crystallizing solvate crystal layer is formed;

[0012] 3) forming a perovskite layer on the self-assembled monolayer on which the crystallizing solvate crystal layer is formed.

[0013] (4) The method according to (2) or (3), wherein the self-assembled monolayer comprises one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 2-(3,6-dimethoxycarbazole-9-yl)ethylphosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, (4-(9H-dibenzo[a,c]carbazole-9-yl)butyl)phosphonic acid, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid, (2-(pyrene-1-yl)ethyl)phosphonic acid and (4-(3,6-diphenyl-9H-carbazole-9-yl)butyl)phosphonic acid.

[0014] (5) According to the method of (1), the thickness of the crystallized solvate crystal layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystallized solvate crystal layer is 1-20 nm.

[0015] (6) According to the method of (1), the seed crystal comprises:

[0016] applying a solution of the crystallized solvate onto the substrate; and

[0017] annealing; wherein the annealing temperature is from room temperature to 200°C and the time is 2-30 min.

[0018] (7) According to the method of (6), wherein the annealing is performed in an inert atmosphere or in ambient air with a humidity not exceeding 80%.

[0019] (8) According to the method of (6), wherein the concentration of the solution of the crystallized solvate is 1-60 mg / mL, and the solvent of the solution is selected from: dimethyl sulfoxide, N',N-dimethylformamide and N-methylpyrrolidone.

[0020] (9) The method according to (6), wherein the solution of the crystalline solvate is applied to the substrate by spin coating; preferably, the spin coating is performed at 1000-5000 rpm for 10-30 seconds; or the solution of the crystalline solvate is applied to the substrate by slot coating, blade coating or spraying.

[0021] (10) The method according to (1), wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H12)2+.

[0022] (11) According to the method of (1), wherein the crystallized solvate crystal layer has an orthorhombic, monoclinic, or tetragonal crystal structure.

[0023] (12) According to the method of (3), wherein the formation of the perovskite layer in step 3) comprises:

[0024] applying a perovskite precursor solution onto the self-assembled monolayer on which the crystallized solvate crystal layer is formed;

[0025] adding an antisolvent dropwise to the perovskite precursor solution; preferably, the antisolvent dropwise is added 0-50 seconds after the application of the perovskite precursor solution; and

[0026] annealing; wherein the annealing temperature is from room temperature to 350°C and the time is 5-50 min; preferably, the annealing is performed in an inert atmosphere or in ambient air with a humidity not greater than 80%.

[0027] (13) According to the method of (1) or (12), the concentration of the perovskite precursor solution is 0.5-1.7 mol / L, and the solvent of the solution is selected from: N',N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, ethanol and water.

[0028] (14) According to the method of (12), the antisolvent is selected from ethyl acetate, chlorobenzene, diethyl ether, methyl acetate, anisole and isopropanol; and

[0029] the perovskite precursor solution is applied to the self-assembled monolayer on which the crystallized solvate layer is formed by spin coating; preferably, the spin coating is performed at 1000-5000 rpm for 10-50 seconds.

[0030] (15) According to the method of (3), the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and a combination of one or more of Cs+ and Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), and methylamine ion (MA+); B is selected from Pb2+, Sn2+ and a combination thereof; X is selected from I-, Br-, Cl- and a combination thereof; preferably, the thickness of the perovskite layer is 200-1000 nm.

[0031] (16) A perovskite film composition comprising a perovskite layer and a self-assembled monolayer, wherein a crystallized solvate crystal layer formed by a crystallizing solvate is present between the perovskite layer and the self-assembled monolayer, wherein the general formula of the crystallizing solvate is AxPbX4·yDMSO, wherein A comprises the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation and N,N-dimethylethylenediamine cation.One or more of the following, X is selected from one or more of the group consisting of I-, Br- and Cl-, x is 1-2; y is 1-3, and DMSO is dimethyl sulfoxide.

[0032] (17) The perovskite film composition according to (16), wherein the thickness of the crystalline solvate crystal layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystalline solvate crystal layer is 1-20 nm.

[0033] (18) The perovskite film composition according to (16), wherein the crystalline solvate crystal layer has an orthorhombic, monoclinic or tetragonal crystal structure.

[0034] (19) The perovskite film composition according to (16), wherein the composition of the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and a combination of one or more of Cs+ and Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), and methylamine ion (MA+); B is selected from Pb2+, Sn2+ and combinations thereof; X is selected from I-, Br-, Cl- and a combination thereof; preferably, the thickness of the perovskite layer is 200-1000 nm.

[0035] (20) The use of the perovskite film composition according to any one of (16)-(19) for the preparation of an inverted perovskite solar cell.

[0036] (21) An inverted perovskite solar cell prepared according to any one of (1)-(15).

[0037] (22) The inverted perovskite solar cell according to (21) comprises a transparent conductive substrate, optionally a hole transport layer, a perovskite film composition according to any one of (16)-(19), optionally a passivation layer, an electron transport layer, a barrier layer and an electrode layer, which are stacked sequentially.

[0038] (23) The inverse perovskite solar cell according to (22), wherein

[0039] the transparent conductive substrate is selected from ITO glass and FTO glass, and the thickness of the transparent conductive substrate is 50-200 nm;

[0040] the hole transport layer includes one or more of NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene) (P3HT) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and the thickness of the hole transport layer is 1-20 nm; Specification 3 / 22 page 7 CN 122270013 A

[0041] the passivation layer includes piperazine bisiodide or piperazine hydroiodide, and the thickness of the passivation layer is 1-10 nm;

[0042] The electron transport layer comprises C60 or [6,6]-phenyl-C61-butyrate methyl ester (PCBM), and the thickness of the electron transport layer is 20-50 nm;

[0043] The barrier layer comprises SnO2, (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) (BCP) or LiF, and the thickness of the barrier layer is 3-30 nm;

[0044] The electrode layer comprises one or more of silver, ITO, copper and gold, and the thickness of the electrode layer is 60-200 nm.

[0045] (24) An electrical device comprising an inverse perovskite solar cell according to any one of (21)-(23).

[0046] (25) A crystalline solvate, wherein the general formula of the crystalline solvate is AxPbX4·yDMSO, wherein A comprises one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation and N,N-dimethylethylenediamine cation, X is selected from one or more of the group consisting of I-, Br- and Cl-, x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide.

[0047] (26) The crystalline solvate according to (25), wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H12)2+.

[0048] (27) Application of the crystalline solvate according to (25) or (26) in the preparation of inverted perovskite solar cells.

[0049] The present invention has the following advantages and positive effects compared with the prior art:

[0050] 1. The method for preparing inverted perovskite solar cells according to the present invention solves the key problems of the microstructure and electronic properties of the bottom interface of the perovskite film in SAM-based inverted PSCs. Due to the unique chemical properties and microstructure of the CSV crystal layer, the wetting of the perovskite precursor solution on SAM is significantly improved, and the annealing of the crystalline solvate is initiated in an unprecedented way, while eliminating morphological defects and electronic defects at the interface.

[0051] 2. The method for preparing inverted perovskite solar cells according to the present invention allows the bottom of the perovskite film to be buried with low-dimensional halides, which can change the interface energy and is beneficial to hole dynamics.

[0052] 3. The present invention can simultaneously improve the microstructure and electronic properties of the perovskite film, achieving an improved PCE of up to 26.13% and a fill factor (FF) of up to 86.75% in a single cell.

[0053] 4. The method of the present invention can alleviate the chemical and mechanical instability of the bottom interface of the trans PSC, thereby improving the operational and thermal stability of the PSC device, which is related to the improvement of microstructure and electronic properties. The PSC device of the present invention can maintain 93% of the initial PCE after 1000 hours of maximum power point tracking under sunlight irradiation, and at 85°C...After isothermal heating for 900 hours, 85% of the initial PCE can be maintained, exhibiting excellent light and thermal stability.

[0054] 5. The method of the present invention is suitable for scalable processing of PSC devices, achieving 23.15% PCE in a slot-coated perovskite solar cell module with an area of ​​49.91×cm2, showing only a small efficiency reduction when the device area is scaled up proportionally.

[0055] 6. Based on the method of the present invention, CSV can be a large class of hybrid materials with a variety of organic cations and solvent choices, which can generate new research directions in the buried film bottom interface of perovskite photovoltaic devices. Crystallization solvent synthesis crystallization and annealing can be used not only for flexible photovoltaic (PV) devices, but also for thin film interface engineering of various optoelectronic devices. Brief Description of the Drawings

[0056] Figure 1 shows the formation process and characterization results of a CSV crystal layer according to an embodiment of the present invention. Figure 1a (page 4 / 22 of the specification, CN 122270013 A) shows a schematic diagram of the CSV seeding method; Figure 1b shows a scanning electron microscope (SEM) image of the CSV crystal layer formed by spin coating on SAM and annealing, with the inset showing the morphology of the rod-shaped nanocrystals; Figure 1c compares the contact angles of SAM (top) and SAM with the CSV crystal layer formed thereon (bottom); Figure 1d compares the X-ray diffraction (XRD) results of CSV crystal powder (blue curve) and the CSV crystal layer of the present invention (yellow curve); Figure 1e shows the in-situ UV-Vis absorption spectrum tracking results of the perovskite film after thermal annealing at 100°C; the bottom figure shows the result of the perovskite film formed on SAM with the CSV crystal layer formed thereon, and the top figure shows the result of the perovskite film formed directly on SAM.

[0057] Figure 2 shows the change in absorbance at 750 nm as a function of annealing time on the perovskite films formed after thermal annealing at 100 °C on SAM (control group) and SAM (target group) on which a CSV crystal layer is formed.

[0058] Figure 3 shows the steady-state fluorescence spectrum of the CSV crystal layer of the present invention.

[0059] Figure 4 shows the perovskite films of the target group and the control group, as well as the microstructure details of the bottom of each film. Figure 4a shows a cross-sectional SEM image of the perovskite film in the control group; Figure 4b shows a cross-sectional SEM image of the perovskite film in the target group; Figure 4c shows a top-view SEM image of the bottom of the flipped and peeled perovskite film; Figure 4d shows a top-view SEM image of the bottom of the flipped and peeled perovskite film in Figure 4b; Figure 4e shows 3D atomic force microscopy (AFM) images of surface grain boundary trenches at the grain boundary region at the bottom of the perovskite films in the control and target groups; Figure 4f shows a comparison of the depth of surface grain boundary trenches at the grain boundary region at the bottom of the perovskite films in the control and target groups; Figure 4g shows a laser scan of PL emission at the bottom of the perovskite film in the control group.Confocal microscopy (CLSM) images; Figure 4h shows a CLSM image of PL emission at the bottom of the perovskite film of the target group. In Figures 4g and 4h, the collection range of the red area is 700-800 nm, and the collection range of the green area is 450-550 nm;

[0060] Figure 5 shows the grain analysis results of the perovskite films of the control group and the target group. Figure 5a shows the SEM image of the perovskite film grains of the control group; Figure 5b shows the SEM image of the perovskite film grains of the target group; Figure 5c shows the grain size distribution map of the perovskite film of the control group; Figure 5d shows the grain size distribution map of the perovskite film of the target group.

[0061] Figure 6 shows that the perovskite film of the present invention has excellent charge transport, chemical and mechanical properties. Figure 6a (control group) and Figure 6b (target group) show the transient absorption spectra of the quenching rate of the perovskite film; Figure 6c shows the time-resolved photoluminescence (TRPL) spectra of the perovskite films of the control group and the target group; Figure 6d shows a comparison of the band arrangement diagrams of the bottom interface of the perovskite film in the control group; Figure 6e shows a comparison of the band arrangement diagrams of the bottom interface of the perovskite film in the target group; Figure 6f shows a statistical graph of the adhesion test results of ASTM D3359 (6 samples each from the control group and the target group); Figure 6g shows photographs of samples with an adhesion of 1B for the perovskite film in the control group and an adhesion of 4B for the perovskite film in the target group; Figure 6h shows cross-sectional SEM photographs of the perovskite films of the control group and the target group after 100 hours of continuous irradiation.

[0062] Figure 7 shows the ultraviolet photoelectron spectroscopy (UPS) of the top and bottom surfaces of the perovskite film. Figures 7a and 7b show the UPS of the top surface of the perovskite film; Figures 7c and 7d show the UPS of the bottom surface of the perovskite film.

[0063] Figure 8 shows the conduction band bottom estimated based on the Tauc curve of the UV-vis absorption spectrum.

[0064] Figure 9 shows photographs of the adhesion test samples of the perovskite films in the control group and the target group.

[0065] Figure 10 shows representative cross-sectional SEM images of the device structures of the inverted perovskite solar cell (control group) without the CSV crystal layer and the inverted perovskite solar cell (target group) according to the present invention.

[0066] Figure 11 shows the performance parameters of the inverted perovskite solar cells obtained using CSV solutions of different concentrations. Figure 11a shows the open-circuit voltage as a function of CSV solution concentration; Figure 11b shows the short-circuit current density as a function of CSV solution concentration; Figure 11c shows the fill factor as a function of CSV solution concentration; Figure 11d shows the photoelectric conversion efficiency as a function of CSV solution concentration.

[0067] Figure 12 shows the performance of the best-performing PSC in the control group (without CSV seeding) and the target group (with CSV seeding). Figure 12a shows the current density-voltage (J-V) curve from open-circuit voltage (VOC) to short-circuit current density (JSC).The specification is on page 5 / 22, page 9, CN 122270013 A line, where the inset shows the steady-state output photoelectric conversion efficiency (SPO PCE) as a function of time; Figure 12b shows the PCE statistics of the control group and the target group (n=30); Figure 12c shows the FF statistics of the control group and the target group (n=30); Figure 12d shows the maximum power point tracking stability test results; Figure 12e shows the thermal stability test results of the PSC; Figure 12f shows the J-V curve and performance parameters of the perovskite solar cell device according to the present invention with an area of ​​49.91 cm2; Figure 12g compares the efficiency changes of the perovskite solar cell of the present invention with those of the perovskite solar cells in the prior art with photoelectric conversion efficiencies exceeding 24% in the cross-scale fabrication from cell to module, and the references Ref 23-28 mentioned in the figure are as follows:

[0068] Ref .23: Huang , Y . et al . Finite perovskite hierarchical structures via ligand confinement leading to efficient inverted perovskite solar cells.Energy Environ.Sci.16,557‑564(2023);

[0069] Ref.24:Chen,S.et al.Stabilizing perovskite‑substrate interfaces for high‑performance perovskite modules.Science 373,902‑907(2021);

[0070] Ref.25:Wang,H.et al .Impurity‑healing interface engineering for efficient perovskite submodules.Nature 634,1091‑1095(2024);

[0071] Ref .26: Kim,M.et al.Conformal quantum dot‑SnO2 layers as electron transporters for efficient perovskite solar cells.Science 375,302‑306(2022);

[0072] Ref .27:Shi ,P.et al .Oriented nucleation in formamidinium perovskitefor photovoltaics. Nature 620, 323-327 (2023);

[0073] Ref. 28: Bu, T. et al. Modulating crystal growth of formamidinium–caesium perovskites for over 200cm2 photovoltaic sub-modules. Nat. Energy 7, 528-536 (2022).

[0074] Figure 13 shows the performance statistics of PSCs (n=30) for the control group (without CSV seeding) and the target group (with CSV seeding). Figure 13a shows the statistical results of VOC; Figure 13b shows the statistical results of JSC.

[0075] Figure 14 shows the external quantum efficiency (EQE) spectrum and integrated current density of the inverted perovskite solar cells of the control group and the target group.

[0076] Figure 15 shows the performance measurement results of the PSC devices of the control group and the target group. Figure 15a shows the built-in field voltage (Vbi) determined by the Mott-Schottky curve; Figure 15b shows the EQE of electroluminescence, with an inset showing the electroluminescence (EL) intensity versus wavelength and a photograph of the PSC device.

[0077] Figure 16 shows the performance measurement results of the PSC devices in the control group and the target group with only holes. Figure 16a shows the test results of the all-hole device (control group) without using CSV seed crystals; Figure 16b shows the test results of the all-hole device (target group) using CSV seed crystals, with an inset showing the structure of the perovskite solar cell.

[0078] Figure 17 shows the relationship between the open-circuit voltage and light intensity of the PSCs in the control group (without using CSV seed crystals) and the target group (using CSV seed crystals) under different light intensities. Detailed Embodiments

[0079] The present invention will be further described below through specific embodiments, but this is not a limitation of the present invention. Those skilled in the art can make various modifications or improvements based on the basic idea of ​​the present invention, but as long as they do not depart from the basic idea of ​​the present invention, they are all within the scope of the present invention.

[0080] In one aspect, the present invention provides a method for preparing an inverted perovskite solar cell, characterized in that: Before applying a perovskite precursor solution to a substrate, a crystallizing solvate is used to seed crystals on the substrate to obtain a substrate on which a crystallizing solvate crystal layer is formed, wherein the general formula of the crystallizing solvate is AxPbX4·yDMSO, wherein A comprises ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethyl...One or more of the following groups are selected from: ethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation; X is selected from one or more of the following groups are selected from: I-, Br-, and Cl-; x is 1-2; y is 1-3; and DMSO is dimethyl sulfoxide.

[0081] In one embodiment, the substrate may be a self-assembled monolayer. Self-assembled monolayers may include one or more of the following: [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACZ), 2-(3,6-dimethoxycarbazole-9-yl)ethylphosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, (4-(9H-dibenzo[a,c]carbazole-9-yl)butyl)phosphonic acid, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid, (2-(pyrene-1-yl)ethyl)phosphonic acid, and (4-(3,6-diphenyl-9H-carbazole-9-yl)butyl)phosphonic acid.

[0082] In some embodiments, the self-assembled monolayer is located on the hole transport material and serves as part of the hole transport layer. In other embodiments, the hole transport layer may be replaced by a self-assembled monolayer, i.e., the hole transport layer is not included. The hole transport material may be selected from NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene) (P3HT), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), etc. Hole transport materials known in the art may be used.

[0083] In some embodiments, the substrate may be the hole transport layer, that is, the crystalline solvate crystal layer may be formed directly on the hole transport layer.

[0084] In one embodiment, the method for preparing an inverted perovskite solar cell according to the present invention includes the following steps:

[0085] 1) providing a self-assembled monolayer;

[0086] 2) seeding the self-assembled monolayer with a crystalline solvate to obtain a self-assembled monolayer on which a crystalline solvate crystal layer is formed;

[0087] 3) forming a perovskite layer on the self-assembled monolayer on which the crystalline solvate crystal layer is formed.

[0088] In some embodiments, the seeding includes: applying a solution of the crystalline solvate to a substrate; and annealing. Preferably, the annealing temperature is from room temperature to 200°C, and the annealing time is 2-30 min. Preferably, the annealing is performed in an inert atmosphere or in ambient air with a humidity not exceeding 80%.

[0089] Preferably, the concentration of the crystalline solvate solution is 1-60 mg / mL, more preferably 1-10 mg / mL, and even more preferably...The selected concentration is 5 mg / mL. The solvent for the solution can be selected from dimethyl sulfoxide (DMSO), N',N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP).

[0090] In some embodiments, the solution of the crystalline solvate is applied to the substrate by spin coating; preferably, spin coating is performed at 1000-5000 rpm for 10-30 seconds. In other embodiments, the solution of the crystalline solvate is applied to the substrate by slot coating, blade coating, spraying, etc.

[0091] Preferably, the thickness of the crystalline solvate crystal layer is 1-100 nm, more preferably 1-20 nm. The thickness of the crystalline solvate crystal layer is discontinuous.

[0092] In some preferred embodiments, the crystalline solvate is PDPbI4·DMSO, wherein PD is a piperazine cation, and PD = (C4N2H12)2+.

[0093] Based on single-crystal X-ray diffraction (XRD) analysis, it can be determined that the crystallized solvate crystal layer obtained in this invention has an orthorhombic, monoclinic, or tetragonal crystal structure, depending on the composition of the crystallized solvate. For example, when the solvate is PDPbI4·DMSO, where PD = (C4N2H12)2+, the crystallized solvate crystal layer has an orthorhombic crystal structure; when the crystallized solvate is P2PbI4·2DMSO, where P is a piperazine cation and P = (C4N2H11)+, the crystallized solvate crystal layer has a monoclinic crystal structure.

[0094] In some embodiments, the formation of the perovskite layer in step 3) above includes: applying a perovskite precursor solution to a self-assembled monolayer on which the crystallized solvate crystal layer is formed; adding an antisolvent to the perovskite precursor solution; and annealing.

[0095] Preferably, the antisolvent is added dropwise 0-50 seconds after the perovskite precursor solution is applied. More preferably, the annealing temperature is from room temperature to 350°C, and the annealing time is 5-50 min. More preferably, the annealing is carried out in an inert atmosphere or in ambient air with a humidity not exceeding 80%.

[0096] In some embodiments, the concentration of the perovskite precursor solution is 0.5-1.7 mol / L, preferably 1-1.7 mol / L. The solvent of the solution may be selected from N',N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, ethanol, and water.

[0097] In some embodiments, the antisolvent is selected from ethyl acetate, chlorobenzene, diethyl ether, methyl acetate, anisole, and isopropanol.

[0098] The perovskite precursor solution can be applied by spin coating onto a self-assembled monolayer on which a crystalline solvate crystal layer is formed. Preferably, the spin coating is performed at 1000-5000 rpm for 10-50 seconds.

[0099] Preferably, the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and combinations of Cs+ with Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), and methylamine ion (MA+); B is selected from Pb2+, Sn2+, and combinations thereof; and X is selected from I-, Br-, Cl-, and combinations thereof.

[0100] Preferably, the thickness of the perovskite layer is 200-1000 nm.

[0101] Preferably, the thickness of the self-assembled monolayer is 2-10 nm.

[0102] In another aspect, the present invention also provides a perovskite film composition comprising a perovskite layer and a self-assembled monolayer, wherein a crystalline solvate crystal layer formed by a crystalline solvate is present between the perovskite layer and the self-assembled monolayer, wherein the general formula of the crystalline solvate is AxPbX4·yDMSO, wherein A comprises one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation and N,N-dimethylethylenediamine cation, X is selected from one or more of the group consisting of I-, Br- and Cl-, x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide.

[0103] In some embodiments, the thickness of the crystalline solvate crystal layer may be 1-100 nm. Preferably, the thickness of the crystalline solvate crystal layer is 1-20 nm. The crystallization solvate crystal layer is discontinuous.

[0104] In some embodiments, the crystallization solvate may be PDPbI4·DMSO, wherein PD is a piperazine cation and PD = (C4N2H12)2+. The crystallization solvate crystal layer may have an orthorhombic crystal structure.

[0105] In some embodiments, the crystallization solvate may be P2PbI4·2DMSO, wherein P is a piperazine cation and P = (C4N2H11)+. The crystallization solvate crystal layer may have a monoclinic crystal structure.

[0106] Preferably, the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs+, and combinations of Cs+ with Ru+, K+, Na+, Li+, dimethylamine ion (DMA+), formamidinium ion (FA+), methylamine ion (MA+); B is selected from Pb2+, Sn2+ and combinations thereof; X is selected from I-, Br-, Cl- and combinations thereof.

[0107] Preferably, the thickness of the perovskite layer is 200-1000 nm.

[0108] The self-assembled monolayer may include [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACZ), 2-(3, ... (Specification)Page 8 / 22, CN 122270013 A 6-Dimethoxycarbazole-9-yl)ethylphosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, (4-(9H-dibenzo[a,c]carbazole-9-yl)butyl)phosphonic acid, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid, (2-(pyrene-1-yl)ethyl)phosphonic acid, and (4-(3,6-diphenyl-9H-carbazole-9-yl)butyl)phosphonic acid.

[0109] In another aspect, the present invention also provides the application of the perovskite film composition in the preparation of inverted perovskite solar cells.

[0110] In another aspect, the present invention provides a crystalline solvate having the general formula AxPbX4·yDMSO, wherein A comprises one or more of the group consisting of ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation, X is selected from one or more of the group consisting of I-, Br-, and Cl-, x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide.

[0111] In some embodiments, the crystalline solvate according to the present invention is PDPbI4·DMSO, wherein PD is a piperazine cation, and PD = (C4N2H12)2+.

[0112] In yet another aspect, the present invention provides the application of this crystalline solvate in the preparation of inverted perovskite solar cells.

[0113] The crystallized solvate crystal layer according to the present invention has some inherent advantages, which the inventors have rationalized as a guiding principle to regulate the bottom interface formation of SAM-based inverted perovskite solar cells. PDPbI4·DMSOCSV is used as an example. First, the organic piperazine cation PD and DMSO solvent molecules can interact strongly with Pb. Then, due to its low-dimensional crystallization, PDPbI4·DMSO tends to grow as a nanorod structure with a high aspect ratio, which can guide liquid diffusion. Furthermore, DMSO molecules in the crystalline state can be thermally released at a controlled rate, initiating annealing of the crystallized solvate at the bottom of the film in an unprecedented manner, thereby mitigating microstructural and electronic defects at the interface.

[0114] Figure 1a shows a schematic diagram of a CSV seeding method according to an embodiment of the present invention to illustrate the process of the CSV seeding method and how it obtains a better perovskite film bottom than conventional methods, wherein the crystallized solvate is PDPbI4·DMSOCSV.DMSO. In CSV, Pb-I6 octahedra are arranged in a serrated structure with shared vertices, separated by PDI2 and DMSO along the c-axis. To prepare a thin CSV crystal layer on Me-4PACz SAM, it is only necessary to spin-coat the precursor solution (e.g., a DMF solution of PDPbI4·DMSO) and perform thermal annealing (e.g., annealing at 100°C for 2 min). Figure 1b shows a scanning electron microscope (SEM) image of the CSV crystal layer spin-coated on SAM, which shows that the spin-coated CSV crystal layer consists of uniformly distributed rod-shaped nanocrystals. In particular, the inset (SEM image) in Figure 1b shows the morphology of the rod-shaped nanocrystals.

[0115] The unique chemical and microstructural characteristics of CSV can significantly promote the wetting of the perovskite precursor solution on SAM. As shown in Figure 1c, the wetting angle (contact angle) on the SAM (top) is 31.29°, while the wetting angle on the SAM (bottom) with the CSV crystal layer formed thereon is significantly reduced to 17.97°.

[0116] As shown in Figure 1d, the X-ray diffraction (XRD) of the CSV crystal layer prepared by spin coating of PDPbI4·DMSO crystals exhibits the same main diffraction peaks as those of crystals obtained by single-crystal growth (i.e., single crystals as described below).

[0117] Figure 1e shows the in-situ UV-Vis absorption spectrum tracking of the perovskite film after thermal annealing at 100°C; the bottom figure shows the results of the perovskite film formed on the SAM with the CSV crystal layer formed thereon, and the top figure shows the results of the perovskite film formed directly on the SAM. Figure 1e is a 2D contour plot showing the change of absorption characteristics with annealing time at all wavelengths. It was found that the CSV seeding method of the present invention generally accelerates perovskite crystallization. The formation of light-absorbing perovskite on SAM with a CSV crystal layer is much faster than on SAM. (Specification 9 / 22, page 13, CN 122270013 A)

[0118] Figure 2 further shows the change in absorbance at 750 nm as a function of annealing time after 100°C thermal annealing on SAM (control group) and SAM with a CSV crystal layer formed thereon (target group). It can be seen that the absorbance of the target group perovskite film rapidly reaches 0.5 within 100 s. In contrast, the absorbance of the control group perovskite film only reaches 0.2. The accelerated crystallization of perovskite in the target group is attributed to more efficient heterogeneous nucleation at the film bottom induced by the CSV seed crystals of the nanostructure.

[0119] Figure 3 shows the steady-state fluorescence spectrum of the CSV crystal layer.

[0120] Figure 4 shows the perovskite films of the target group and the control group, as well as the microstructural details of their respective film bottoms. Figures 4a and 4b show cross-sectional SEM images of the perovskite films in the control and target groups, respectively. Figures 4c and 4d show the flipped images.Top-view SEM image of the bottom of the peeled perovskite film. It can be observed that, in the absence of CSV seed crystals (control group), the bottom of the perovskite film includes many nanoscale voids, mainly present at grain boundaries. The formation of voids at the bottom of the perovskite film is a commonly observed complex problem, which is related to non-uniform wetting and crystallization behavior. These buried nanoscale voids generated during crystallization inevitably hinder grain growth and coarsening, thereby limiting grain growth. However, the method of the present invention, through improved solution wetting and crystallization solvate annealing, enables the grains in the perovskite film of the target group to form a dense microstructure and grow through the thickness of the film.

[0121] Figure 5 further shows the grain analysis results of the perovskite films of the control group and the target group. Figures 5a and 5b show SEM images of the perovskite film grains in the control group and the target group, respectively; Figures 5c and 5d compare the grain size distribution in the two perovskite films, showing that after CSV seeding, the average grain size in the perovskite film changed from 443.9 nm (control group, Figure 5c) to 607.6 nm (target group, Figure 5d), and the grain size distribution was more uniform.

[0122] In addition to interfacial voids, there are also buried grain boundary trenches at the bottom of the perovskite film, which is an inherent feature of polycrystalline materials and can have an important influence in PSC. Therefore, these grain boundary trenches were detected using atomic force microscopy (AFM). Figure 4e shows atomic force microscopy (AFM) images of the grain boundary trenches at the bottom grain boundary region of the perovskite film in the control group and the target group. It can be seen that the bottom of the perovskite film in the target group shows a trend of becoming shallower at the grain boundary region. As shown in Figure 4f, the grain boundary trench at the bottom of the perovskite film in the control group was 23.9°, while the grain boundary trench at the bottom of the perovskite film in the target group was shallower to 7.8°.

[0123] The phase composition at the bottom surface of the perovskite films in the control group and the target group was detected using laser confocal scanning microscopy (CLSM). As shown in Figures 4g and 4h, the bottom of the perovskite film in the control group showed typical PL emission of perovskite only at 800 nm (Figure 4g); in contrast, the bottom of the perovskite film in the target group also showed PL emission at 500-600 nm (Figure 4h), which should be attributed to the residual structure from the DMSO removed from the CSV.

[0124] The perovskite film according to the present invention has excellent charge transport, chemical and mechanical properties. The carrier transport dynamics at the bottom perovskite / SAM interface of the perovskite film of the present invention were studied by transient absorption spectroscopy (TAS). The relative optical density (ΔA) of the ground-state bleached (GSB) peak reflects the photogenerated carrier density. As shown in Figure 6a (control group) and Figure 6b (target group), the perovskite film in the target group exhibits a faster quenching rate, reflecting a faster carrier transfer from perovskite to SAM.Figure 6c shows the time-resolved photoluminescence (TRPL) spectra of the perovskite films in the control and target groups. The perovskite film in the target group, after CSV seeding, exhibits faster photoluminescence (PL) decay, indicating that the perovskite film in the target group has improved hole extraction capability.

[0125] Figure 7 shows the UV photoelectron spectroscopy (UPS) of the top (perovskite layer side) and bottom (SAM side) surfaces of the perovskite film. The valence band maximum (VBM) at the bottom of the target group perovskite film shifts upward, where the energy level position of the valence band maximum at the bottom of the perovskite film is higher than that at the surface, which promotes the alignment of the interfacial bands, thereby promoting effective hole extraction. Specification 10 / 22 pages 14 CN 122270013 A

[0126] Figure 8 shows the conduction band minimum (CBM) estimated based on the Tauc curve of the UV-vis absorption spectrum. The shallower CBM at the bottom of the perovskite can establish an electronic barrier to hinder electron transport to the SAM. In contrast, the energy levels at the top and bottom surfaces of the control group perovskite film did not change significantly. Compared to the top surface, the secondary electron cutoff at the bottom surface of the target group perovskite film shifted towards lower binding energy (towards lower values), indicating a deeper work function at the bottom perovskite film, consistent with the KPFM results.

[0127] As shown in Figure 6d, the Fermi level determined by the initial energy shifted towards VBM (0.26 eV), thereby weakening the n-type of the bottom perovskite and generating an upward band bend at the bottom interface, which can significantly promote hole extraction and collection at the bottom interface of the perovskite film.

[0128] The bottom heterointerface of the perovskite film according to the present invention also has excellent mechanical properties. Adhesion tests (cross-section tests) were conducted on 6 control group perovskite films and 6 target group perovskite films respectively. Adhesion was graded based on retention in the cross-section area, with six grades (0B, 1B, 2B, 3B, 4B and 5B, where 0B is the lowest adhesion, indicating complete removal; 5B is the highest adhesion, indicating no adhesion loss) as defined by ASTM D3359. Figure 9 shows sample photographs of the control group and target group perovskite films after the adhesion test, and the statistical results are shown in Figure 6f. The adhesion of the perovskite layer of the experimental group sample was rated as 4B, while that of the control group sample was 0B, indicating that the perovskite film of the present invention has stronger adhesion than the control group sample. This enhanced mechanical strength can more effectively prevent interfacial voids and peeling.

[0129] To further evaluate the durability of the perovskite film, the photothermal fatigue of the perovskite-SAM heterostructure of the control group and target group perovskite films under the same irradiation stress was compared by SEM images of the perovskite film cross-section. As shown in Figure 6hAs shown, after 100 hours of continuous irradiation, obvious voids were observed at the perovskite-SAM heterostructure interface in the control group perovskite film, while the heterostructure interface of the dense perovskite film in the target group remained intact, without obvious void formation or interface peeling.

[0130] In another aspect, the present invention provides an inverted perovskite solar cell prepared according to the method of the present invention.

[0131] In some embodiments, the inverted perovskite solar cell of the present invention comprises a transparent conductive substrate, optionally including a hole transport layer, the perovskite film composition of the present invention, optionally including a passivation layer, an electron transport layer, a barrier layer, and an electrode layer, which are stacked sequentially. The barrier layer is also referred to as a “buffer layer”.

[0132] In some embodiments, a self-assembled monolayer may be used instead of a hole transport layer, i.e., the hole transport layer is not included. In some embodiments, the passivation layer may not be included.

[0133] The transparent conductive substrate of the inverted perovskite solar cell may be selected from ITO glass and FTO glass. The thickness of the transparent conductive substrate may be 50-200 nm. The hole transport layer may include one or more of NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene) (P3HT), and poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT:PSS). The thickness of the hole transport layer may be 1-20 nm. The passivation layer may include piperazine bisiodide (PDI2) or piperazine hydroiodide. The thickness of the passivation layer may be 1-10 nm. The electron transport layer may include C60 and methyl [6,6]-phenyl-C61-butyrate (PCBM). The thickness of the electron transport layer may be 20-50 nm. The blocking layer may include SnO2, (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) (BCP), and LiF. The thickness of the blocking layer may be 3-30 nm. The electrode layer may include one or more of silver (Ag), ITO, copper (Cu), and gold (Au). The thickness of the electrode layer can be 60-200 nm.

[0134] In a specific embodiment, the inverted perovskite solar cell of the present invention comprises an ITO glass / NiOx layer / Me-4PACz SAM layer / CSV crystal layer / perovskite layer / passivation layer / C60 layer / SnO2 layer / Ag layer stacked sequentially. Figure 10 shows representative cross-sectional SEM images of the device structures of an inverted perovskite solar cell (other layers are the same, control group) and the inverted perovskite solar cell of the present invention (target group) without the CSV crystal layer. By changing the solution concentration of the CSV seed crystal (wherein the concentration of the DMF solution of PDPbI4·DMSO used is 0 mg / mL, 4 mg / mL, 5 mg / mL, 8 mg / mL and specification page 11 / 22 15 CN 122270013 A)According to the obtained device performance parameters, the preferred solution concentration of CSV is 5 mg / mL N,N-dimethylformamide (DMF) solution (Figure 11).

[0135] Figure 12 shows the performance of the best-performing PSC of the above-mentioned inverted perovskite solar cell control group (without CSV seed crystal) and target group (with CSV seed crystal). As shown in Figure 12a, the open-circuit voltage (VOC) of the target group PSC is 1.17V and the short-circuit current density (JSC) is 25.78 mA / cm2; Figure 12b shows that the photoelectric conversion efficiency (PCE) of the target group PSC is 26.13%; and Figure 12c shows that the fill factor (FF) of the target group PSC is as high as 86.75%. In comparison, the PCE of the control group PSC is 24.82%, the VOC is 1.15V, the JSC is 25.78 mA / cm2, and it has a moderate FF of 83.73%. The most significant improvement is the FF, which may be related to the reduction in series resistance and the increase in shunt resistance in the PSC device of the present invention.

[0136] As shown in the inset of Figure 12a, under sunlight irradiation and at maximum power point tracking, the PCE output of the target group PSC device stabilized at 25.61% within 300 seconds, higher than the PCE output of 23.99% of the control group PSC device. Compared with the JSC obtained from the J-V measurement results, the current density of the target group PSC device, integrated from the external quantum efficiency (EQE) spectrum, is 25.31 mA / cm2 (Figure 14).

[0137] To further understand the improvement of the PSC device by CSV seeding, the built-in field voltage (Vbi) was measured by Mott-Schottky curve. As shown in Figure 15a, the Vbi of the target group PSC device is 1.09V, higher than the Vbi (1.06V) of the control group PSC device, which allows for more efficient separation of photogenerated charge carriers in the target group PSC device. This is also consistent with the high VOC of the target group PSC device. Furthermore, a steeper slope was observed for the target group PSC devices, indicating a reduction in charge accumulation at the PSC device interface.

[0138] In one embodiment, for both the target group and the control group (without the CSV crystal layer), the space charge confinement current (SCLC) of hole-only PSC devices with the Ag / 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD) / perovskite / CSV crystal layer / SAM / NiOx structure was also tested to test hole transport. As shown in Figure 16, the trap density of the target group PSC devices was calculated to be 1.26 × 10¹⁵ cm⁻³, and the trap density of the control group PSC devices was 1.90 × 10¹⁵ cm⁻³, by measuring the trap fill voltage (VTFL). This is also reflected in the ideality factor (nid) changing from 1.76.The 1.49 after CSV seeding (Fig. 17). For the reasons mentioned above, CSV seeding improves the EQE of electroluminescence of the PSC device by 80% at injection levels close to those of the JSC (Fig. 15b), thus demonstrating that the target group of PSC devices has improved interfacial carrier dynamics.

[0139] The PSC device of the present invention also has excellent operational stability and thermal stability. Under maximum power point tracking under continuous sunlight irradiation (55±5°C), the T90 lifetime (maintaining more than 90% of the initial PCE) of the PSC device of the present invention is greater than 1000 hours. In one embodiment, under 1000 hours of maximum power point tracking under continuous sunlight irradiation (55±5°C), the PSC device of the present invention can maintain 93% of its initial photoelectric conversion efficiency. In comparison, the control group PSC device (without the CSV crystal layer) can only maintain 71.3% of the initial PCE after 1000 hours (Fig. 12d). In the thermal stability test, the packaged PSC device was subjected to a temperature of 85°C in the ambient environment. As shown in Figure 12e, after 970 hours, the target group PSC device maintained 84.2% of its initial PCE, while the control group PSC device maintained 75.9% of its initial PCE.

[0140] In another aspect, the present invention provides an electrical device comprising the inverted perovskite solar cell of the present invention. The method of preparing inverted perovskite solar cells using CSV seeding of the present invention advantageously improves the diffusion and wetting of the perovskite precursor solution and the formation of microstructures at the bottom of the perovskite film, thus making it particularly suitable for scale-up of devices.

[0141] In one embodiment, an inverted perovskite solar cell module is prepared using slot coating and based on the crystallization solvent synthesis seeding method of the present invention. Figure 12f shows a battery module according to the present invention with an area of ​​49.91 cm2, which is based on FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO and has a PCE of up to 23.15%, indicating that only a small efficiency reduction is shown when the device area is scaled up to the specified size (Figure 12g).

[0142] The present invention will be further explained or illustrated by way of example below, but these examples should not be construed as limiting the scope of protection of the present invention.

[0143] Examples

[0144] Unless otherwise specified, the experimental methods used in the following examples are all performed using conventional experimental procedures, operations, materials and conditions in the field of solar cells.

[0145] Example 1. Preparation of PSC device of the present invention

[0146] ITO glass (8Ω sq-1) was continuously superheated with detergent (12BASIC), deionized water and ethanol respectively.Acoustic treatment was performed for 30 minutes each. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg of NiOx nanoparticles (5-10 nm particle size, purchased from Liaoning Youxuan New Materials Technology Co., Ltd.) were dispersed in 1 mL of deionized water (or a mixed solvent of deionized water and isopropanol (IPA, purchased from Sigma) at a volume ratio of 3:1) and ultrasonically treated for 30 minutes before use. Then, 70 μL of NiOx dispersion was spin-coated onto the treated ITO glass at 4000 rpm / 25 s and annealed at 140 °C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, 50 μL of a methanol solution (purchased from Sigma) of Me-4PACZ (TCI product, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.) was spin-coated onto the NiOx hole transport layer prepared above at 3000 rpm / 25 s, and then annealed at 100 °C for 10 minutes to form a self-assembled monolayer of about 2 nm.

[0147] Next, in a nitrogen glove box, 50 μL of a 5 mg / mL DMF solution of a crystalline solvate (PDPbI4·DMSO, where PD = (C4N2H12)2+ (piperazine cation)) was spin-coated onto the Me-4PACZ self-assembled monolayer at 3000 rpm / 25 s, and annealed at 100 °C for 2 minutes to form a 10 nm crystalline solvate crystal layer. The preparation process of the crystalline solvate is as follows: 1M PDI2 and PbI2 are dissolved in DMSO, stirred at room temperature overnight, and then allowed to stand. The supernatant is taken into a 4mL vial, and then the vial is placed open in a 20mL bottle. 3mL of tetrahydrofuran is added to the bottle, the bottle cap is tightened, and the vial is allowed to stand for 5 days to obtain the crystalline solvate.

[0148] In a nitrogen glove box, 50 μL of a perovskite precursor solution of Cs0.05(MA0.05FA0.95)0.95PbI3 (concentration 1.5mol / L, solvent DMF:DMSO = 4:1 (v / v), DMF and DMSO are both purchased from Sigma) is taken and spin-coated onto the crystal layer of the crystalline solvate prepared above at speeds of 1000rpm / 10s and 5000rpm / 30s. 300 μL of ethyl acetate antisolvent is added dropwise 20s after the spin-coating begins. Annealing was performed at 100°C for 30 minutes to form a perovskite layer with a thickness of approximately 700 nm. In a nitrogen glove box, 50 μL of PDI2 (1 mg / mL IPA solution, filtered through a 0.22 μm filter membrane) was spin-coated onto the top of the perovskite layer at 5000 rpm for 25 s to form a passivation layer of approximately 2 nm. Then, a 25 nm C60 (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) electron transport layer was deposited on top via thermal evaporation at a rate of [missing information]. C60 was deposited at 100°C.Afterwards, an ALD-SnO2 (Sn source: TDMASn, purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source: pure water from Wahaha) barrier layer (thickness approximately 15nm) was deposited. Finally, a silver electrode layer with a thickness of 100nm was thermally evaporated at a rate of

[0149] .

[0149] The annealing steps in the above preparation process that were not specified to be operated in a nitrogen glove box were all carried out in ambient air with a humidity of no more than 80%.

[0150] The perovskite film and PSC device described in the accompanying drawings and related descriptions were all prepared by the method of Example 1.

[0151] Example 2. Preparation of the PSC device of the present invention

[0152] ITO glass (8Ω sq-1) was continuously ultrasonically treated with detergent, deionized water and ethanol for 30 minutes each. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. In a nitrogen glove box, 50 μL of a 1 mg / mL PTAA ([poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], Mn<6000, purchased from Xi'an Yuri Solar Energy Technology Co., Ltd., page 13 / 22, CN 122270013 A) chlorobenzene (purchased from Sigma) solution was spin-coated onto the prepared substrate at 3000 rpm / 25 s, and then annealed at 100 °C for 10 minutes to obtain a hole transport layer with a thickness of approximately 2 nm.

[0153] Next, in a nitrogen glove box, 60 μL of an 8 mg / mL crystalline solvate (PDPbI4·DMSO, where PD = (C4N2H12)2+(piperazine cation)) DMF solution was spin-coated onto the PTAA at 3000 rpm / 25 s, and annealed at 100 °C for 2 minutes to obtain a crystalline solvate crystal layer with a thickness of approximately 20 nm.

[0154] In a nitrogen glove box, 60 μL of a perovskite precursor solution (concentration 1.5 mol / L, solvent DMF:DMSO = 4:1 (v / v)) of Cs0.05(MA0.1FA0.9)0.95PbI3, stirred for 8 hours, was spin-coated onto the crystallized solvate layer prepared above at 1000 rpm / 10 s and 5000 rpm / 30 s. 150 μL of chlorobenzene antisolvent was added dropwise 5 s before the end of spin-coating. The mixture was annealed at 110 °C for 20 minutes to obtain a perovskite layer with a thickness of approximately 800 nm. In a nitrogen glove box, 60 μL of PI (piperazine hydroiodide) (1 mg / mL IPA solution, filtered through a 0.22 μm filter membrane) was spin-coated onto the top of the perovskite layer at 5000 rpm / 25 s to form a passivation layer with a thickness of approximately 2 nm. Then, in a nitrogen glove box, a 20 mg / mL PCBM (purchased from Xi'an Sunlight Energy Technology Co., Ltd.) chlorobenzene (purchased from Sigma) solution was spin-coated onto the top of the passivation layer at 1500 rpm / 25 s to form a thick layer.An electron transport layer with a thickness of approximately 30 nm was formed, and a solution of 0.5 mg / mL BCP (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) in isopropanol (purchased from Sigma) was spin-coated at 5000 rpm / 25 s to form a buffer layer with a thickness of approximately 5 nm. Finally, a silver electrode layer with a thickness of 100 nm was thermally evaporated at a rate of

[0155] .

[0156] The annealing steps in the above preparation process, unless otherwise specified, were performed in ambient air with a humidity of no more than 80%.

[0157] Example 3. Preparation of the PSC device of the present invention

[0158] ITO glass (8 Ω sq-1) was continuously ultrasonically treated with detergent, deionized water and ethanol for 30 minutes each. The cleaned ITO glass substrate was treated with ultraviolet ozone for 15 minutes, and then NiOx was used as the hole transport layer. It was spin-coated at 4000 rpm / 30 s and annealed on a hot stage at 140°C for 10 minutes to form a hole transport layer with a thickness of approximately 10 nm. The substrate was then transferred into a glove box under a nitrogen atmosphere, and the SAM layer (Me-4PACZ) was spin-coated onto the NiOx layer at 3000 rpm / 30 s. The substrate was then annealed on a hot plate at 100 °C for 10 minutes. The thickness of the SAM layer was approximately 2 nm.

[0158] In a nitrogen glove box, 60 μL of a DMF solution of 5 mg / mL of the crystalline solvate C4N2H14PbBr4·DMSO (the organic cation is N,N-dimethylethylenediamine cation) was taken and dynamically spin-coated onto the SAM layer at 3000 rpm / 30 s. The solution was then annealed on a hot plate at 100 °C for 2 minutes to obtain a crystalline solvate layer with a thickness of approximately 5 nm. The preparation process of the DMF solution of the crystalline solvate is as follows: 1M C4N2H14Br2 and PbBr2 are dissolved in DMSO, stirred overnight at room temperature, and then allowed to stand. The supernatant is taken into a 4mL vial, and then the vial is placed openly into a 20mL bottle. 3mL of tetrahydrofuran is added to the bottle, the cap is tightened, and the solution is allowed to stand for 5 days to obtain the crystalline solvate. Then, 5mg of the crystalline solvate is weighed and dissolved in DMF.

[0159] In a nitrogen glove box, 60 μL of a perovskite precursor solution of Cs0.05(MA0.05FA0.95)0.95Pb(I0.95Br0.05)3 (concentration 1.5 mol / L, solvent DMF:DMSO = 4:1 (v / v)) stirred for 8 hours was spin-coated onto the crystallized solvate layer prepared above at 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate antisolvent was added dropwise 20 s after the spin-coating began. The resulting perovskite film was then annealed on a hot plate at 100 °C for 30 minutes to obtain a perovskite layer with a thickness of approximately 700 nm.

[0160] In a nitrogen glove box, ethylenediamine hydroiodate (1 mg / mL) was dynamically spin-coated onto the perovskite layer at 5000 rpm / 30 s.An isopropanol solution was used to form a 2 nm thick passivation layer. Finally, a C60 electron transport layer (25 nm thick), a BCP blocking layer (5 nm thick), and an Ag electrode layer (100 nm thick) were deposited sequentially on the passivation layer under conventional conditions to prepare the inverse perovskite solar cell according to the present invention.

[0161] The annealing steps in the above preparation process that are not specified to be operated in a nitrogen glove box were all carried out in ambient air and the humidity was not greater than 80%.

[0162] Example 4. Preparation of PSC device of the present invention

[0163] FTO glass (8 Ω sq-1) was continuously ultrasonically treated with detergent, deionized water and ethanol for 30 minutes each. The cleaned ITO glass substrate was treated with ultraviolet ozone for 15 minutes, followed by spin-coating with NiOx as the hole transport layer at 4000 rpm for 30 seconds, and then annealed at 140°C for 10 minutes to form a hole transport layer with a thickness of approximately 10 nm. The substrate was then transferred to a glove box under a nitrogen atmosphere, and a methanol solution of Me-4PACZ was spin-coated onto the NiOx hole transport layer at 3000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes to form a self-assembled monolayer with a thickness of approximately 2 nm.

[0164] In a nitrogen glove box, 60 μL of a DMF solution containing 5 mg / mL of the crystalline solvate PDPbCl4·DMSO (where PD = (C4N2H12)2+ (piperazine cation)) was dynamically spin-coated onto the self-assembled monolayer prepared above at 3000 rpm / 30 s. The mixture was then annealed at 100°C for 2 minutes to obtain a crystalline solvate layer with a thickness of approximately 5 nm. The preparation process of the DMF solution of the crystalline solvate was as follows: 1 M of PDCl2 and PbCl2 were dissolved in DMSO, stirred overnight at room temperature, and allowed to stand. The supernatant was collected in a 4 mL vial, and the vial was placed open into a 20 mL bottle. 3 mL of tetrahydrofuran was added to the bottle, the cap was tightened, and the solution was allowed to stand for 5 days to obtain the crystalline solvate. Then, 5 mg of the crystalline solvate was weighed and dissolved in DMF.

[0165] In a nitrogen glove box, 60 μL of a perovskite precursor solution (concentration 1.5 mol / L, solvent DMF:DMSO = 4:1 (v / v)) of Cs0.05(MA0.05FA0.95)0.95Pb(I0.95Br0.05)3, stirred for 8 hours, was spin-coated onto the crystallized solvate layer prepared above at speeds of 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate antisolvent was added dropwise 20 s after the spin-coating began. The resulting perovskite film was then annealed on a hot plate at 100 °C for 30 minutes to obtain a perovskite layer with a thickness of approximately 700 nm.

[0166] In a nitrogen glove box, ethylenediamine hydroiodide (1 mg / mL isopropanol solution) was dynamically spin-coated onto the perovskite layer at 5000 rpm / 30 s to form a 2 nm thick passivation layer. Finally, a C60 electron transport layer (25 nm thick), a BCP blocking layer (5 nm thick), and an Ag electrode layer (100 nm thick) were deposited sequentially on the passivation layer under conventional conditions to prepare the inverse perovskite solar cell according to the present invention.

[0167] Annealing steps not specified to be performed in a nitrogen glove box in the above preparation process were all performed in ambient air with a humidity not exceeding 80%.

[0168] Comparative Example 1. Preparation of Control Group PSC Device

[0169] The PSC device was prepared using essentially the same steps as in Example 1, except that spin-coating of the crystallization solvate was not performed.

[0170] ITO glass (8 Ω sq-1) was continuously ultrasonically treated with detergent, deionized water, and ethanol for 30 minutes each. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg of NiOx nanoparticles (5-10 nm particle size, purchased from Liaoning Youxuan New Materials Technology Co., Ltd.) were dispersed in 1 mL of deionized water (or a 3:1 volume ratio of deionized water to IPA) and sonicated for 30 minutes before use. Then, 70 μL of the NiOx dispersion was spin-coated onto the treated ITO glass at 4000 rpm / 25 s and annealed at 140 °C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, 50 μL of a methanol solution of Me-4PACZ (TCI product, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.) was spin-coated onto the prepared NiOx hole transport layer at 3000 rpm / 25 s and then annealed at 100 °C for 10 minutes to form a self-assembled monolayer of approximately 2 nm.

[0171] In a nitrogen glove box, 50 μL of a 1.5 mol / L perovskite precursor solution (solvent: DMF:DMSO = 4:1 (v / v)) of Cs0.05(MA0.05FA0.95)0.95PbI3, stirred for 8 hours, was spin-coated onto the self-assembled monolayer prepared above at speeds of 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate anti-solvent was added dropwise 20 s after the start of spin-coating. The mixture was annealed at 100 °C for 30 minutes to form a perovskite layer with a thickness of approximately 700 nm. In a nitrogen glove box, 50 μL of PDI2 (1 mg / mL IPA solution, filtered through a 0.22 μm filter membrane) was spin-coated onto the top of the perovskite layer at 5000 rpm for 25 s, according to the instructions on page 15 / 22, section 19, CN 122270013 A, to form a passivation layer of approximately 2 nm. Then, a 25 nm layer of C60 (purchased from [unspecified source]) was deposited on top via thermal evaporation at a rate of [unspecified].Xi'an Sunlight Energy Technology Co., Ltd.) Electron transport layer. After depositing C60 at 100°C, an ALD-SnO2 (Sn source: TDMASn purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source from Wahaha's pure water) barrier layer (thickness approximately 15nm) was deposited. Finally, a silver electrode layer with a thickness of 100nm was thermally evaporated at a rate of

[0172] .

[0173] The annealing steps in the above preparation process that were not specified to be operated in a nitrogen glove box were all carried out in ambient air with a humidity of no more than 80%.

[0174] The perovskite film and PSC device described in the accompanying drawings and related descriptions were prepared by the method of Comparative Example 1.

[0175] Comparative Example 2. Preparation of PSC device

[0176] The PSC device was prepared by basically the same steps as in Example 1, except that the compound forming the crystallized solvate layer was different from the crystallized solvate of the present invention.

[0176] ITO glass (8Ω sq-1) was continuously ultrasonically treated with detergent, deionized water, and ethanol for 30 minutes each. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg of NiOx nanoparticles (5-10 nm particle size, purchased from Liaoning Youxuan New Materials Technology Co., Ltd.) were dispersed in 1 mL of deionized water (or a mixed solvent with a deionized water:IPA volume ratio of 3:1) and ultrasonically treated for 30 minutes before use. Then, 70 μL of NiOx dispersion was spin-coated onto the treated ITO glass at 4000 rpm / 25 s and annealed at 140 °C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, 50 μL of a methanol solution of Me-4PACZ (TCI product, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.) was spin-coated onto the NiOx hole transport layer prepared above at 3000 rpm / 25 s, and then annealed at 100 °C for 10 minutes to form a self-assembled monolayer of about 2 nm.

[0177] In a nitrogen glove box, 60 μL of a DMF solution of 5 mg / mL two-dimensional crystal BA2PbI4 (BA is a butylamine cation) was taken and dynamically spin-coated onto the self-assembled monolayer prepared above at 3000 rpm / 30 s, and annealed on a hot plate at 100 °C for 2 minutes to obtain a crystal layer with a thickness of about 5 nm. The preparation process of DMF solution of BA2PbI4 (BA is butylamine cation) is as follows: 1M BAI and PbI2 are dissolved in hydroiodic acid, stirred at 120℃ and placed in an oven for 60 hours, and crystals are grown by gradient cooling (10℃ / 6 hours). Then, 5mg of crystals are weighed and dissolved in DMF.

[0178] In a nitrogen glove box, a 1.5mol / L concentration of Cs0.05(MA0.05FA0.95)0.95Pb(I0.95Br0) is stirred for 8 hours.50 μL of a 0.05% DMF:DMSO solution (4:1 v / v) was spin-coated onto the prepared crystal layer at 1000 rpm for 10 s and 5000 rpm for 30 s. 300 μL of ethyl acetate was added dropwise 20 s after the spin-coating began. The mixture was annealed at 100 °C for 30 min to form a perovskite layer approximately 700 nm thick. In a nitrogen glove box, 50 μL of PDI2 (1 mg / mL IPA solution, filtered through a 0.22 μm filter) was spin-coated onto the top of the perovskite layer at 5000 rpm for 25 s to form a passivation layer of approximately 2 nm. Then, a 25 nm C60 (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) electron transport layer was deposited on top via thermal evaporation at a rate of [missing value]. After depositing C60 at 100℃, an ALD-SnO2 (Sn source: TDMASn purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source from Wahaha's pure water) barrier layer (thickness approximately 15nm) was deposited. Finally, a silver electrode layer with a thickness of 100nm was thermally evaporated at a rate of

[0179] The performance parameters of the PSC devices prepared in Examples 1-4 and Comparative Examples 1-2 are shown in Table 1.

[0180] Table 1. Performance parameters of PSC devices Specification 16 / 22 pages 20 CN 122270013 A

[0181]

[0182] Example 5. Preparation of the inverse perovskite solar cell module of the present invention

[0183] A solar cell module was prepared on an FTO substrate with an area of ​​10cm×10cm2 based on FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO. FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO were prepared using a method similar to that in Example 1, except that: FTO glass was used as the transparent conductive substrate; the SAM layer was not included; the perovskite film was prepared by a slot coating process with a gap of 200 μm between the slot die and the substrate and a speed of 20 mm / s; the electron transport layer was PCBM with a thickness of 40 nm; the electrode layer was ITO with a thickness of 100 nm; the composition and thickness of the remaining layers were the same as those of the PSC device prepared in Example 1.

[0184] A 1064 nm laser (Trotec) with a power of 20 W was used to separate the sub-cells in the laser marking system. The parameters were: P1 line, laser power 60%, speed 300 mm / s, frequency 65 kHz, pulse duration 120 ns; P2 line was completed with 15% laser power, speed 1000 mm / s, frequency 65 kHz and pulse duration 120 ns; the process of P3 line was the same as that of P2 line. The widths of P1, P2, and P3 are 40 μm, 100 μm, and 40 μm, respectively. The total dead zone width is approximately 280 μm, and the geometric fill factor is 95.7%.

[0185] The slit-coated perovskite solar cell module with an area of ​​49.91×cm2 prepared by the above method obtained a PCE of 23.15%.

[0186] Example 6. Characterization method and related sample description of the present invention

[0187] Figure 1

[0188] Scanning electron microscope

[0189] The crystal layer prepared in Example 1 has a structure of ITO / NiOx / Me-4PACZ / CSV. A Carl Zeiss field emission scanning electron microscope was used with a scanning voltage of 2kV, in inlense mode, and magnification of 20000x.

[0190] X-ray diffraction

[0191] The crystal layer prepared in Example 1 has a structure of ITO / CSV. The crystal film was scraped off with a knife and powder XRD was tested. The preparation method of CSV single crystal powder is as follows: 1M PDI2 and PbI2 are dissolved in DMSO, stirred at room temperature overnight, and then allowed to stand. The supernatant is taken into a 4mL vial, and the vial is placed open in a 20mL bottle. 3mL of tetrahydrofuran is added to the bottle, the cap is tightened, and the vial is allowed to stand for 5 days to obtain crystals. The grown crystals are then removed with tweezers, the residual solvent on the crystals is wiped off with a non-woven cloth, and the crystals are ground into powder with an agate mortar and pestle for XRD testing.

[0192] XRD was performed using a Shimadzu SmartLab9KW XRD device from Japan. The X-ray source was Cuα, the wavelength was 1.54 Å, the collection range was 3-50 degrees, and the scanning speed was 20 degrees per minute.

[0193] Contact Angle Test Instruction Manual 17 / 22 pages 21 CN 122270013 A

[0194] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV and ITO / NiOx / Me-4PACZ, respectively. A Theat instrument was used, and the amount of perovskite solution (with the same composition as the perovskite precursor solution used in Example 1) added was 0.8 mL.

[0195] In-situ UV-Vis Absorption Spectroscopy

[0196] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The UV-Vis absorption spectra were measured by QE Pro (Marine Optics) with an integration time of 100 ms. One curve was collected every ten seconds for a total of 10 min.

[0197] Figure 2

[0198] Absorbance at 750 nm as a function of annealing time

[0199] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The UV-Vis absorption spectra were measured by QE Pro (Marine Optics), with an integration time of .100ms. One curve is collected every ten seconds for a total of 10 minutes. The intensity at 750nm is plotted against time.

[0200] Figure 3

[0201] Steady-state fluorescence spectrum

[0202] The sample prepared in Example 1, with the structure ITO / NiOx / Me-4PACZ / CSV / perovskite, was used to record the steady-state fluorescence spectrum using a Perkin LS-55 fluorescence spectrometer. The laser wavelength was 450nm and the collection time was 5000ms.

[0203] Figure 4

[0204] Scanning electron microscope

[0205] The samples prepared in Example 1 and Comparative Example 1, with the structures ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite respectively, were peeled off from the substrate using UV-curable adhesive, and the exposed bottom interface was tested. A Carl Zeiss field emission scanning electron microscope was used with a scanning voltage of 2kV, in inlense mode, and a magnification of 50,000x.

[0206] Atomic Force Microscopy

[0207] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The perovskite film was peeled off from the substrate using UV-cured adhesive, and the exposed bottom interface was tested. Atomic force imaging was performed using a multifunctional scanning probe microscope (Bruker), in tapping mode, using a Si cantilever of model RTESPA-300.

[0208] Laser Scanning Confocal Microscopy

[0209] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The perovskite film was peeled off from the substrate using UV-cured adhesive, and the exposed bottom interface was tested. The laser confocal microscopy was performed using an Olympus FV1000 CLSM system with a laser of 405 nm. The collection range for perovskite was 700-800 nm, and the collection range for CSV was 450-550 nm.

[0210] Figure 5

[0211] Scanning Electron Microscopy

[0212] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. A Carl Zeiss field emission scanning electron microscope was used, with a scanning voltage of 2kV, in inlense mode, and a magnification of 20,000x.

[0213] Grain analysis

[0214] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite and specification 18 / 22 pages 22 CN 122270013 AITO / NiOx / Me-4PACZ / perovskite was analyzed using a Carl Zeiss field emission scanning electron microscope at a scanning voltage of 2 kV, in inlense mode, and magnification of 20,000x. Grain size was statistically analyzed using Nano Measurer software.

[0215] Figure 6

[0216] Transient absorption spectra of quenching rate

[0217] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. Transient absorption spectra were measured under ambient conditions using an electro-optical delay line on a pump probe system (Helios, an ultrafast system) with a maximum time delay of approximately 8 ns. A 400 nm pump pulse was provided by an ultrafast optical parametric amplifier excited by a regenerative amplifier, which seeded a mode-locked Ti:sapphire oscillator and was pumped by an LBO laser.

[0218] Time-Resolved PL Spectroscopy

[0219] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. Time-resolved PL was measured using a HORIBA Fluorolog time-correlated single-photon counting system with a photomultiplier tube detector. Light was irradiated from the top surface of the perovskite film. A green laser diode (λ = 450 nm) was used as the excitation source, with an excitation power density of 5 mW / cm2, a slit width of 2 nm, and a collection timescale of 400 ns.

[0220] Adhesion Test (including Figure 9)

[0221] Adhesion and delamination classification followed ASTM D3359. The thin film samples consisted of a multilayer structure: the control group had a structure of glass / ITO / NiOx / SAM / perovskite / PMMA / epoxy resin / glass (where SAM was Me-4PACZ), and the target group had a structure of glass / ITO / NiOx / SAM / CSV / perovskite / PMMA / epoxy resin / glass (where SAM was Me-4PACZ). A cross-shading pattern (1 mm²) was created on the perovskite film surface using a precise cutting tool, with the cut penetrating the perovskite layer down to the SAM layer. The adhesive epoxy resin was then firmly applied to the cross-section under pressure to ensure tight contact between the epoxy resin and the multilayer structure of the film. By applying a constant force (F), the perovskite film gradually delaminated from the SAM-coated ITO glass. Based on the observed retention in the cross-section, the film adhesion was classified from 0B to 5B, where 5B indicates no adhesion loss and 0B indicates complete delamination.

[0222] Scanning electron microscope

[0223] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite andITO / NiOx / Me-4PACZ / perovskite was analyzed using a Carl Zeiss field emission scanning electron microscope at a scanning voltage of 2 kV in inlense mode at a magnification of 50,000x.

[0224] Figure 7

[0225] Ultraviolet photoelectron spectroscopy

[0226] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The perovskite film was peeled off from the substrate using UV-curable adhesive, and the exposed bottom interface was tested. UPS testing was performed using the AXIS SUPRA+ photoelectron spectroscopy model from Thermo Fisher Scientific. The results were obtained using a He vacuum ultraviolet (VUV) discharge lamp with copper attenuation holes to limit VUV intensity and surface charging. All scans were performed under He1α (21.22 eV) excitation and a constant pass energy of 5 eV, with an electron takeoff angle of 0°, a sampling depth of 1–10 nm, and a scanning area of ​​500 × 500 μm². During the measurement, the exposure time of the sample was only 15 minutes. Au was used as a reference.

[0227] Figure 8

[0228] Conduction band bottom estimated based on Tauc curves of UV-vis absorption spectra

[0229] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The UV-Vis absorption spectra were measured by QE Pro (Marine Optics), and the integration time was 100 ms. According to the Tauc formula (αhv)^m=hv–Eg, where α is the absorption coefficient, hv is the photon energy, Eg is the band gap width, and m is an exponent related to the band gap type of the material (for direct band gap transitions, m=1 / 2, for indirect band gap transitions, m=2). By plotting the experimental data into a Tauc diagram and analyzing the slope and intercept of its linear part, the optical band gap width of the material can be calculated. From the UPS test, the valence band top can be obtained: EVB=21.22-(Ecutoff–Eonset); the conduction band bottom ECB-EVB=Eg is used to calculate the value of the conduction band bottom.

[0230] Figure 10

[0231] Scanning electron microscope

[0232] The samples prepared in Example 1 and Comparative Example 1 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The thin films were broken for cross-sectional testing. A Carl Zeiss field emission scanning electron microscope was used, with a scanning voltage of 2kV, in inlense mode, and a magnification of 50,000x.

[0233] Figure 11

[0234] Performance parameters of inverted perovskite solar cells obtained using CSV solutions of different concentrations

[0235] Samples were prepared using the method described in Example 1. The sample structure was ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag. A series of samples were prepared using CSV solutions of different concentrations (CSV solution concentrations were 0 mg / mL, 4 mg / mL, 5 mg / mL, 8 mg / mL, and 20 mg / mL, respectively). Under air conditions of 25°C and humidity below 30%, a simulated single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one-solar AM 1.5G illumination) was used. The source meter was a Keithley 2400, and the reverse scan rate was 200mV / s (voltage step size of 20mV, no delay time). The typical effective area of ​​the PSC was 0.09cm2. The device parameters of 20 batteries were statistically analyzed and presented as a box plot.

[0236] Figure 12

[0237] Current density-voltage (J-V) curve measurement experiment

[0238] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Under air conditions of 25°C and humidity below 30%, a simulated single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one-solar AM 1.5G illumination) was used. The source meter was Keithley 2400, and the scanning rate in both the reverse and forward directions was 200mV / s (voltage step size of 20mV, no delay time). The typical effective area of ​​a PSC is 0.09 cm².

[0239] Fill factor determination test

[0240] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Under air conditions of 25°C and humidity below 30%, the intensity of one solar AM 1.5G illumination was calibrated using a simulated single-solar AM 1.5G 100mW / cm² (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell). The source meter is Keithley.2400, reverse scan rate of 200mV / s (voltage step size of 20mV, no delay). Typical effective area of ​​PSC is 0.09cm². Collect device fill factor.

[0241] Photoelectric Conversion Efficiency Measurement Test

[0242] The samples prepared in Example 1 and Comparative Example 1 had the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Under air conditions of 25°C and humidity below 30%, a simulated single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell) was used to calibrate the intensity of one-solar AM 1.5G illumination. The source meter was a Keithley 2400, page 20 / 22 of the specification, CN 122270013 A, with a reverse scan rate of 200mV / s (voltage step size of 20mV, no delay time). The typical effective area of ​​the PSC was 0.09cm2.

[0243] Maximum Power Point Tracking Stability Test

[0244] The samples prepared in Example 1 and Comparative Example 1 had the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. The SPO was measured by tracking the current at a fixed voltage determined by the voltage at the maximum power point of the J-V curve. Here, the fixed voltage of the control group device was 0.983V; the fixed voltage of the target group device was 1.041V.

[0245] Thermal Stability Test

[0246] The devices used for stability testing were manufactured using Example 1 and Comparative Example 1. The sample structures are ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. For better testing, ALD-SnO2 was used for internal encapsulation, and UV-cured adhesive (UV-cured sealant, triple bond 3035B) was used for external encapsulation through a combination of glass-to-glass encapsulation technology and edge sealing.

[0247] To evaluate the device stability under the ISOS-T-1 protocol, the encapsulated battery was placed in ambient air at 25°C and 30% humidity and heated to 85°C for testing. Every 48 hours, the battery was removed and calibrated using a simulated single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell).The recording device performance was achieved using a Keithley 2400 source meter with a scan rate of 200 mV / s (voltage step size of 20 mV, no delay time) at an intensity of 1.5 G illumination.

[0248] Figure 13

[0249] VOC Statistics

[0250] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Under air conditions of 25°C and humidity below 30%, a single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell) was used to calibrate the intensity of one-solar AM 1.5G illumination. The source meter was a Keithley 2400, and the reverse scan rate was 200mV / s (voltage step size of 20mV, no delay time). The typical effective area of ​​the PSC is 0.09cm2. Box plots were made of the VOC of the devices under different conditions.

[0251] JSC Statistics

[0252] The samples prepared in Example 1 and Comparative Example 1 had the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Under air conditions of 25°C and humidity below 30%, a simulated single-solar AM 1.5G 100mW / cm2 (Oriel Sol3A AAA grade, Newport, National Renewable Energy Laboratory certified silicon reference cell) was used to calibrate the intensity of one-solar AM 1.5G illumination. The source meter was a Keithley 2400, and the reverse scan rate was 200mV / s (voltage step size 20mV, no delay). The typical effective area of ​​the PSC was 0.09cm2. Box plots were generated for the JSC of the devices under different conditions.

[0253] Figure 14

[0254] External Quantum Efficiency Measurement Experiment

[0255] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / Perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / Perovskite / PDI2 / C60 / SnO2 / Ag, respectively. The EQE was calculated and measured using an Enlitech (Taiwan) certified incident photon to current conversion efficiency device. Spectral calibration was performed using a standard Si cell with a collection range of 300-900 nm, a step size of 5 nm, and an AC frequency of 210 Hz.

[0256] Figure 15 Specification 21 / 22 pages 25 CN122270013 A

[0257] Figure 15a: Mott-Schottky test - built-in field voltage measurement

[0258] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. Capacitance was measured using an impedance spectrometer (potentiostat / galvanostat, Autolab BV, Switzerland) with a scanning frequency of 1MHz to 1Hz (10mV AC voltage). The capacitance voltage was monitored by varying the voltage from -0.2V to 1.2V while maintaining the frequency at 1kHz. The vertical axis represents capacitance, the horizontal axis represents voltage, and the intersection of the tangents of the curves represents the built-in electric field voltage of the device.

[0259] Figure 15b: EQE measurement of electroluminescence

[0260] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. The EQE was calculated using an Enlitech (Taiwan) certified incident photon to current conversion efficiency device. The standard Si cell was used for spectral calibration. The collection range was 300-900 nm, the step size was 5 nm, and the AC frequency was 210 Hz.

[0261] Figure 16

[0262] SCLC test - space-confined current test

[0263] The sample structures are ITO / NiOx / Me-4PACZ / CSV / perovskite / Spiro-OMeTAD / Ag and ITO / NiOx / Me-4PACZ / perovskite / Spiro-OMeTAD / Ag (except for Spiro-OMeTAD, the preparation methods of the other layers are the same as in Example 1 or Comparative Example 1, and the thickness of the Spiro-OMeTAD layer is 50nm); under dark conditions, the source meter is Keithley2400, the test range is -0.3V to 5V, the reverse scan rate is 353mV / s, and there is no delay time.

[0264] Figure 17

[0265] Ideal Factor Test

[0266] The samples prepared in Example 1 and Comparative Example 1 have the following structures: ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively; under air conditions of 25°C and humidity below 30%, a simulated single-solar AM 1.5G 100mW / cm2 was used, along with Oriel Sol3A AAA grade, Newport News, and other domestic testing equipment.The silicon reference cell, certified by a National Renewable Energy Laboratory, was calibrated using a shading plate to reflect solar intensity at 1.18, 5, 10.5, 15.5, 38, 53, and 100 times the intensity of solar illumination. The source meter was a Keithley 2400 with a reverse scan rate of 200 mV / s (voltage step size of 20 mV, no delay). Instruction manual, page 22 / 22; Figure 1 (CN 122270013 A); Figure 2 (CN 122270013 A); Figure 3 (CN 122270013 A); Figure 4 (CN 122270013 A); Figure 3 (CN 122270013 A); Figure 5 (CN 122270013 A); Figure 4 (CN 122270013 A); Figure 6 (CN 122270013 A); Figure 7 (CN 122270013 A); Figure 8 (CN 122270013 A); Figure 9 (CN 122270013 A); Figure 10 (CN 122270013 A); Figure 11 (CN 122270013 A); Figure 11 (CN 122270013 A); Figure 12 (CN 122270013 A); Figure 11 (CN 122270013 A); Figure 12 (CN 122270013 A); Figure 11 (CN 122270013 A); Figure 12 (CN 122270013 A); Figure 13 (CN 122270013 A); Figure 14 (CN 122270013 A); Figure 15 (CN 122270013 A); Figure 10 (CN 122270013 A); Figure 11 (CN 122270013 A); Figure 15 ...6 (CN 122270013 A); Figure 17 ( Figure 12, Figure 13, Figure 14, Figure 15, Figure 16, Figure 17, Figure 18, Figure 19, Figure 10, Figure 10, Figure 15, Figure 16, Figure 17, Figure 18, Figure 19, Figure 10, Figure 10, Figure 11, Figure 15, Figure 16, Figure 19, Figure 10 ...substrate using crystal solvates prior to applying the perovskite precursor solution to the substrate; the crystal solvates are represented by the general formula AxPbX4·yDMSO, where A is selected from the following cations: ethylenediamine, butanediamine, heptanediamine, phenethylamine, piperazine, N,N'-dimethylethylenediamine, N- methylethylenediamine, N,N,N',N'- tetramethyl ethylenediamine, N,N,N'- trimethylethylenediamine, N, N-dimethylethylenediamine; X is selected from I⁻, Br⁻, Cl⁻; x is 1~2; y is 1~3. The PSC of the invention achieves a power conversion efficiencies (PCEs) of 26.13% and a fill factor (FF) of 86.75%; after 1,000 hours maximum power point tracking, it maintains 93% of its initial PCE, and after 900 hours isothermal heating at 85°C, it maintains 85% of its initial PCE.

Claims

1. A method for preparing an inverted perovskite solar cell, characterized in that: Before applying a perovskite precursor solution to the substrate, a crystallizing solvate is used to seed crystals on the substrate to obtain a substrate on which a crystallizing solvate layer is formed; wherein the general formula of the crystallizing solvate is A. x PbX4·yDMSO, wherein A comprises one or more of the following groups: ethylenediamine cation, butanediamine cation, heptamethamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation; X is selected from I. - ,Br - and Cl - One or more of the group; x is 1-2; y is 1-3; DMSO is dimethyl sulfoxide.

2. The method according to claim 1, wherein the substrate is a self-assembled monolayer or a hole transport layer.

3. The method according to claim 1, comprising the following steps: 1) Provides self-assembled single-layer; 2) Seed crystals are grown on the self-assembled monolayer using the crystallizing solvate to obtain a self-assembled monolayer on which a crystallizing solvate crystal layer is formed; 3) A perovskite layer is formed on the self-assembled monolayer on which the crystalline solvate crystal layer is formed.

4. The method according to claim 2 or 3, wherein the self-assembled monolayer comprises one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 2-(3,6-dimethoxycarbazole-9-yl)ethylphosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, (4-(9H-dibenzo[a,c]carbazole-9-yl)butyl)phosphonic acid, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid, (2-(pyrene-1-yl)ethyl)phosphonic acid, and (4-(3,6-diphenyl-9H-carbazole-9-yl)butyl)phosphonic acid.

5. The method according to claim 1, wherein the thickness of the crystalline solvate crystal layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystalline solvate crystal layer is 1-20 nm.

6. The method according to claim 1, wherein the seed crystal comprises: A solution of the crystalline solvate is applied to the substrate; as well as Perform annealing; The annealing temperature is from room temperature to 200°C, and the time is 2-30 minutes.

7. The method of claim 6, wherein the annealing is performed in an inert atmosphere or in ambient air with a humidity of not more than 80%.

8. The method according to claim 6, wherein the concentration of the solution of the crystalline solvate is 1-60 mg / mL, and the solvent of the solution is selected from: dimethyl sulfoxide, N',N-dimethylformamide and N-methylpyrrolidone.

9. The method of claim 6, wherein the solution of the crystalline solvate is applied to the substrate by spin coating; preferably, the spin coating is performed at 1000-5000 rpm for 10-30 seconds; or the solution of the crystalline solvate is applied to the substrate by slot coating, blade coating or spray coating.

10. The method according to claim 1, wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H 12 ) 2+ .

11. The method according to claim 1, wherein the crystallized solvate crystal layer has an orthorhombic, monoclinic, or tetragonal crystal structure.

12. The method of claim 3, wherein step 3) of forming the perovskite layer comprises: The perovskite precursor solution is applied to the self-assembled monolayer on which the crystallized solvate crystal layer is formed; Add an antisolvent dropwise to the perovskite precursor solution; preferably, the antisolvent is added 0-50 seconds after the application of the perovskite precursor solution; and Annealing is performed; the annealing temperature is from room temperature to 350°C, and the time is 5-50 minutes; preferably, the annealing is performed in an inert atmosphere or in ambient air with a humidity of not more than 80%.

13. The method according to claim 1 or 12, wherein the concentration of the perovskite precursor solution is 0.5-1.7 mol / L, and the solvent of the solution is selected from: N',N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, ethanol, and water.

14. The method of claim 12, wherein the antisolvent is selected from ethyl acetate, chlorobenzene, diethyl ether, methyl acetate, anisole, and isopropanol; and The perovskite precursor solution is applied to the self-assembled monolayer on which the crystalline solvate crystal layer is formed by spin coating; preferably, the spin coating is performed at 1000-5000 rpm for 10-50 seconds.

15. The method according to claim 3, wherein the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs. + and Cs + With Ru + K + Na + Li + Dimethylamine ion (DMA) + ), formamidinium ion (FA) + ), Methylamine ion (MA + One or more combinations of ) ; B is selected from Pb 2+ Sn 2+ And their combinations; X is selected from I - ,Br - Cl - One or more combinations thereof; preferably, the thickness of the perovskite layer is 200-1000 nm.

16. A perovskite film composition comprising a perovskite layer and a self-assembled monolayer, wherein a crystalline solvate crystal layer formed of a crystalline solvate is present between the perovskite layer and the self-assembled monolayer, wherein the crystalline solvate has the general formula A. x PbX4·yDMSO, wherein A comprises one or more of the following groups: ethylenediamine cation, butanediamine cation, heptaminediamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation, and X is selected from I. - ,Br - and Cl - One or more of the groups, where x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide.

17. The perovskite film composition according to claim 16, wherein the thickness of the crystalline solvate crystal layer is 1-100 nm and is discontinuous; preferably, the thickness of the crystalline solvate crystal layer is 1-20 nm.

18. The perovskite film composition according to claim 16, wherein the crystalline solvate crystal layer has an orthorhombic, monoclinic, or tetragonal crystal structure.

19. The perovskite film composition according to claim 16, wherein the perovskite layer has the general formula A'BX3, wherein A' is selected from Cs. + and Cs + With Ru + K + Na + Li + Dimethylamine ion (DMA) + ), formamidinium ion (FA) + ), Methylamine ion (MA + One or more combinations of ) ; B is selected from Pb 2+ Sn 2+ And their combinations; X is selected from I - ,Br - Cl - One or more combinations thereof; preferably, the thickness of the perovskite layer is 200-1000 nm.

20. The use of the perovskite film composition according to any one of claims 16-19 in the preparation of inverted perovskite solar cells.

21. An inverted perovskite solar cell prepared by the method according to any one of claims 1-15.

22. The inverted perovskite solar cell of claim 21, comprising a transparent conductive substrate, optionally a hole transport layer, a perovskite film composition according to any one of claims 16-19, optionally a passivation layer, an electron transport layer, a blocking layer, and an electrode layer, stacked sequentially.

23. The inverted perovskite solar cell according to claim 22, wherein... The transparent conductive substrate is selected from ITO glass and FTO glass, and the thickness of the transparent conductive substrate is 50-200nm; The hole transport layer comprises one or more of NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene) (P3HT), and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and the thickness of the hole transport layer is 1-20 nm. The passivation layer comprises piperazine bisiodide or piperazine hydroiodide, and the thickness of the passivation layer is 1-10 nm; The electron transport layer comprises C60 or [6,6]-phenyl-C61-butyrate methyl ester (PCBM), and the thickness of the electron transport layer is 20-50 nm; The barrier layer comprises SnO2, (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)(BCP) or LiF, and the thickness of the barrier layer is 3-30 nm. The electrode layer comprises one or more of silver, ITO, copper, and gold, and the thickness of the electrode layer is 60-200 nm.

24. An electrical device comprising an inverted perovskite solar cell according to any one of claims 21-23.

25. A crystalline solvate, wherein the general formula of the crystalline solvate is A x PbX4·yDMSO, wherein A comprises one or more of the following groups: ethylenediamine cation, butanediamine cation, heptaminediamine cation, phenylethylamine cation, piperazine cation, N,N'-dimethylethylenediamine cation, N-methylethylenediamine cation, N,N,N',N'-tetramethylethylenediamine cation, N,N,N'-trimethylethylenediamine cation, and N,N-dimethylethylenediamine cation, and X is selected from I. - ,Br - and Cl - One or more of the groups, where x is 1-2, y is 1-3, and DMSO is dimethyl sulfoxide.

26. The crystalline solvate according to claim 25, wherein the crystalline solvate is PDPbI4·DMSO, wherein PD = (C4N2H 12 ) 2+ .

27. The application of the crystalline solvate according to claim 25 or 26 in the preparation of inverted perovskite solar cells.

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