Transitional perovskite solar cell and preparation method thereof, perovskite film composition, crystalline solvate, electrical device, and application thereof

Abstract

This invention provides an inverted perovskite solar cell, its fabrication method, a perovskite film composition, a crystallizing solvate, an electrical device, and its applications. The method includes: seeding crystals on a substrate with a crystallizing solvate before applying a perovskite precursor solution; the general formula of the crystallizing solvate is A. x PbX4·yDMSO, where A is a cation selected from 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.

Description

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 Technology

[0002] In recent years, the power conversion efficiency (PCE) of inverted pin perovskite solar cells (PSCs) has rapidly increased, demonstrating enormous commercial potential. These advances are attributed to effective strategies for tuning interface defects in inverted PSCs. While grain boundaries within the perovskite film bulk have been proven crucial, heterojunctions on the top (n) and bottom (p) sides of the perovskite film also play a significant role in inverted PSCs. Early research focused primarily on modifying the top (n) side heterojunction to significantly improve the photovoltaic performance and stability of PSCs. Later, increasing attention was paid to the bottom (p) heterojunction; however, the bottom heterojunction is relatively difficult to customize because it is buried beneath the perovskite film bulk.

[0003] Currently, existing trans-PSCs employ a so-called self-assembled monolayer (SAM) as the hole transport layer (HTL), such as [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz). Customizing the intrinsic molecular chemistry of the SAM can modulate perovskite crystallization and interface formation, thereby improving PSC performance and stability. However, these SAMs remain relatively hydrophobic due to the presence of dangling benzene rings after formation on transparent conductive oxides. This poses problems for the diffusion and wetting of the perovskite precursor solution over large areas. 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 inevitably form at the bottom of the perovskite film, 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, customizing the bottom of the perovskite film in pin devices using the molecular additive pre-masking method commonly used in nip devices becomes impractical. In this regard, during the fabrication of inverted pin devices, it is difficult to access those prominent surface nanogrooves located at the grain boundaries and intragranular regions at the bottom of the perovskite film, thus limiting the microstructure design for optimal device performance and stability. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention utilizes low-dimensional halide crystallized solvate (CSV) seed crystals to regulate the crystallization and bottom surface structure of perovskite films. CSV is highly effective in promoting heterogeneous nucleation and accelerating crystallization of perovskite, thereby achieving a dense microstructure of grains at the bottom of the perovskite film. 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 passivating agent 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 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 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.

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

[0009] (3) The method according to (1) includes the following steps:

[0010] 1) Provides self-assembled single-layer;

[0011] 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;

[0012] 3) A perovskite layer is formed on the self-assembled monolayer on which the crystalline 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), wherein the seed crystal comprises:

[0016] Applying a solution of the crystalline solvate to the substrate; and

[0017] Annealing is performed; the annealing temperature is from room temperature to 200°C, and the time is 2-30 minutes.

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

[0019] (8) According to the method of (6), 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.

[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 spray coating.

[0021] (10) According to the method of (1), wherein the crystalline solvate is PDPbI4·DMSO, wherein PD=(C4N2H 12 ) 2+ .

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

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

[0024] The perovskite precursor solution is applied to the self-assembled monolayer on which the crystallized solvate crystal layer is formed;

[0025] 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

[0026] 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%.

[0027] (13) The method according to (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.

[0028] (14) The method according to (12), wherein 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 crystalline solvate crystal 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 a general compositional formula of 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.

[0031] (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.

[0032] (17) The perovskite film composition according to (16), wherein 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.

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

[0034] (19) The perovskite film composition according to (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.

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

[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 inverted 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 50-200nm;

[0040] 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.

[0041] The passivation layer comprises 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 inverted perovskite solar cell according to any one of (21)-(23).

[0046] (25) A crystalline solvate, wherein the general formula of the crystalline solvate is A xPbX4·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.

[0047] (26) The crystalline solvate according to (25), wherein the crystalline solvate is PDPbI4·DMSO, wherein PD=(C4N2H 12 ) 2+ .

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

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

[0050] 1. The method for preparing inverted perovskite solar cells according to the present invention solves the key problems of 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 crystallized solvate is initiated in an unprecedented manner, while eliminating morphological and electronic defects at the interface.

[0051] 2. The method for preparing an inverted perovskite solar cell according to the present invention allows for the burial of low-dimensional halides at the bottom of the perovskite film, which can alter the interfacial energy and is beneficial to hole dynamics.

[0052] 3. The present invention can simultaneously improve the microstructure and electronic properties of perovskite films, 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 this invention can mitigate the chemical and mechanical instability of the bottom interface of the trans PSC, thereby improving the operational and thermal stability of the PSC device. This is related to improvements in microstructure and electronic properties. The PSC device of this invention retains 93% of its initial PCE after 1000 hours of maximum power point tracking under sunlight irradiation, and retains 85% of its initial PCE after 900 hours of isothermal heating at 85°C, exhibiting excellent light and thermal stability.

[0054] 5. The method of the present invention is suitable for the scalable fabrication of PSC devices, in an area of ​​49.91 × cm 2 A PCE of 23.15% was achieved in the slot-coated perovskite solar cell module, showing only a small efficiency reduction as the device area was scaled up.

[0055] 6. Based on the method of this 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 bottom interface of buried films in 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. Attached Figure Description

[0056] Figure 1 The formation process and characterization results of a CSV crystal layer according to one embodiment of the present invention are shown. Figure 1 a shows a schematic diagram of the CSV seeding method; Figure 1 b shows a scanning electron microscope (SEM) image of a CSV crystal layer spin-coated onto SAM and annealed, with the inset showing the morphology of the rod-shaped nanocrystals; Figure 1 c compares the contact angles of SAM (top image) and SAM with a CSV crystal layer formed on it (bottom image); Figure 1 d. X-ray diffraction (XRD) results of CSV crystal powder (blue curve) and CSV crystal layer of the present invention (yellow curve) were compared; Figure 1 Figure e shows the in-situ UV-Vis absorption spectrum tracking results of the perovskite film after thermal annealing at 100℃; the lower figure shows the results of the perovskite film formed on SAM with a CSV crystal layer formed thereon, and the upper figure shows the results of the perovskite film formed directly on SAM.

[0057] Figure 2 The absorbance of the perovskite film formed after 100°C thermal annealing on SAM (control group) and SAM (target group) with CSV crystal layer formed thereon is shown as a function of annealing time.

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

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

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

[0061] Figure 6 The perovskite films of the present invention exhibit excellent charge transport, chemical, and mechanical properties. Figure 6 a (control group) and Figure 6 b (target group) is the transient absorption spectrum showing the quenching rate of the perovskite film; Figure 6 c represents the time-resolved PL spectra (TRPL) of the perovskite films in the control group and the target group; Figure 6 Figure d shows a comparison of the band arrangement diagrams at the bottom interface of the perovskite film in the control group; Figure 6 e shows a comparison of the band arrangement diagrams at the bottom interface of the perovskite films 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 6 g shows a photograph of a sample where the adhesion of the control group perovskite film was 1B and the adhesion of the target group perovskite film was 4B. Figure 6 h shows cross-sectional SEM images of the perovskite films in the control and target groups after 100 hours of continuous irradiation.

[0062] Figure 7 The ultraviolet photoelectron spectra (UPS) of the top and bottom surfaces of the perovskite film are shown. Figure 7 a and Figure 7 b represents the UPS on the top surface of the perovskite film; Figure 7 c and Figure 7 d represents the UPS of the bottom surface of the perovskite film.

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

[0064] Figure 9 Photographs of perovskite films from the control and target groups are shown in the adhesion test samples.

[0065] Figure 10 Representative cross-sectional SEM images of the device structures of an inverted perovskite solar cell (control group) excluding the CSV crystal layer and an inverted perovskite solar cell (target group) according to the present invention are shown.

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

[0067] Figure 12 The best-performing PSC performance is shown for the control group (without CSV seeding) and the target group (with CSV seeding). Figure 12 a shows the open-circuit voltage (V) OC ) to short-circuit current density (J SC The current density-voltage (JV) curves of the scan are shown, with the inset showing the steady-state output photoelectric conversion efficiency (SPOPCE) as a function of time; Figure 12 b shows the PCE statistics of PSC in the control group and the target group (n=30); Figure 12 c shows the FF statistics of PSC in the control group and the target group (n=30); Figure 12 d shows the results of the maximum power point tracking stability test; Figure 12 e shows the thermal stability test results of PSC; Figure 12 f shows an area of ​​49.91 cm². 2 JV curves and performance parameters of the perovskite solar cell device according to the present invention; Figure 12 g compares the efficiency changes of the perovskite solar cell of the present invention with those of existing perovskite solar cells with photoelectric conversion efficiencies exceeding 24% in the cross-scale fabrication from cell to module. The references Ref23-28 mentioned in the figure are as follows:

[0068] Ref.23: Huang, Y. et al. Finite perovskite hierarchical structures vialigand 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 electrontransporters for efficient perovskite solar cells.Science 375,302-306(2022);

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

[0073] Ref.28:Bu,T.et al.Modulating crystal growth of formamidinium–caesiumperovskites for over 200cm 2 Photovoltaic sub-modules. Nat. Energy 7,528-536(2022).

[0074] Figure 13 The performance statistics of PSC for the control group (without CSV seeding) and the target group (with CSV seeding) are shown (n=30). Figure 13 a shows V OC Statistical results; Figure 13 b shows J SC The statistical results.

[0075] Figure 14 The external quantum efficiency (EQE) spectra and integrated current densities of the inverted perovskite solar cells of the control and target groups are shown.

[0076] Figure 15 The performance measurement results of the PSC devices in the control group and the target group are shown. Figure 15 a shows the determination of the built-in field voltage (V) using the Mott-Schottky curve. bi ); Figure 15 b shows the electroluminescent EQE, with an inset of a graph of electroluminescence (EL) intensity versus wavelength and a photograph of the PSC device.

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

[0078] Figure 17 The relationship between the open-circuit voltage and light intensity of the PSC of the control group (without CSV seeding) and the target group (with CSV seeding) under different light intensities is shown. Detailed Implementation

[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 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.

[0081] In one embodiment, the substrate may be a self-assembled monolayer. The self-assembled monolayer may include one or more of [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 self-assembled monolayer may replace the hole transport layer, 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 implementations, the substrate may be a hole transport layer, that is, the crystallized solvate crystal layer may be formed directly on the hole transport layer.

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

[0085] 1) Provides self-assembled single-layer;

[0086] 2) Seeding crystals are performed on the self-assembled monolayer using a crystalline solvate to obtain a self-assembled monolayer with a crystalline solvate crystal layer formed on it;

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

[0088] In some embodiments, the seed crystal includes: applying a solution of a crystallizing solvate to a substrate; and annealing. Preferably, the annealing temperature is from room temperature to 200°C, and the annealing time is 2-30 minutes. 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 5 mg / mL. The solvent for the solution may 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, or other methods.

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

[0092] In some preferred embodiments, the crystalline solvate is PDPbI4·DMSO, wherein PD is a piperazine cation, and PD = (C4N2H) 12 ) 2+ .

[0093] Based on single-crystal X-ray diffraction (XRD) analysis, it can be determined that the crystallized solvate 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 crystallized solvate is PDPbI4·DMSO, where PD=(C4N2H 12) 2+ When the crystallization solvate has an orthorhombic crystal structure, the crystal layer of the solvate is P2PbI4·2DMSO, where P is a piperazine cation and P = (C4N2H 11 ) + At that time, the crystal layer of the crystalline solvate 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 onto a self-assembled monolayer on which a crystalline solvate crystal layer has been 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 minutes. Even 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 for 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] A perovskite precursor solution can be applied to a self-assembled monolayer having a crystalline solvate layer formed by spin coating. 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, where 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 - and one or more 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 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.

[0103] In some embodiments, the thickness of the crystallized solvate layer can be 1-100 nm. Preferably, the thickness of the crystallized solvate layer is 1-20 nm. The crystallized solvate layer is discontinuous.

[0104] In some embodiments, the crystallization solvate may be PDPbI4·DMSO, wherein PD is a piperazine cation and PD = (C4N2H 12 ) 2+ The crystal layers of a crystalline solvate can have an orthorhombic crystal structure.

[0105] In some embodiments, the crystallization solvate may be P2PbI4·2DMSO, wherein P is a piperazine cation and P = (C4N2H 11 ) + The crystal layers of a crystalline solvate can have a monoclinic crystal structure.

[0106] Preferably, the perovskite layer has the general formula A'BX3, where 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 - and one or more combinations thereof.

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

[0108] 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.

[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 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.

[0111] In some embodiments, the crystallization solvate according to the invention is PDPbI4·DMSO, wherein PD is a piperazine cation, and PD = (C4N2H 12 ) 2+ .

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

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

[0114] Figure 1 Figure a 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 crystallization solvate is PDPbI4·DMSO. In the CSV, Pb-I6 octahedra are arranged in a zigzag structure with shared vertices, spaced along the c-axis by PDI2 and DMSO. To prepare a CSV crystalline thin layer on Me-4PACz SAM, it is simply 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 1 Image b shows a scanning electron microscope (SEM) image of a CSV crystal layer spin-coated onto SAM, revealing that the spin-coated CSV crystal layer consists of uniformly distributed rod-shaped nanocrystals. Specifically, Figure 1 The inset (SEM image) in b shows the morphology of the rod-shaped nanocrystals.

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

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

[0117] Figure 1Figure e shows the in-situ UV-Vis absorption spectrum tracking of the perovskite film after thermal annealing at 100°C; the lower figure shows the results of the perovskite film formed on SAM with a CSV crystal layer formed thereon, and the upper figure shows the results of the perovskite film formed directly on SAM. Figure 1 e is a 2D contour plot showing the absorption characteristics at all wavelengths as a function of annealing time. Studies have found that the CSV seeding method of this invention generally accelerates perovskite crystallization. Light-absorbing perovskite is formed much faster on SAMs with a CSV crystal layer on them than on SAMs.

[0118] Figure 2 The absorbance at 750 nm of the perovskite films formed after 100°C thermal annealing on SAM (control group) and SAM with a CSV crystal layer formed thereon (target group) is further shown as a function of annealing time. 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 bottom of the film induced by the CSV seed crystals of the nanostructure.

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

[0120] Figure 4 The perovskite films of the target group and the control group, as well as the microstructure details of the bottom of their respective films, are shown. Figure 4 a and Figure 4 b shows cross-sectional SEM images of the perovskite films in the control group and the target group, respectively. Figure 4 c and Figure 4 Figure d shows top-view SEM images of the bottom of the aforementioned perovskite film after flipping and peeling. It can be observed that, in the absence of CSV seed crystals (control group), the bottom of the perovskite film includes numerous nanoscale voids, primarily located at grain boundaries. Void formation at the bottom of perovskite films is a commonly observed complex problem, related to inhomogeneous wetting and crystallization behavior. These buried nanoscale voids generated during crystallization inevitably hinder grain growth and coarsening, thus limiting grain growth. However, the method of the present invention, through improved solution wetting and annealing with crystallization solvates, enables the grains in the target group of perovskite films to form a dense microstructure and grow throughout the film thickness.

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

[0122] In addition to interfacial voids, buried grain boundary trenches also exist at the bottom of the perovskite film; this is an inherent characteristic of polycrystalline materials and can have a significant impact on PSC. Therefore, these grain boundary trenches were examined using atomic force microscopy (AFM). Figure 4 Image e shows atomic force microscopy (AFM) images of grain boundary trenches at the bottom grain boundary regions of the perovskite films in the control and target groups. It can be seen that the bottom of the perovskite film in the target group tends to be shallower at the grain boundary regions. Figure 4 As shown in f, the grain boundary trenches at the bottom of the perovskite film in the control group were 23.9°, while the grain boundary trenches at the bottom of the perovskite film in the target group were shallower, at 7.8°.

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

[0124] The perovskite film according to the present invention exhibits 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. Figure 6 a (control group) and Figure 6 As shown in b (target group), the perovskite films in the target group exhibit a faster quenching rate, reflecting faster carrier transport from perovskite to SAM. Figure 6 c 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 decay, indicating that the target group perovskite film has improved hole extraction capability.

[0125] Figure 7The ultraviolet photoelectron spectroscopy (UPS) of the top (perovskite layer side) and bottom (SAM side) surfaces of the perovskite film is shown. The valence band maximum (VBM) at the bottom of the target group perovskite film shifts upward, meaning the energy level at the bottom VBM is higher than that at the surface. This promotes interfacial band alignment, thereby facilitating efficient hole extraction.

[0126] Figure 8 The conduction band minimum (CBM) estimated based on Tauc curves from UV-vis absorption spectra is shown. The shallow CBM at the bottom of the perovskite film can establish an electronic barrier, hindering 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's perovskite film shifts towards lower binding energies (towards lower values), indicating a deeper work function at the bottom of the perovskite film, consistent with KPFM results.

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

[0128] The bottom heterogeneous interface of the perovskite film according to the present invention also has excellent mechanical properties. Adhesion tests (cross-section tests) were performed on six control group perovskite films and six target group perovskite films, respectively. The adhesion was graded based on the retention in the cross-section area, with six levels (0B, 1B, 2B, 3B, 4B and 5B) as defined by ASTM D3359, where 0B is the lowest adhesion, indicating complete removal; and 5B is the highest adhesion, indicating no adhesion loss. Figure 9 Photographs of perovskite films from the control and target groups after adhesion tests are shown. Statistical results are presented below. Figure 6 In the experimental group, the adhesion of the perovskite layer was rated 4B, while the control group was rated 0B, indicating that the perovskite film of the present invention has stronger adhesion than the control group. 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 heterointerface in the control and target groups was compared using SEM images of the perovskite film cross-sections under the same irradiation stress. Figure 6As shown in h, 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, with no 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, in sequence, a transparent conductive substrate, optionally a hole transport layer, the perovskite film composition of the present invention, optionally a passivation layer, an electron transport layer, a barrier layer, and an electrode layer. The barrier layer is also referred to as a "buffer layer".

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

[0133] The transparent conductive substrate for the inverted perovskite solar cell can be selected from ITO glass and FTO glass. The thickness of the transparent conductive substrate can be 50-200 nm. The hole transport layer can 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 can be 1-20 nm. The passivation layer can include piperazine bisiodide (PDI2) and piperazine hydroiodide. The thickness of the passivation layer can be 1-10 nm. The electron transport layer can include C60 and methyl [6,6]-phenyl-C61-butyrate (PCBM). The thickness of the electron transport layer can be 20-50 nm. The blocking layer can include SnO2, (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) (BCP), and LiF. The thickness of the barrier layer can be 3-30 nm. The electrode layer can 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 one specific embodiment, the inverse perovskite solar cell of the present invention comprises ITO glass / NiO stacked sequentially. x Layer / Me-4PACz SAM layer / CSV crystal layer / Perovskite layer / Passivation layer / C60 layer / SnO2 layer / Ag. Figure 10Representative cross-sectional SEM images of the device structures of an inverted perovskite solar cell (excluding the CSV crystal layer, other layers are the same, control group) and the inverted perovskite solar cell of the present invention (target group) are shown. By varying 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 20 mg / mL, respectively), based on the obtained device performance parameters, the preferred solution concentration of the CSV is a 5 mg / mL N,N-dimethylformamide (DMF) solution. Figure 11 ).

[0135] Figure 12 The performance of the best-performing PSC is shown in the above-mentioned inverted perovskite solar cell control group (without CSV seeding) and target group (with CSV seeding). Figure 12 As shown in Figure a, the open-circuit voltage (V) of the target group PSC OC The voltage is 1.17V, and the short-circuit current density (J) is... SC The value is 25.78 mA / cm. 2 ; Figure 12 b shows that the photoelectric conversion efficiency (PCE) of the target group PSC is 26.13%; and Figure 12 c 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%, V OC 1.15V, J SC 25.78 mA / cm 2 It also has a moderate FF of 83.73%. The most significant improvement is the FF, which is likely related to the reduction in series resistance and the increase in shunt resistance in the PSC device of this invention.

[0136] like Figure 12 As shown in the illustration of figure a, under sunlight illumination 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% for the control group PSC device. This is consistent with the JV measurement results. SC In comparison, the target group of PSC devices has a current density of 25.31 mA / cm² integrated from the external quantum efficiency (EQE) spectrum. 2 ( Figure 14 ).

[0137] To further understand the improvement of PSC devices through CSV seeding, the built-in field voltage (V) was measured using Mott-Schottky curves. bi ).like Figure 15 As shown in figure a, the V of the target group PSC device bi The voltage is 1.09V, which is higher than the voltage of the control group PSC device.bi (1.06V), which allows for more efficient separation of photogenerated charge carriers in the target group of PSC devices. This is also related to the high V of the target group of PSC devices. OC Consistent. Furthermore, for the target group of PSC devices, a steeper slope can be observed, indicating a reduction in charge accumulation at the PSC device interface.

[0138] In one implementation, for both the target group and the control group (without the CSV crystal layer), the Ag / 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD) / perovskite / CSV crystal layer / SAM / NiO crystal layer was also detected. x The space charge-limited current (SCLC) of hole-only PSC devices was used to test hole transport. For example... Figure 16 As shown, by measuring the trap filling voltage (V) TFL The calculated trap density of the target group of PSC devices is 1.26 × 10⁻⁶. 15 cm -3 The trap density of the control group PSC device was 1.90 × 10⁻⁶. 15 cm -3 This is also reflected in the ideal factor (n) id The value changed from 1.76 to 1.49 after CSV seeding. Figure 17 For the reasons mentioned above, CSV seeding enables PSC devices to operate close to J. SC The EQE of electroluminescence at the injection level was increased by 80%. Figure 15 b), thus demonstrating that the target group of PSC devices has improved interfacial carrier dynamics.

[0139] The PSC device of the present invention also exhibits excellent operational and thermal stability. Under continuous maximum power point tracking (MPPT) exposure for one day (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 continuous maximum power point tracking (MPPT) exposure for one day (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 a CSV crystal layer) can only maintain 71.3% of the initial PCE after 1000 hours. Figure 12 d). In the thermal stability test, the packaged PSC device is subjected to a temperature of 85°C in the ambient environment. For example... Figure 12 As shown in e, after 970 hours, the target group PSC devices maintained 84.2% of their initial PCE, while the control group PSC devices maintained 75.9% of their initial PCE.

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

[0141] In one embodiment, an inverted perovskite solar cell module is prepared using slit coating and based on the crystallization solvent synthesis method of the present invention. Figure 12 f shows an area of ​​49.91 cm². 2 The battery module according to the present invention, based on FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO, achieves a PCE of 23.15%, indicating only a small efficiency reduction when the device area is scaled up. Figure 12 g).

[0142] The following examples further explain or illustrate the content of the present invention, but these examples should not be construed as limiting the scope of protection of the present invention.

[0143] Example

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

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

[0146] ITO glass (8Ωsq) -1 ) respectively with detergent ( 12BASIC), deionized water, and ethanol were continuously sonicated for 30 minutes each. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg NiO was added. x 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 sonicated for 30 minutes before use. Then, 70 μL of NiO was added at 4000 rpm for 25 s. x The dispersion was spin-coated onto treated ITO glass and annealed at 140°C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, a 50 μL methanol solution of Me-4PACZ (TCI product, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.) (purchased from Sigma) was spin-coated onto the prepared NiOx hole transport layer at 3000 rpm for 25 s, followed by annealing at 100°C for 10 minutes to form a self-assembled monolayer of approximately 2 nm.

[0147] Next, in a nitrogen glove box, 50 μL of a 5 mg / mL crystalline solvate (PDPbI₄·DMSO, where PD = (C₄N₂H₂O)) was added. 12 ) 2+ A DMF solution of piperazine cations was spin-coated onto a Me-4PACZ self-assembled monolayer at 3000 rpm for 25 s and annealed at 100 °C for 2 minutes to form a 10 nm crystalline solvate layer. The preparation process of the crystalline solvate is as follows: 1 M of PDI2 and PbI2 were dissolved in DMSO, stirred overnight at room temperature, and then allowed to stand. The supernatant was taken into a 4 mL vial, and then the vial was placed openly into a 20 mL bottle. 3 mL of tetrahydrofuran was added to the bottle, the bottle cap was tightened, and the bottle was allowed to stand for 5 days to obtain the crystalline solvate.

[0148] In a nitrogen glove box, Cs was stirred for 8 hours. 0.05 (MA 0.05 FA 0.95 ) 0.95 A 50 μL solution of PbI3 perovskite precursor (1.5 mol / L, DMF:DMSO = 4:1 (v / v), both DMF and DMSO purchased from Sigma) was spin-coated onto the prepared crystalline solvate layer at 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate was added dropwise 20 s after the start of spin-coating. Annealing was performed 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 / 25 s to form a passivation layer of approximately 2 nm. Then, [further details omitted]. A 25nm C60 (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) electron transport layer was deposited on top via thermal evaporation. After depositing C60 at 100°C, an ALD-SnO2 (Sn source: TDMASn, purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source: purified water from Wahaha) barrier layer (approximately 15nm thick) was deposited. Finally, with... A silver electrode layer with a thickness of 100 nm is thermally evaporated at a rate of [missing information].

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

[0150] The perovskite films and PSC devices described in the accompanying drawings and related descriptions are all prepared by the method of Example 1.

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

[0152] ITO glass (8Ωsq) -1 The substrate was subjected to continuous ultrasonic treatment for 30 minutes each with detergent, deionized water, and ethanol. 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.]) chlorobenzene (purchased from Sigma) solution was spin-coated onto the prepared substrate at 3000 rpm for 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, 8 mg / mL of the crystallization solvate (PDPbI4·DMSO, where PD = (C4N2H)) was added. 12 ) 2+ 60 μL of a DMF solution of piperazine cation was spin-coated onto PTAA at 3000 rpm for 25 s and annealed at 100 °C for 2 minutes to obtain a crystalline solvate layer with a thickness of approximately 20 nm.

[0154] In a nitrogen glove box, Cs was stirred for 8 hours. 0.05 (MA 0.1 FA 0.9 ) 0.95 A 60 μL solution of PbI3 perovskite precursor (1.5 mol / L, DMF:DMSO = 4:1 (v / v)) was spin-coated onto the prepared crystalline solvate layer 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 min to obtain a perovskite layer with a thickness of approximately 800 nm. In a nitrogen glove box, a 60 μL solution of PI (piperazine hydroiodide) (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 / 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 Yu Ri Solar Energy Technology Co., Ltd.) solution of chlorobenzene (purchased from Sigma) was spin-coated on top of the passivation layer at 1500 rpm / 25 s to form an electron transport layer with a thickness of approximately 30 nm. A 0.5 mg / mL BCP (purchased from Xi'an Yu Ri Solar Energy Technology Co., Ltd.) solution of isopropanol (purchased from Sigma) was then spin-coated at 5000 rpm / 25 s to form a buffer layer with a thickness of approximately 5 nm. Finally, with... A silver electrode layer with a thickness of 100 nm is thermally evaporated at a rate of [missing information].

[0155] The annealing steps in the above preparation process that are not specified to be performed in a nitrogen glove box are all carried out in ambient air with a humidity of no more than 80%.

[0156] Example 3. Fabrication of the PSC device of the present invention

[0157] ITO glass (8Ωsq) -1 The ITO glass substrate was subjected to continuous ultrasonic treatment for 30 minutes each with detergent, deionized water, and ethanol. The cleaned ITO glass substrate was then treated with ultraviolet ozone for 15 minutes, followed by NiO treatment. x To form a hole transport layer, a spin-coating process was performed at 4000 rpm for 30 s, followed by annealing at 140°C for 10 minutes to create a hole transport layer with a thickness of approximately 10 nm. This substrate was then transferred to a glove box under a nitrogen atmosphere, where a SAM layer (Me-4PACZ) was spin-coated onto the NiO substrate at 3000 rpm for 30 s. x The SAM layer was annealed on a hot plate at 100°C for 10 minutes, and the thickness of the SAM layer was approximately 2nm.

[0158] In a nitrogen glove box, 5 mg / mL of the crystalline solvate C4N2H was added. 14 A 60 μL solution of PbBr4·DMSO (with N,N-dimethylethylenediamine cation as the organic cation) was spin-coated onto a SAM layer at 3000 rpm for 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 crystalline solvate DMF solution is as follows: 1 M of C4N2H... 14 Br2 and PbBr2 were dissolved in DMSO and stirred overnight at room temperature. After standing, the supernatant was collected into a 4 mL vial. The vial was then placed open into a 20 mL bottle, and 3 mL of tetrahydrofuran was added to the bottle. The bottle cap was tightened, and the mixture was allowed to stand for 5 days to obtain a crystalline solvate. Then, 5 mg of the crystalline solvate was weighed and dissolved in DMF.

[0159] In a nitrogen glove box, Cs was stirred for 8 hours. 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 A 60 μL solution of the perovskite precursor (1.5 mol / L, DMF:DMSO = 4:1 (v / v)) was spin-coated onto the prepared crystalline solvate layer at 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate was added dropwise 20 s after the spin-coating began. The resulting perovskite film was then annealed 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 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 sequentially deposited 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 performed in a nitrogen glove box are all carried out in ambient air with a humidity of no more than 80%.

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

[0163] FTO glass (8Ωsq) -1 The ITO glass substrate was subjected to continuous ultrasonic treatment for 30 minutes each with detergent, deionized water, and ethanol. The cleaned ITO glass substrate was then treated with ultraviolet ozone for 15 minutes, followed by NiO treatment. x To form a hole transport layer, a spin-coating process was performed at 4000 rpm for 30 s, followed by annealing at 140 °C for 10 minutes to achieve a hole transport layer with a thickness of approximately 10 nm. This substrate was then transferred to a glove box under a nitrogen atmosphere, where a methanol solution of Me-4PACZ was spin-coated onto NiO at 3000 rpm for 30 s. x On the hole transport layer, annealing was performed on a hot stage 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, 5 mg / mL of the crystallization solvate PDPbCl4·DMSO (where PD = (C4N2H)) was added. 12 ) 2+ A 60 μL solution of (piperazine cation) in DMF was spin-coated onto the self-assembled monolayer prepared above at 3000 rpm for 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 PDCl2 and PbCl2 were dissolved in DMSO and stirred overnight at room temperature. After standing, the supernatant was collected into a 4 mL vial. The vial was then placed openly into a 20 mL bottle, and 3 mL of tetrahydrofuran was added to the bottle. The bottle 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, Cs was stirred for 8 hours. 0.05 (MA 0.05 FA 0.95 ) 0.95Pb(I 0.95 Br 0.05 A 60 μL solution of the perovskite precursor (1.5 mol / L, DMF:DMSO = 4:1 (v / v)) was spin-coated onto the prepared crystalline solvate layer at 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate was added dropwise 20 s after the spin-coating began. The resulting perovskite film was then annealed 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 hydroiodate (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 sequentially deposited on the passivation layer under conventional conditions to prepare the inverse perovskite solar cell according to the present invention.

[0167] The annealing steps in the above preparation process that are not specified to be performed in a nitrogen glove box are all carried out in ambient air with a humidity of no more than 80%.

[0168] Comparative Example 1. Fabrication of PSC devices in the control group

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

[0170] ITO glass (8Ωsq) -1 The ITO glass was subjected to continuous ultrasonic treatment for 30 minutes each with detergent, deionized water, and ethanol, respectively. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg of NiO was added... x 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 IPA at a volume ratio of 3:1) and sonicated for 30 minutes before use. Then, 70 μL of NiO was added at 4000 rpm for 25 s. x The dispersion was spin-coated onto treated ITO glass and annealed at 140°C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, a 50 μL 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 for 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, Cs at a concentration of 1.5 mol / L was stirred for 8 hours. 0.05 (MA 0.05 FA 0.95 ) 0.95 50 μL of a PbI3 perovskite precursor solution (DMF:DMSO = 4:1 (v / v)) was spin-coated onto the self-assembled monolayer 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 start of spin-coating. Annealing was performed at 100 °C for 30 min 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 / 25 s to form a passivation layer of approximately 2 nm. Then, [the process was repeated - the original text is incomplete]. A 25nm C60 (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) electron transport layer was deposited on top via thermal evaporation. After depositing C60 at 100°C, an ALD-SnO2 (Sn source: TDMASn purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source: purified water from Wahaha) barrier layer (approximately 15nm thick) was deposited. Finally, with... A silver electrode layer with a thickness of 100 nm is thermally evaporated at a rate of [missing information].

[0172] The annealing steps in the above preparation process that are not specified to be performed in a nitrogen glove box are all carried out in ambient air with a humidity of no more than 80%.

[0173] The perovskite film and PSC device described in the accompanying drawings and related descriptions were prepared by the method of Comparative Example 1.

[0174] Comparative Example 2. Fabrication of PSC Devices

[0175] The PSC device was prepared using essentially 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 (8Ωsq) -1 The ITO glass was subjected to continuous ultrasonic treatment for 30 minutes each with detergent, deionized water, and ethanol, respectively. Then, before use, the cleaned ITO glass was treated with ultraviolet ozone for 15 minutes. 10 mg of NiO was added... x 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 IPA at a volume ratio of 3:1) and sonicated for 30 minutes before use. Then, 70 μL of NiO was added at 4000 rpm for 25 s. xThe dispersion was spin-coated onto treated ITO glass and annealed at 140°C for 10 minutes to form a 10 nm thick NiOx hole transport layer. In a nitrogen glove box, a 50 μL 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 for 25 s, and then annealed at 100°C for 10 minutes to form a self-assembled monolayer of approximately 2 nm.

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

[0178] In a nitrogen glove box, Cs at a concentration of 1.5 mol / L was stirred for 8 hours. 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 50 μL of a perovskite precursor solution (DMF:DMSO = 4:1 (v / v)) was spin-coated onto the prepared crystal layer at 1000 rpm / 10 s and 5000 rpm / 30 s. 300 μL of ethyl acetate was added dropwise 20 s after the start of spin-coating. 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 / 25 s to form a passivation layer of approximately 2 nm. Then, [the process was repeated - the original text is incomplete]. A 25nm C60 (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd.) electron transport layer was deposited on top via thermal evaporation. After depositing C60 at 100°C, an ALD-SnO2 (Sn source: TDMASn purchased from Hefei Andekeming Semiconductor Technology Co., Ltd. ≥6N; O source: purified water from Wahaha) barrier layer (approximately 15nm thick) was deposited. Finally, with... A silver electrode layer with a thickness of 100 nm is thermally evaporated at a rate of [missing information].

[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

[0181]

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

[0183] Based on FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO, in an area of ​​10cm×10cm 2 Solar cell modules were fabricated on an FTO substrate. A FTO / NiOx / CSV / perovskite / PCBM / SnO2 / ITO structure was prepared using a method similar to that in Example 1, with the following differences: FTO glass was used as the transparent conductive substrate; the SAM layer was not included; the perovskite thin film was prepared using 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 20W 1064nm laser (Trotec) was used to separate sub-cells for the laser marking system. The parameters were as follows: P1 line: 60% laser power, velocity 300mm / s, frequency 65kHz, pulse duration 120ns; P2 line: 15% laser power, 1000mm / s velocity, 65kHz frequency, and 120ns pulse duration; P3 line: fabricated using the same process as P2 line. The widths of P1, P2, and P3 were 40μm, 100μm, and 40μm, respectively. The total dead zone width was approximately 280μm, with a geometric fill factor of 95.7%.

[0185] The area prepared by the above method is 49.91 × cm. 2 The slot-coated perovskite solar cell module achieved 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 2 kV in inlense mode and a magnification of 20,000x.

[0190] X-ray diffraction

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

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

[0193] Contact angle test

[0194] The samples prepared in Example 1 and Comparative Example 1 had 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 10 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 using QE Pro (Marine Optics) with an integration time of 100 ms. One curve was collected every ten seconds for a total of 10 minutes. The intensity at 750 nm was plotted against time.

[0200] Figure 3

[0201] Steady-state fluorescence spectroscopy

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

[0203] Figure 4

[0204] Scanning electron microscope

[0205] 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 films were peeled off from the substrate using UV-curable adhesive, and the exposed interface was tested. A Carl Zeiss field emission scanning electron microscope was used with a scanning voltage of 2 kV in inlense mode and a magnification of 50,000x.

[0206] Atomic force microscope

[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 films were peeled off the substrate using UV-cured adhesive, and the exposed interface was tested. Atomic force imaging was performed using a Bruker multi-functional scanning probe microscope in tapping mode, using a Si cantilever of model RTESPA-300.

[0208] Laser scanning confocal microscope

[0209] 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 films were peeled off from the substrate using UV-curable adhesive, and the exposed interface was tested. Laser confocal microscopy was performed using an Olympus FV1000 CLSM system with a laser wavelength of 405 nm. The collection range for the perovskite was 700-800 nm, and the collection range for the CSV was 450-550 nm.

[0210] Figure 5

[0211] Scanning electron microscope

[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 2 kV in inlense mode and a magnification of 20,000x.

[0213] Grain analysis

[0214] 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. They were examined using a Carl Zeiss field emission scanning electron microscope at a scanning voltage of 2kV in inlense mode at a magnification of 20,000x. The 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 have 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 was seeded with a mode-locked Ti:sapphire oscillator and pumped by an LBO laser.

[0218] Time-resolved PL spectroscopy

[0219] 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. Time-resolved photon count (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. 2 The slit width is 2 nm and the collection timescale is 400 ns.

[0220] Adhesion test (including) Figure 9 )

[0221] Adhesion and delamination classification followed ASTM D3359. The film samples consisted of a multilayer structure: the control group film sample structure was glass / ITO / NiOx / SAM / perovskite / PMMA / epoxy / glass (where SAM was Me-4PACZ), and the target group film sample structure was glass / ITO / NiOx / SAM / CSV / perovskite / PMMA / epoxy / 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. Adhesive epoxy was then firmly applied to the cross-section under pressure to ensure tight contact between the epoxy 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 and ITO / NiOx / Me-4PACZ / perovskite, respectively. They were examined 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 films were peeled from the substrate using UV-curable adhesive, and the exposed interface was tested. UPS testing was performed using the AXIS SUPRA+ photoelectron spectroscopy model from Thermo Fisher Scientific. He vacuum ultraviolet (VUV) discharge lamps with copper attenuation holes were used to limit VUV intensity and surface charging. All scans were performed at He1α (21.22 eV) excitation and a constant through energy of 5 eV, with an electron take-off angle of 0°, a sampling depth of 1–10 nm, and a scan area of ​​500 × 500 μm. 2 During the measurement process, the sample was exposed for 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 have structures of ITO / NiOx / Me-4PACZ / CSV / perovskite and ITO / NiOx / Me-4PACZ / perovskite, respectively. The UV-Vis absorption spectra were measured using QE Pro (Marine Optics) with an integration time of 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 bandgap width, and m is an exponent related to the bandgap type of the material (m=1 / 2 for direct bandgap transitions and m=2 for indirect bandgap transitions), the optical bandgap width of the material can be calculated by plotting the experimental data into a Tauc plot and analyzing the slope and intercept of its linear portion. The valence band peak can be obtained from UPS measurements: E VB =21.22-(E cutoff –E onset ); Conductor band bottom E CB -E VB =E g 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 had 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 2 kV 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). The samples were tested under simulated single-solar AM 1.5G 100mW / cm² conditions at 25°C and humidity below 30%. 2(An Oriel Sol3A AAA-grade, Newport, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination) with a Keithley 2400 source meter and a reverse scan rate of 200 mV / s (voltage step size 20 mV, no delay). The typical effective area of ​​the PSC is 0.09 cm². 2 The device parameters of 20 batteries were statistically analyzed and plotted as a box plot.

[0236] Figure 12

[0237] Current density-voltage (JV) curve measurement test

[0238] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 (An Oriel Sol3A AAA-grade, Newport News, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination), source meter is Keithley 2400, with a scan rate of 200 mV / s in both reverse and forward directions (voltage step size 20 mV, no delay). The typical effective area of ​​the PSC is 0.09 cm². 2 .

[0239] Filler factor determination test

[0240] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 (An Oriel Sol3A AAA-grade, Newport News, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination), source meter is Keithley 2400, reverse scan rate is 200 mV / s (voltage step size 20 mV, no delay). Typical effective area of ​​the PSC is 0.09 cm². 2 Collect device fill factor.

[0241] Photoelectric conversion efficiency measurement test

[0242] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 (An Oriel Sol3A AAA-grade, Newport News, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination), source meter is Keithley 2400, reverse scan rate is 200 mV / s (voltage step size 20 mV, no delay). Typical effective area of ​​the PSC is 0.09 cm². 2 .

[0243] Maximum power point tracking stability test

[0244] The samples prepared in Example 1 and Comparative Example 1 had structures of ITO / NiOx / Me-4PACZ / CSV / perovskite / PDI2 / C60 / SnO2 / Ag and ITO / NiOx / Me-4PACZ / perovskite / PDI2 / C60 / SnO2 / Ag, respectively. SpO was measured by tracking the current at a fixed voltage determined by the voltage at the maximum power point on the JV curve. Here, the fixed voltage for the control group device was 0.983V; the fixed voltage for 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 were 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 then UV-curable adhesive (UV-curable sealant, triple bond 3035B) was used for outer encapsulation using a combination of glass-to-glass encapsulation technology and edge sealing.

[0247] To evaluate the device stability under the ISOS-T-1 protocol, the packaged battery was placed in ambient air at 25°C and 30% humidity and heated to 85°C for testing. The battery was removed every 48 hours and tested using a simulated single-solar AM1.5G 100mW / cm². 2(An Oriel Sol3A AAA-grade, Newport, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of a solar AM 1.5G illumination), source meter Keithley 2400, scan rate of 200 mV / s (voltage step of 20 mV, no delay) recording device performance.

[0248] Figure 13

[0249] V OC Statistics

[0250] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 (An Oriel Sol3A AAA-grade, Newport News, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination), source meter is Keithley 2400, reverse scan rate is 200 mV / s (voltage step size 20 mV, no delay). Typical effective area of ​​the PSC is 0.09 cm². 2 Statistical analysis of V values ​​for devices under different conditions. OC Create a box plot.

[0251] J SC Statistics

[0252] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 (An Oriel Sol3A AAA-grade, Newport News, National Renewable Energy Laboratory certified silicon reference cell calibrated to the intensity of one solar AM 1.5G illumination), source meter is Keithley 2400, reverse scan rate is 200 mV / s (voltage step size 20 mV, no delay). Typical effective area of ​​the PSC is 0.09 cm². 2 Statistical analysis of J values ​​for devices under different conditions. SC Create a box plot.

[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

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

[0258] The samples prepared in Example 1 and Comparative Example 1 had structures of 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 scan frequency of 1 MHz to 1 Hz (10 mV AC voltage). The capacitance voltage was monitored by varying the voltage from -0.2 V to 1.2 V while maintaining the frequency at 1 kHz. The vertical axis represents capacitance, the horizontal axis represents voltage, and the intersection of the tangent lines represents the built-in electric field voltage of the device.

[0259] Figure 15 b: 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 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.

[0261] Figure 16

[0262] SCLC Testing - Space-Confined Current Testing

[0263] The sample structures were ITO / NiOx / Me-4PACZ / CSV / perovskite / Spiro-OMeTAD / Ag and ITO / NiOx / Me-4PACZ / perovskite / Spiro-OMeTAD / Ag, respectively (except for Spiro-OMeTAD, the preparation methods of the other layers were the same as in Example 1 or Comparative Example 1, and the thickness of the Spiro-OMeTAD layer was 50 nm). Under dark conditions, the source was a Keithley 2400, the test range was -0.3 V to 5 V, the reverse scan rate was 353 mV / s, and there was no delay time.

[0264] Figure 17

[0265] Ideal Factor Test

[0266] The samples prepared in Example 1 and Comparative Example 1 have the 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-sun AM 1.5G 100mW / cm² test was performed. 2 The Oriel Sol3A AAA-grade, Newport, National Renewable Energy Laboratory certified silicon reference cell was calibrated with solar irradiance 1.18, 5, 10.5, 15.5, 38, 53, and 100 times the intensity of solar illumination using a shading device. The source meter was a Keithley 2400 with a reverse scan rate of 200 mV / s (voltage step size of 20 mV, no delay).

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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