Perovskite layer, preparation method thereof and photoelectric device

Abstract

The invention provides a perovskite layer, a preparation method thereof and a photoelectric device. The polymer embedded perovskite layer includes a cross-linked polymer matrix including a first repeating unit represented by-CH2CH2SO2CH2CH2-and a second repeating unit represented by a polyol group, and a perovskite compound represented by Formula 1: (A +) y [(A '+) 1-x (A' '+) x] 1-y (M2 +) (X-) 3, where x is a value ranging from 0 to 0.99, and y is a value ranging from 0.01 to 0.99. According to the polymer embedded perovskite layer, enhanced perovskite crystal orderliness can be realized, the perovskite surface can be effectively passivated, the mechanical property of the perovskite layer can be improved, and an effective waterproof barrier can be provided, so that the performance and the stability of the polymer embedded perovskite layer in a photovoltaic device can be enhanced.

Description

Technical Field

[0001] This disclosure relates to perovskite layers, methods for their preparation, and optoelectronic devices. Background Technology

[0002] Photovoltaic (PV) technology has shown great potential in providing clean and sustainable solutions to the global energy shortage. Attention to organic-inorganic hybrid perovskite materials has grown rapidly due to their advantageous properties, such as high carrier mobility and lifetime, tunable band gap, high absorption coefficient, and good solubility in common polar aprotic solvents. These materials are already widely used in various optoelectronic and electronic applications, including solar cells, light-emitting devices, lasers, and photodetectors. Among these, organic-inorganic halide perovskite (OIHP) based solar cells have become a leading technology in the emerging photovoltaic field.

[0003] However, the inherent stability of the perovskite layer and key interfaces remains a major challenge for the commercialization of perovskite solar cells (PSCs). This challenge stems primarily from the brittleness and ionic properties of halide perovskite materials, making them highly sensitive and reactive to their surroundings. Solution deposition of perovskite films spontaneously induces high concentrations of intrinsic defects (e.g., halide vacancies, undercoordinated lead cations) on the perovskite surface and at grain boundaries (GBs). Such defects can negatively impact device performance (especially open-circuit voltage, V0). OC Furthermore, environmental conditions (especially humidity) accelerate perovskite degradation. It is well known that precise control of perovskite formation and crystallization kinetics (nucleation and crystal growth rates), as well as various passivation strategies, are crucial for mitigating perovskite defect problems to a large extent.

[0004] Interfacial strain caused by lattice distortion in the microscopic perovskite crystal structure directly affects its photoelectric properties and also accelerates perovskite degradation. Strain engineering has been developed to further enhance device performance (e.g., VT). OC New methods for V and operational stability. To date, this field still lacks new approaches in V. OC The report indicates that 95% of the SQ limit has been met.

[0005] The soft and elastic properties of polymers are highly valuable in regulating residual strain during perovskite formation and provide inherent moisture resistance. However, polymer-based complexes tend to precipitate from the perovskite solution when incorporated in large quantities for regulation due to strong coordination interactions with the perovskite precursor. Alternative approaches include incorporating crosslinkable ligands into the perovskite precursor solution or using antisolvent techniques, as well as initiating in-situ polymerization under thermal or UV stimulation during or after perovskite film curing. To date, most related work involves the simultaneous introduction of monomers into the perovskite and the induction of spontaneous but uncontrolled polymerization, which can lead to uncertainties in the stoichiometry and colloidal size of the perovskite precursor, thereby disrupting the fine perovskite crystallization process.

[0006] There is a lack of methods to achieve precise perovskite crystallization and provide comprehensive protection for perovskites. Furthermore, there is still a need to improve power conversion efficiency (PCE) and open-circuit voltage (V). OC And minimize voltage drop in perovskite solar cells. The topics described in this paper address at least some of these unmet needs. Summary of the Invention

[0007] This disclosure provides a method for in-situ embedding of a polymer matrix during the formation of a perovskite layer, as well as a polymer-embedded perovskite layer. This polymer-embedded perovskite layer can achieve enhanced perovskite crystallization order and effectively passivate the perovskite surface, enhance the regulation of perovskite crystallization, improve the mechanical properties of the perovskite layer, and provide an effective waterproof barrier, thereby improving the performance and stability of perovskite compounds in photovoltaic devices.

[0008] In a first aspect, this document provides a polymer-intercalated perovskite layer comprising a crosslinked polymer matrix and a perovskite compound, wherein the crosslinked polymer matrix comprises a first repeating unit represented by -CH2CH2SO2CH2CH2- and a second repeating unit represented by a polyol group, and the perovskite compound is represented by Formula 1:

[0009] (A + ) y [(A' + ) 1-x (A” + ) x ] 1-y (M 2+ (X) - )3 1

[0010] Where x is a value ranging from 0 to 0.99, and y is a value ranging from 0.01 to 0.99; M 2+ It is Pb 2+ Sn 2+ Or Ge2+ ;

[0011] A + It is Cs + or Rb + ;

[0012] A' + It is H(C=NH2)NH2 + ;

[0013] A” + It is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + ;and

[0014] X - It is Cl - ,Br - or I - One or more of them.

[0015] In some embodiments, the polyol group comprises diolyl, triolyl, tetraolyl, or a mixture thereof.

[0016] In some embodiments, the polyol group comprises ethylene glycolyl, propylene glycolyl, glyceryl, trimethylolpropanyl, trimethylolethanyl, erythritolyl, pentaerythritolyl, bis-trimethylolpropanyl, diethylene glycolyl, dipropylene glycolyl, ethoxylated pentaerythritolyl, sorbitolyl, or mixtures thereof.

[0017] In some implementations, M 2+ It is Pb 2+ A + It is Cs + And A” + It is CH3NH3 + .

[0018] In some embodiments, the perovskite contains (Cs) +) y [(H(C=NH2)NH2 + ) 1-x (CH3NH3 + ) x ] 1-y (Pb 2+ )[(I - ) 1-z (Br - ) z )]3, where each of x, y and z is a value in the range of 0.01-0.99.

[0019] In some implementations, the polyol group is a glycerol group.

[0020] In some implementations, each of x and y is independently a value in the range of 0.01 to 0.1.

[0021] In some embodiments, the crosslinked polymer matrix has a weight-average molecular weight in the range of 20,000 to 140,000.

[0022] In some implementations, the molar ratio of the second repeating unit to the first repeating unit is 4 to 64:100.

[0023] In a second aspect, this document provides a method for producing the polymer-intercalated perovskite layer of the first aspect, the method comprising:

[0024] A perovskite precursor solution is provided, the solution comprising one or more metal salts, each independently represented by the formula MX2, three or more salts, each independently represented by the formula AZ, A'Z, or A”Z, divinyl sulfone (DVS), and a solvent, wherein M is Pb. 2+ Sn 2+ Or Ge 2+ A is Cs + or Rb + A' is H(C=NH2)NH2 + "A" is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + X is Cl independently in each case. - ,Br - or I - And Z is Cl independently in each case. - ,Br - or I - ;

[0025] The perovskite precursor solution is contacted with a polyol to form a crosslinking precursor solution; and

[0026] The crosslinking precursor solution is annealed to form the perovskite layer.

[0027] In some embodiments, the perovskite precursor solution contains (Cs) + (I) - ), (H(C=NH2)NH2 + (I) - (CH3NH3) + (Br) - (CH3NH3) + (Cl) - (Pb) 2+ (Br) - )2 and (Pb 2+ (I) - )2.

[0028] In some embodiments, the solvent comprises dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), N,N'-dimethylacrylurea (DMPU), or a mixture thereof.

[0029] In some embodiments, the volume ratio of divinyl sulfone to solvent is 1 to 20:100.

[0030] In some embodiments, one or more metal salts have a concentration of 0.2 M to 1.5 M in the perovskite precursor solution.

[0031] In some embodiments, the molar ratio of polyol to divinyl sulfone is 4 to 64:100.

[0032] In some embodiments, the crosslinking precursor solution is annealed at a temperature of 100-120°C.

[0033] In a third aspect, this paper provides an optoelectronic device comprising the polymer-intercalated perovskite layer described in the first aspect.

[0034] In some implementations, the optoelectronic device is a perovskite solar cell, a perovskite light-emitting diode, a perovskite laser, or a perovskite photodetector.

[0035] In some implementations, the open-circuit voltage of the perovskite solar cell is 1.162-1.347V.

[0036] In some implementations, the photoelectric conversion efficiency of perovskite solar cells is 17.78-25.98%. Attached Figure Description

[0037] The foregoing aspects and many incidental advantages of the invention will become more readily apparent and understood when taken in conjunction with the accompanying drawings and the following detailed description.

[0038] Figure 1 A schematic diagram of asynchronous crosslinking and the properties of divinyl sulfone are depicted. a) Schematic diagram of perovskite crystallization dominated by pre-intercalated DVS and intermediates protected by omnidirectional copolymerization via glycerol (gly) post-treatment. b) Schematic diagram of the selected organic solvent. 23 Linear fitting of Na NMR chemical shift and donor number (DN) was performed to calculate the DN of DVS. c represents formamidinium iodide (FAI), DVS, and FAI / DVS in DMSO-d6 solution, respectively. 1 ¹H NMR spectra. d, Formamidinium cation (FA) under different solvent conditions. + Density functional theory (DFT) calculation of adsorption energy.

[0039] Figure 2 Crystallization kinetics in intermediate complex formation and perovskite formation were depicted. MD simulations of the perovskite precursor in DMF / DMSO and DMF / DVS solvent systems were performed from the start after approximately 20 ps, ​​where iodopide polyhedra were displayed. Within the cutoff range. b, Changes in two-dimensional pseudo-color absorption intensity mapping with spin-coating time during in-situ measurements. c, Changes in pseudo-color mapping of UV-Vis absorption spectra with annealing time. d, In-situ XRD measurements of control samples and DVS-gly-based perovskite films during thermal annealing (intermediate phases indicated by # and * symbols can be attributed to FAI-DVS solvates). e, Changes in corresponding XRD spectra with annealing time. f, XRD intensity evolution of the perovskite main peak at 2θ = 14.01°.

[0040] Figure 3 Crosslinking and defect passivation are depicted. a, Fourier transform infrared (FITR) spectra of DVS solvent, as-cast DVS-based perovskite films, and the final DVS-gly-based perovskite films after annealing in selected regions. b, MALDI-TOF-MS measurements of the DVS / gly mixed solution. cd, Grazing incidence X-ray diffraction (GI-XRD) spectra of the control sample (c) and the DVS-gly-based perovskite film (d) in 2θ–sin2ψ mode in the near-surface region (50 nm depth). e, Deep XPS spectra of the DVS-gly-based perovskite film. f, TRPL decay of the control sample, DVS, and DVS-gly-based perovskite films.

[0041] Figure 4The device performance is depicted. a) JV curves of the best-performing control sample (TiO2 electron transport layer (ETL)), the control sample (TiO2 / SnO2 quantum dot ETL), and the DVS-gly-based device. b) EQE spectrum of the DVS-gly-based PSC. c) VL of the control sample (TiO2 ETL), the control sample (TiO2 / SnO2 QDs ETL), 7% DVS, and the DVS-gly-based device. OC Distribution. d, V under different bandgap conditions of PSC in the literature. OC Comparison with the work of this invention. e, EQE EL The nonradiative recombination loss was calculated by varying the injected current density. f represents the energy distribution of the trap density of the control sample and the PSC based on DVS-gly, as measured by admittance spectroscopy.

[0042] Figure 5 The water resistance and device stability of the perovskite film are depicted. a, Image of the control perovskite film. b, Image of the DVS-gly based perovskite film directly immersed in water. cd, Long-term maximum power point (MPP) tracking under elevated temperature (one standard solar intensity (1-sun), 65±5℃, 50±5% relative humidity (RH) for packaged devices: FTO / TiO2 / SnO2 / perovskite (PVSK) / PTAA / Au) and room temperature (one standard solar intensity, 30±5℃, 60±5% RH for packaged devices: FTO / TiO2 / SnO2 / PVSK / spiro-OMeTAD / Au), respectively. e, Thermal stability (darkness, 85±5℃, N2, unpackaged device: FTO / TiO2 / SnO2 / PVSK / PTAA / Au).

[0043] Figure 6 A range of common organic solvents and DVS are described. 23 Na nuclear magnetic resonance (NMR) spectrum.

[0044] Figure 7 Photographs depicting PbI2 powder dissolved in DVS (left), FAI powder dissolved in DVS (middle), and DVS solvent (right).

[0045] Figure 8 XRD patterns of FAI powder and quasi-wet films deposited by FAI / DMSO and FAI / DVS solutions, respectively, were depicted. Inset: Diffraction peaks of FAI-DVS solvates from 12° to 15°.

[0046] Figure 9 The relative permittivity of DVS is shown by cyclic calculations using DFT and MD simulations.

[0047] Figure 10 The implicit solvation model used in the DFT calculation is shown to reflect the solution environment with the corresponding solvent εr and nD values.

[0048] Figure 11 The distribution and coordination of Pb-I pairings are depicted. a, radial distribution function, and b, coordination number of Pb-I pairings in DMF / DMSO and DMF / DVS systems, respectively.

[0049] Figure 12 The evolution of UV-vis absorption intensity at 450 nm wavelength during antisolvent-assisted spin coating of control samples and DVS-based perovskite inks was depicted.

[0050] Figure 13 The evolution of in-situ UV–vis absorption intensity at 450 nm wavelength for control samples and DVS-gly-based perovskite films during thermal annealing, as well as their corresponding crystal growth rates, is depicted.

[0051] Figure 14 XRD patterns of the control sample and the DVS-based perovskite film were depicted; as well as XRD patterns of the DVS-based perovskite film at different annealing times. a, XRD patterns of the as-cast control sample and the DVS-based perovskite film (intermediate phases indicated by # and * symbols are attributable to FAI-DVS solvates); inset: intermediate phases indicated by @ are attributable to MAI-PbI2-DMSO-based solvates. b, XRD patterns of the DVS-based sample as a function of annealing time, with an annealing time interval of 4 minutes for each sample (▲ corresponds to the perovskite main peak).

[0052] Figure 15 Full and magnified FTIR spectra were depicted. a) Full FTIR spectra of the DVS solvent, the cast DVS-based perovskite film, and the final DVS-gly-based perovskite film after annealing. b) Magnified FTIR spectra in several schemes to provide a clear comparison of characteristic signals between the cast DVS-based perovskite film and the final DVS-gly-based perovskite film.

[0053] Figure 16 The nucleophile-mediated oxa-Michael addition reaction between DVS and gly was described.

[0054] Figure 17 Gel permeation chromatography (GPC) analysis shows the molecular weight distribution and cumulative percentage curves under different molar ratios of gly to DVS.

[0055] Figure 18 XRD patterns and full width at half maximum (FWHM) are shown. a) XRD patterns of the final control sample after thermal annealing, the DVS-based perovskite film, and the DVS-gly-based perovskite film. b) FWHM of the perovskite main peak at 2θ = 14.01° for the corresponding samples.

[0056] Figure 19 SEM top-view images of the control sample, the DVS-based perovskite film, and the DVS-gly-based perovskite film are shown; scale bar: 1 μm.

[0057] Figure 20 The GI-XRD spectra are shown: near-surface versus bulk. GI-XRD spectra of the DVS-gly-based perovskite film at different tilt angles are presented for the near-surface (50 nm depth, a) and bulk (200 nm depth, b) regions. Different curves correspond to tilt angles of 10°, 20°, 30°, 40°, and 50°, respectively, representing the intensity variation with 2θ at different sampling angles.

[0058] Figure 21 Steady-state PL spectra of the control sample and the DVS-gly-based perovskite film are shown.

[0059] Figure 22 The UPS results at the cutoff region are shown for the control sample, the DVS-based perovskite film, and the DVS-gly-based perovskite film.

[0060] Figure 23 JV curves with different DVS ratios and hysteresis effects are shown. a, JV curves of PSCs based on inks with different DVS volume ratios. b, Representative JV curves of devices based on DVS-gly under forward and reverse scanning conditions, respectively.

[0061] Figure 24 JV curves (molar ratio of gly to DVS, from 0 to 64 mol%) were plotted under different gly concentration conditions.

[0062] Figure 25 The certified PCE results from the photovoltaic certification laboratory (EnliTech Optoelectronic Calibration Lab., Taiwan) are displayed. The certified PCE is 24.63% - the certified aperture area is 0.067 cm². 2 .

[0063] Figure 26 The accreditation certificate of Guangyan Technology's photoelectric calibration laboratory is displayed.

[0064] Figure 27 The band gap of the perovskite film based on DVS-gly, calculated using EQE spectroscopy, is shown. g IP It can be determined by the maximum derivative of EQE.

[0065] Figure 28 JV curves for devices with different perovskite band gaps are shown. JV characteristics of the control sample and the DVS-gly based device (pin structure with different perovskite band gaps) are shown (a, 1.53 eV; b, 1.65 eV; c, 1.77 eV; d, 1.85 eV).

[0066] Figure 29 The JV curve of the DVS-gly-based micromodule (3 sub-cells, 3.6*3.6cm) is shown. 2 Substrate, active area: 5.85 cm² 2 ).

[0067] Figure 30 EQE was displayed EL and EL spectrum. a, when operating as an LED for a DVS-gly based PSC, EQE EL b, EL spectra of a representative DVS-gly-based device under bias voltage conditions from 1V to 1.5V, varying with the applied bias voltage.

[0068] Figure 31 The derived dark radiation recombination current and V are described. OC Loss analysis. a) External quantum efficiency and derived dark radiation recombination current. b) Vcomparison of control sample and DVS-gly based perovskite. OC Loss analysis.

[0069] Figure 32 Nyquist plots and impedance analysis are depicted. a) Nyquist plots of the control sample and the DVS-gly-based PSC, inset: equivalent circuit used to simulate charge transfer and recombination processes. b) Nyquist plot of the control sample in darkness at bias voltages from 0.7 to 1.0 V. c) Bias voltage versus series resistance (R) for the corresponding PSC. S The relationship between d and the composite resistance (R) for the corresponding PSC. rec The relationship between ).

[0070] Figure 33Long-term thermal stability and shelf-storage stability were depicted. a) Long-term thermal stability (darkness, 85±5℃, N2, unpackaged device: FTO / TiO2 / SnO2 / PVSK / Spiral-OMeTAD / Au). b) Shelf-storage stability (darkness, 25±5℃, 20±5% RH, unpackaged device: FTO / TiO2 / SnO2 / PVSK / Spiral-OMeTAD / Au).

[0071] Figure 34 Table 1 is described, which lists a range of common organic solvents. 23 Na NMR displacement was used to calculate the DN of the DVS.

[0072] Figure 35 Table 2 is described, which lists the FAs. + DFT calculation results of adsorption energy between different solvents.

[0073] Figure 36 Table 3 illustrates the average molecular weights of the copolymers obtained at different molar ratios of gly to DVS, as determined by gel permeation chromatography.

[0074] Figure 37 Table 4 is presented, showing the instrument angle settings (ω, ψ, φ) based on the GI-XRD from previous work.

[0075] Figure 38 Table 5 illustrates the fitting parameters of the double exponential decay function in the TRPL spectra of the corresponding perovskite films.

[0076] Figure 39 Table 6 illustrates the photovoltaic parameters of DVS-based devices under different volume ratios of DVS to DMF as the bulk solvent.

[0077] Figure 40 Table 7 illustrates the photovoltaic parameters at different molar ratios of gly versus DVS.

[0078] Figure 41 Table 8 is depicted, showing the V as reported in previous work and implemented in this work. OC Loss and nonradiative composite loss (ΔV) OC Summary of the values ​​of ,nr).

[0079] Figure 42 Table 9 illustrates the photovoltaic parameters of pin structure devices based on different perovskite compositions.

[0080] Figure 43 Table 10 is depicted, showing V OC Summary of parameters for loss analysis.

[0081] Figure 44 Table 11 illustrates the changes in photovoltaic parameters of unencapsulated devices immersed in water over time.

[0082] Figure 45 Showing Figure 3 MALDI-TOF-MS data of some segments in the DVS-gly network in b. Detailed Implementation

[0083] definition

[0084] Throughout this disclosure, unless the context otherwise requires, the words “comprise,” “comprises,” or “comprising” will be understood to imply inclusion of the whole or group of wholes, but not to exclude any other whole or group of wholes. It should also be noted that in this disclosure, particularly in the claims and / or paragraphs, terms such as “comprises,” “comprised,” and “comprising” may mean “includes,” etc.; and terms such as “consisting essentially of” or “consists essentially of” allow for elements not explicitly referenced, but exclude elements found in the prior art or affecting the essential or novel features of the invention.

[0085] Furthermore, throughout this disclosure and claims, unless the context otherwise requires, the word “include” will be understood to imply inclusion of the whole or group of wholes, but does not exclude any other whole or group of wholes.

[0086] Unless otherwise expressly stated, the singular as used herein includes the plural (and vice versa). Additionally, if the term “about” is used before a quantity value, this teaching also includes the specific quantity value itself, unless otherwise specified. As used herein, unless otherwise stated or inferred, the term “about” means a variation of ±10%, ±7%, ±5%, ±3%, ±1%, or ±0% of an index value.

[0087] As used herein, the terms “weight percent,” “wt-%,” “percent by weight,” “weight %,” and their variations refer to the concentration of a substance, calculated by dividing the weight of the substance by the total weight of the composition and multiplying by 100. It should be understood that, as used herein, “percentage,” “%,” etc., are intended to be synonymous with “weight percent,” “wt-%,” etc.

[0088] The methods and compositions disclosed herein may comprise, consist substantially of, or consist of the components and ingredients of this disclosure, as well as other ingredients described herein. As used herein, “consistently of” means that the methods and compositions may include additional steps, components, or ingredients, provided that such additional steps, components, or ingredients do not materially alter the essential and novel characteristics of the claimed methods and compositions.

[0089] As used herein, the term "polyhydric alcohol" refers to a straight-chain or branched alcohol compound in which each molecule contains two or more hydroxyl groups (e.g., 2 to 8, 3 to 5, or 3 to 4 hydroxyl groups). The number of hydroxyl groups in a polyhydric alcohol compound is a measure of the amount of potentially reactive hydroxyl groups available for reaction.

[0090] As used herein, the term "polyol" refers to a group obtained by removing a hydrogen atom from the hydroxyl group of a polyol compound. Polyol groups in this article include diol groups, triol groups, tetraol groups, etc. A polyol group can be represented by the following formula 2:

[0091] (CR1R2)mX(CR1R2)n 2

[0092] Each of m and n is an integer selected from 1, 2, 3, and 4;

[0093] X is oxygen or a chemical bond;

[0094] R1 is independently hydrogen or alkyl in each case; and

[0095] R2 is independently an oxygen radical, hydroxyl, hydrogen, or alkyl in each case, with at least two R2s being oxygen radicals.

[0096] As used herein, the term "diol group" refers to a diradical obtained by removing two hydrogen atoms from the hydroxyl group of a diol compound. Similarly, "triol group" refers to a triradical obtained by removing three hydrogen atoms from the hydroxyl group of a triol compound, and so on.

[0097] The term "perovskite solar cell" as used in this article refers to a solar cell that uses a perovskite structure material as the light-absorbing layer. When light is incident on a perovskite material, it excites electrons in the material, generating electron-hole pairs. Perovskite materials have excellent charge transport properties, allowing electrons and holes to separate and transport to the electrodes, where they can be collected into an electric current.

[0098] A typical perovskite solar cell with a normal structure consists of a transparent conductive oxide (TCO) layer, an electron transport layer (ETL), a perovskite light-absorbing layer, a hole transport layer (HTL), and a metal electrode. In a perovskite solar cell with an inverted structure, the order of the layers is reversed compared to the normal structure: the TCO layer is followed by the HTL layer, the perovskite layer, the ETL, and the metal electrode.

[0099] This disclosure provides insightful strategies for synergistically achieving fine perovskite crystallization manipulation and providing comprehensive protection at the perovskite surface and grain boundaries (GBs) during the perovskite formation process. During the fine manipulation of perovskite crystallization, DVS units in the pre-embedded polymer dominate the formamidinium (FA)-based intermediate transformation and induce three-dimensional copolymerization via nucleophilic post-treatment on the cast film. This disclosure demonstrates that the polymer scaffold not only passivates intrinsic defects at the perovskite surface and GBs but also releases residual strain in the near-surface region. Among all perovskite systems, the lowest Vg is achieved. OC This strategy achieves superior device performance by mitigating the loss of performance. It significantly improves the moisture resistance of the perovskite film and greatly enhances device stability, which could advance the commercialization of this promising PV technology.

[0100] This resulted in a maximum PCE of 25.22% (certified value 24.6%), with a maximum V... OC The voltage drop is 1.229V, corresponding to a loss of only 0.30V (for a bandgap of approximately 1.53eV, compared to the loss from EQE). EL The measured nonradiative recombination loss of only 52.5 mV is consistent with the theoretical SQ V. OC The limiting value of 97.5% is higher than all reported perovskite systems. The perovskite layer in this disclosure is universal for various perovskite compositions and device architectures, and can achieve a promising PCE of 25.98% for certain pin-structured devices. Figure 42 Table 9 (in the table). Entirely copolymerization significantly enhances the moisture resistance of perovskite films and devices, and also improves the resistance at elevated temperatures (ISOS-L-3: MPP, 65°C, 50% RH, T). 98 =1350h) and room temperature (ISOS-L-1: MPP, 60% RH, T 90 Excellent operational stability was achieved under conditions of 1800 h, as well as thermal stability in the dark (ISOS-D-2I: 85℃, N2, T). 95 =1560h).

[0101] This disclosure provides a polymer-intercalated perovskite layer comprising a crosslinked polymer matrix and a perovskite compound, wherein the crosslinked polymer matrix comprises a first repeating unit represented by -CH2CH2SO2CH2CH2- and a second repeating unit represented by a polyol group, and the perovskite compound is represented by Formula 1:

[0102] (A + ) y [(A' + ) 1-x (A” + ) x ] 1-y (M 2+ (X) - )3 1

[0103] Where x is a value ranging from 0 to 0.99, and y is a value ranging from 0.01 to 0.99;

[0104] M 2+ It is Pb 2+ Sn 2+ Or Ge 2+ ;

[0105] A + It is Cs + or Rb + ;

[0106] A' + It is H(C=NH2)NH2 + ;

[0107] A” + It is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + ;and

[0108] X - It is Cl - ,Br - or I - One or more of them.

[0109] In some implementations, M 2+ It is Pb 2+ A + It is Cs + And A” + It is CH3NH3 + .

[0110] In some embodiments, the perovskite contains (Cs) + ) y [(H(C=NH2)NH2 +) 1-x (CH3NH3 + ) x ] 1-y (Pb 2+ )[(I - ) 1-z (Br - ) z )]3, where each of x, y and z is an independent value ranging from 0.01 to 0.99.

[0111] In some embodiments, the perovskite compound contains Cs 0.03 (FA 0.97 MA 0.03 ) 0.97 Pb(I 0.97 Br 0.03 3. Cs 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 3. Cs 0.35 FA 0.65 PbI 0.8 Br 0.2 Cs 0.2 FA 0.8 PbI 0.7 Br 0.3 Cs 0.2 FA 0.8 PbI 0.5 Br 0.5 Or any mixture thereof.

[0112] In some implementations, x is a value ranging from 0 to 0.50 or from 0.01 to 0.1. In some implementations, x is 0.01, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 0.99.

[0113] In some implementations, y is a value ranging from 0.01 to 0.50 or from 0.01 to 0.1. In some implementations, y is 0.01, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 0.99.

[0114] In some implementations, z is a value ranging from 0 to 0.99, 0 to 0.5, or 0.01 to 0.1. In some implementations, z is 0.01, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 0.99.

[0115] In some embodiments, the polyol group comprises a diol group, a triol group, a tetraol group, or a mixture thereof.

[0116] In some embodiments, the polyol group comprises ethylene glycol, propylene glycol, glycerol, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, bis(trimethylolpropane), diethylene glycol, dipropylene glycol, ethoxylated pentaerythritol, sorbitol, or mixtures thereof.

[0117] In some embodiments, the crosslinked polymer matrix has a weight-average molecular weight in the range of 20,000 to 140,000. In some embodiments, the crosslinked polymer matrix has the following weight-average molecular weights: 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 105,000, 110,000, 115,000, 120,000, 125,000, 130,000, 135,000, or 140,000, or any value or range therebetween.

[0118] In some embodiments, the crosslinked polymer matrix has a number average molecular weight in the range of 10,000 to 125,000. In some embodiments, the crosslinked polymer matrix has the following number average molecular weights: 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 105,000, 110,000, 115,000, or 120,000, or any value or range therebetween.

[0119] In some embodiments, the crosslinked polymer matrix has a polydispersity index of 1.10-1.80, for example, the polydispersity index is 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, 1.70 or 1.75, or any value or range therebetween.

[0120] In some embodiments, the molar ratio of the second repeating unit to the first repeating unit is 4-64:100. In some embodiments, the molar ratio of the second repeating unit to the first repeating unit is 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, or 60:100, or any value or range thereof.

[0121] In some embodiments, the perovskite grains have an average size in the range of 50-900 nm, 100-500 nm, or 300-500 nm. In some embodiments, the perovskite compound grains have the following sizes: 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, or any value or range therebetween.

[0122] This disclosure further provides a method for producing a polymer-intercalated perovskite layer, the method comprising:

[0123] A perovskite precursor solution is provided, the solution comprising one or more metal salts, each independently represented by the formula MX2, three or more salts, each independently represented by the formula AZ, A'Z, or A”Z, divinyl sulfone, and a solvent, wherein M is Pb. 2+ Sn 2+ Or Ge 2+ A is Cs + or Rb + A' is H(C=NH2)NH2 + "A" is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + X is Cl independently in each case. - ,Br - or I - And Z is Cl independently in each case. - ,Br - or I - ;

[0124] The perovskite precursor solution is contacted with a polyol to form a crosslinking precursor solution; and

[0125] The crosslinking precursor solution is annealed to form the perovskite layer.

[0126] Depending on the stoichiometry of the polyols and reagents used and the choice of reaction conditions, the reaction product of polyols and divinyl sulfones (polyol groups) may include a portion of the reaction product containing unreacted alcohols.

[0127] In the above method, the perovskite precursor solution is first coated onto a surface to obtain a perovskite precursor film (semi-wet film). Then, the surface of the perovskite precursor film is treated with a polyol solution to ensure sufficient contact between the pre-embedded crosslinking initiator divinyl sulfone and the polyol. In the subsequent annealing process, the polyol-treated perovskite precursor film is crystallized to form the perovskite layer, and simultaneously, a polymer matrix is ​​in situ embedded in the perovskite layer.

[0128] In some embodiments, the perovskite precursor solution contains (Cs) + (I) - ), (H(C=NH2)NH2 + (I) - (CH3NH3) + (Cl) - (Pb) 2+ (Br) - )2、(Pb 2+ (I) - )2 or a mixture thereof.

[0129] In some embodiments, the solvent comprises dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), N,N'-dimethylacrylurea (DMPU), or a mixture thereof.

[0130] The selection and combination of these solvents can be optimized based on the specific perovskite composition and preparation process to achieve optimal film or layer quality and device performance. In some embodiments, the solvent comprises dimethylformamide (DMF) or is composed of DMF.

[0131] In some embodiments, the volume ratio of divinyl sulfone to solvent (e.g., DMF) is 1-20:100. In some embodiments, the volume ratio of divinyl sulfone to solvent is 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, 15:100, 16:100, 17:100, 18:100, 19:100, or any value or range thereof.

[0132] In some embodiments, each of the one or more metal salts independently has a concentration of 0.2 M to 1.5 M in the perovskite precursor solution. In some embodiments, each of the one or more metal salts independently has a concentration in the perovskite precursor solution of 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1.0 M, 1.1 M, 1.2 M, 1.3 M, or 1.4 M, or any value or range therebetween. In some embodiments, the one or more metal salts have a concentration of 0.2625 M to 1.47 M in the perovskite precursor solution.

[0133] In some embodiments, each of AZ, A'Z, or A”Z independently has a concentration in the perovskite precursor solution ranging from 0.01 to 1.5 M. In some embodiments, each of AZ, A'Z, or A”Z independently has a concentration in the perovskite precursor solution of: 0.02 M, 0.04 M, 0.06 M, 0.08 M, 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1.0 M, 1.1 M, 1.2 M, 1.3 M, or 1.4 M, or any value or range thereof. In some embodiments, each of AZ, A'Z, or A”Z independently has a concentration in the perovskite precursor solution ranging from 0.04 to 1.41 M.

[0134] In some embodiments, the molar ratio of polyol to divinyl sulfone is 4-64:100. In some embodiments, the molar ratio of polyol to divinyl sulfone is 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, or 60:100, or any range thereof.

[0135] In some embodiments, the method further includes depositing a crosslinking precursor solution onto a surface to form a semi-wet film; and annealing the semi-wet film to form the perovskite layer. In some embodiments, the crosslinking precursor solution can be deposited by methods such as spin coating, blade coating, spray coating, slot-die coating, inkjet printing, and vapor deposition. In some embodiments, the crosslinking precursor solution is deposited by spin coating.

[0136] Annealing the crosslinking precursor solution or the semi-wet membrane of the perovskite precursor can significantly affect the membrane quality and device performance. Optimal annealing conditions may vary depending on the specific perovskite composition and the desired characteristics of the membrane or layer. In some embodiments, the crosslinking precursor solution or semi-wet membrane is annealed at the following temperatures: 100-120°C, such as 100°C, 102°C, 104°C, 105°C, 106°C, 108°C, 110°C, 112°C, 114°C, 115°C, 116°C, 118°C, or 120°C, or any value or range thereof.

[0137] In some embodiments, the crosslinking precursor solution or semi-wet film is annealed for a period of 5-80 min or 10-60 min. In some embodiments, the crosslinking precursor solution or semi-wet film is annealed for the following time periods: 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, or 55 min, or any value or range thereof.

[0138] In some embodiments, the method for producing the perovskite layer includes:

[0139] Provide a perovskite precursor solution, the solution comprising (Cs) + (I) - ), (H(C=NH2)NH2 + (I) - (CH3NH3) + (Br) - (CH3NH3) + (Cl) - (Pb) 2+ (Br) - )2、(Pb 2+ (I) - 2. Divinyl sulfone and DMF;

[0140] The perovskite precursor solution is contacted with glycerol to form a crosslinking precursor solution; and

[0141] The crosslinking precursor solution is annealed to form the perovskite layer.

[0142] Depending on the processes and conditions used to produce the perovskite layers, perovskite particles can form monolayer or multilayer structures. For example, monolayer perovskite compound films with large grain sizes can be prepared by using a slot coating process and controlling a specific precursor solution. Monolayer structures are more suitable for reducing grain boundary defects and optimizing carrier transport pathways, especially in large-area fabrication. The formation of multilayer structures is closely related to crystallization kinetics, the stability of the precursor solution, and the solvent evaporation rate during the preparation process. For example, inconsistent crystallization rates between the upper and lower layers can lead to grain stacking in the multilayer. The efficiency of multilayer structures can also be improved by optimizing the combination of perovskite layers with different band gaps.

[0143] In some embodiments, perovskite grains form a monolayer within the perovskite compound film. In other embodiments, perovskite grains form multiple layers within the perovskite compound film.

[0144] This disclosure further provides optoelectronic devices comprising a perovskite layer. These optoelectronic devices include perovskite solar cells (PSCs), perovskite light-emitting diodes (LEDs), perovskite lasers, and perovskite photodetectors.

[0145] In some embodiments, a perovskite solar cell may have a normal structure comprising a transparent or semi-transparent conductive substrate, an electron transport layer, a perovskite compound film or layer as described above, a hole transport layer, and a metal electrode deposited in sequence. In some embodiments, a perovskite solar cell may have an inverted structure comprising a transparent or semi-transparent conductive substrate, a hole transport layer, a perovskite compound film or layer as described above, an electron transport layer, and a metal electrode deposited in sequence.

[0146] Transparent or translucent conductive substrates can be pre-cleaned in solvents such as isopropanol, acetone, and water using ultrasonic cleaning. The substrates can also be surface-activated by UV light treatment.

[0147] The transparent conductive oxide in the conductive substrate is selected from: indium tin oxide (ITO), zinc oxide, doped tin oxide and doped zinc oxide, such as fluorine-doped tin oxide (FTO) or aluminum-doped tin oxide (AZO), etc.

[0148] In some embodiments, the transparent conductive oxide may comprise 90 wt% to 100 wt% of ITO, FTO, or AZO. In some embodiments, the transparent conductive oxide may consist primarily of ITO, FTO, or AZO. In some embodiments, the transparent conductive oxide is ITO.

[0149] In some embodiments, the thickness of the perovskite compound film or layer is from 100 nm to 1000 nm, such as 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or 1000 nm.

[0150] The materials used to form the electron transport layer and hole transport layer can be those commonly used in perovskite solar cells. In some embodiments, the electron transport layer can be formed from materials selected from: titanium dioxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), zinc tin oxide (Zn2SnO4), [6,6]-phenyl-C 61 methyl butyrate (PCBM), perylene diimide (PDI). In some embodiments, the hole transport layer may be formed of materials selected from: 2,2',7,7'-tetratetra(N,N-di-p-methoxyaniline)-9,9'-spirodifluorene (spirocyclic-OMeTAD), poly(triarylamine) (PTAA), poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT:PSS), poly(3-hexylthiophene-2,5-diyl) (P3HT), nickel oxide (NiO). x Copper thiocyanate (I) (CuSCN), 6,13-bis(triisopropylsilylethynyl)pentabenzene (TIPS-pentabenzene) and copper phthalocyanine (CuPc).

[0151] In some embodiments, the perovskite solar cell includes an interface adhesive layer between the perovskite compound film or layer and the charge transport layer (electron transport layer or hole transport layer). The interface adhesive may be selected from (3-iodopropyl)trimethoxysilane (Si(OCH3)3(CH2)3I), potassium tetrafluoroborate (KBF4), trifluoromethanesulfonamide (CF3SO2NH2), aminopropyltriethoxysilane (H2NCH2CH2CH2Si(OC2H5)3), polyhexamethylene guanidine hydrochloride, and 5,6-isopropylpyridine-L-ascorbic acid.

[0152] In this disclosure, asynchronous incorporation of crosslinkable agents (e.g., DVS and Gly) triggers controlled copolymerization at the perovskite surface and GB. Figure 1 a) In the following embodiments, a novel crosslinking initiator, DVS, is first pre-embedded in the perovskite precursor solution. Furthermore, as a cosolvent with low coordination ability (low donor number), DVS facilitates intermediate-dominant perovskite crystallization operations through a favorable FAI-DVS-based solvate transition, while maintaining the kinetic balance between perovskite nucleation and crystal growth, thus providing a high-quality perovskite film or layer with low defect density. More importantly, the pre-embedded crosslinking initiator triggers three-dimensional copolymerization on the cast perovskite film via a post-treated nucleophile, gly, to form a controllable large network structure. The resulting copolymer scaffold not only effectively passivates intrinsic defects on the perovskite surface and at GB, but also releases residual tensile strain in the near-surface region.

[0153] Example

[0154] raw material

[0155] The following chemicals and solvents were used without further purification: lead iodide (PbI2) (Sigma-Aldrich, 99.99%), lead(II) bromide (PbBr2) (Sigma-Aldrich, 99.999%), formamidinium hydroiodide (FAI) (Greatcell Energy), methylammonium bromide (MABr) (Greatcell Energy), and methylammonium chloride (MACl). All solvents were purchased from Sigma-Aldrich, including divinyl sulfone (containing 400-600 hydroquinone as an inhibitor, ≥6%), dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF) (99.8%, anhydrous).

[0156] Fabrication of devices with perovskite layers

[0157] Example 1

[0158] This embodiment involves Cs 0.03 (FA 0.97 MA 0.03 ) 0.97 Pb(I 0.97 Br 0.03 Fabrication of basic devices based on the original perovskite layer of 3.

[0159] FTO / glass substrates with laser patterns (film resistance ≈ 12 Ω / sq.) were cleaned in detergent, distilled water, acetone, and isopropanol, respectively. The FTO glass was immersed in a TiCl4 solution at 70°C for 60 minutes to produce TiO2 via a chemical bath deposition process. The FTO substrate was then repeatedly cleaned with distilled water and ethanol and dried at 200°C for 30 minutes. After a 20-minute UV-ozone treatment, a thin coating of the self-produced SnO2 solution was spin-coated onto the previous TiO2 layer at 4000 rpm for 30 seconds. It was then annealed at 200°C for 60 minutes in ambient atmosphere.

[0160] A mixed powder of FAI (1.41 M), MABr (0.04 M), MACl (0.4 M), PbBr2 (0.04 M), and PbI2 (1.47 M) in DMF / DMSO (4:1, v:v) was combined with 29 μL of CsI (1.5 M, in DMSO) stock solution to generate Cs 0.03 (FA 0.97 MA 0.03 ) 0.97 Pb(I 0.97 Br 0.03 3. Perovskite precursor solution (band gap = 1.53 eV).

[0161] The precursor solution was stirred overnight at room temperature and then filtered before use. 50 μL of the precursor solution was dropped onto the SnO2 ETL surface prepared above. Spin coating was used to deposit a perovskite film. Spin coating is a method of producing a film by distributing a liquid solution onto a substrate and then spinning at high speed, allowing the liquid to diffuse and leaving a uniform layer as the solvent evaporates. Three spin coating speeds were used in three different stages: 1000 rpm for the first 5 seconds to ensure uniform coverage of the substrate, 3000 rpm for the next 5 seconds, and a final 5000 rpm for the last 30 seconds to minimize the thickness of the wet precursor film. In the final 10 seconds, 200 μL of toluene was dropped onto the substrate in 1 second. The deposited layer was immediately annealed on a hot plate at 120°C for 60 min. Thermal annealing is a method of evaporating residual solvent in the cast perovskite precursor film (semi-wet film) and promoting the crystallization of the cast perovskite film. The first step is to set the heating plate to the desired temperature, and then place the deposited layer on the heating plate for the desired time period.

[0162] The sample with the deposited layer was transferred to a glove box and spin-coated with BABr (2 mg / mL, IPA) and spirocyclic-OMeTAD (80 mg / mL in CB, 29 μL tBP, and 17.5 μL Li-TFSI stock solution), respectively, followed by annealing at 100 °C for 10 min. An 80 nm thick Au electrode was then patterned by thermal evaporation on top of the device using a shadow mask.

[0163] Example 2

[0164] This embodiment involves Cs 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 Fabrication of basic devices based on the original perovskite layer of 3.

[0165] The manufacturing procedure is similar to that described in Example 1, except that the perovskite precursor solution is prepared as follows. A mixed powder of FAI (1.40 M), MABr (0.04 M), MACl (0.4 M), PbBr2 (0.04 M), and PbI2 (1.47 M) in DMF / DMSO (4:1, v:v) is combined with 50 μL of a CsI (1.5 M, in DMSO) stock solution to produce CsI. 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 3. Perovskite precursor solution (band gap = 1.53 eV).

[0166] Examples 3-5

[0167] These embodiments relate to the fabrication of basic devices with additional original perovskite layers.

[0168] The manufacturing process is similar to that described in Example 1, except that the perovskite precursor solution is prepared as follows.

[0169] A mixed powder of CsI (0.525 M), FAI (0.975 M), PbI2 (1.05 M), and PbBr2 (0.45 M) was dissolved in 1 mL of a mixed DMF / DMSO solvent (vol / vol, 4:1) to produce Cs 0.35 FA 0.65 (PbI 0.8 Br 0.2 3. Perovskite precursor solution (band gap = 1.65 eV) (Example 3).

[0170] A mixed powder of CsI (0.24 M), FAI (0.96 M), PbI2 (0.66 M), and PbBr2 (0.54 M) was dissolved in 1 ml of a mixed DMF / DMSO solvent (vol / vol, 4:1) to produce Cs 0.2 FA 0.8 (PbI 0.7 Br 0.3 3. Perovskite precursor solution (band gap = 1.77 eV) (Example 4).

[0171] A mixed powder of CsI (0.21 M), FAI (0.84 M), PbI2 (0.2625 M), and PbBr2 (0.7875 M) was dissolved in 1 ml of a mixed DMF / DMSO solvent (vol / vol, 4:1) to produce Cs 0.2 FA 0.8 (PbI 0.5 Br 0.5 3. Perovskite precursor solution (band gap = 1.85 eV) (Example 5).

[0172] Example 6

[0173] This embodiment relates to the fabrication of a target device according to the present invention having a divinyl sulfone (DVS)-based perovskite layer. The main fabrication process is similar to that described in Example 1, except that the perovskite precursor solution is prepared as follows.

[0174] A mixed powder of FAI (1.41 M), MABr (0.04 M), MACl (0.4 M), PbBr2 (0.04 M), and PbI2 (1.47 M) was added to DMF and then combined with 29 μL of a CsI (1.5 M, in DMSO) stock solution to generate Cs 0.03 (FA 0.97 MA 0.03 ) 0.97 Pb(I 0.97 Br 0.03 3. Perovskite solution. Different amounts of DVS were incorporated into the perovskite solution in DMF to form perovskite precursor solutions, wherein the volume ratios of DVS:DMF were 3:100, 7:100, 14:100 and 20:100, respectively.

[0175] Each of the cast perovskite films was post-treated with glycerol (Gly) to form a cross-linked film. The molar ratio of Gly to DVS was 32:100. After post-treatment, the cast perovskite films were transferred to a controlled ambient environment (20%–30% relative humidity, RH) and annealed on a hot plate at 120°C for 60 min to promote spontaneous cross-linking and perovskite crystallization.

[0176] Example 7

[0177] This embodiment relates to the fabrication of a target device having a perovskite layer based on divinyl sulfone (DVS). The main fabrication procedure is similar to that described in Example 6, except that for each sample, the volume ratio of DVS:DMS is 7:100, and the molar ratio of Gly to DVS is 4.3:100, 21.3:100, 32:100, 42.7:100, and 64:100.

[0178] Example 8

[0179] This embodiment relates to the fabrication of a target device according to the present invention having a divinyl sulfone (DVS)-based perovskite layer. The main fabrication process is similar to that described in Example 6, except that for each sample, each perovskite precursor solution sample contains Cs. 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 3. Cs 0.35 FA 0.65 PbI 0.8 Br 0.2 Cs 0.2 FA 0.8 PbI 0.7 Br 0.3 or Cs 0.2 FA0.8 PbI 0.5 Br 0.5 The volume ratio of DVS to DMS is 7:100, and the molar ratio of Gly to DVS is 32:100.

[0180] Characterization

[0181] 1. Method

[0182] The crystal structure was explored using Cu Kα radiation on a Rigaku Smart Lab X-ray diffractometer in 0-2θ scan modes with a step size of 0.01° and a range of 5° to 50°. The morphology of the perovskite film was examined by high-resolution field emission scanning electron microscopy (SEM) (TESCAN VEGA3). A Cu X-ray source (8.05 keV) was used. Grazing-incidence wide-angle X-ray scattering (GIWAXS) was studied using the Xeuss 2.0 SAXS / WAXS laboratory beamline with a Pilatus 3R 300K detector. In-situ UV-vis absorption spectra were measured using an F20-UVX spectrometer (Filmetrics, Inc.) equipped with halogen tungsten and deuterium sources. Sample solutions were prepared by dissolving appropriate amounts of FAI, DVS, and FAI / DVS in DMSO-d6. Their proton spectra were obtained using a 400 MHz NMR spectrometer. Steady-state photoluminescence (PL) and time-resolved decay spectra were measured using a PL spectrometer (Edinburgh Instruments, FLS920) with a 636.2 nm picosecond pulsed diode laser (EPL-635, approximately 5 nJ / cm²) as the excitation source. 2 The TRPL decay spectrum was detected at 780 nm. The TRPL decay spectrum was fitted using a double exponential function:

[0183]

[0184] Ultraviolet photoelectric emission spectroscopy (UPS) measurements were performed using a VGESCLAB 220i-XL surface analysis system equipped with a monochromatic AlK X-ray source (1486.6 eV) at a resolution of 3.0 x 10⁻⁶. -8 The test was conducted in a vacuum. For the completed device, JV curves were obtained using a Keithley 2400 source meter under standard AM 1.5G illumination (Enli Technology Co., Ltd., Taiwan), and the light intensity was calibrated using a standard KG-5Si diode. Forward scans (from -0.2 to 1.25 V) and reverse scans (from 1.25 V to -0.2 V) were performed with a delay of 100 ms. The test area was 0.04 cm². 2Typically defined by a metallic mask with an aperture aligned with the effective area. EQE spectra were measured using a QE-R 3011EQE system (Guangyan Technology Co., Ltd., Taiwan) with 210Hz chopped monochromatic light ranging from 300 to 850 nm. EL EQE spectra were recorded using an LED photoluminescence quantum yield measurement system (Enli Tech LQ-100) equipped with a Keithley 2400 source measurement unit. Nonradiative recombination loss (ΔV) OC ,nr) can be obtained from the injection current density equal to J SC EQE at that time EL It is derived from the following equation:

[0185]

[0186] Thermal admittance spectroscopy (TAS) was performed to estimate the thermal admittance at frequencies from 10 6 The energy distribution of trap density within the perovskite film at an AC voltage reduced to 100 Hz is given by the following equation:

[0187]

[0188] Where V bi Vbi is the built-in potential, W is the depletion region width, C is the capacitance, ω is the applied angular frequency, and β is a temperature-independent parameter from the Arrhenius plot. The Vbi and W of the PSC device can be calculated using Mott-Schottky analysis.

[0189] 2. Detailed Calculation

[0190] All electronic structure calculations were performed using the ORCA (version 5.0.4) software package. ORCA is a versatile quantum chemistry program capable of performing various types of calculations, including density functional theory (DFT), Hartree-Fock (HF), and post-HF methods. All calculations were performed using the RI-B3LYP-D3 (BJ) function with the def2-TZVP basis set. To illustrate dispersive interactions, DFT-D3 correlation corrections were included in the calculations. This correction accounts for long-range dispersion forces not adequately captured by the standard DFT functional. The D3 correction employed a Becke-Johnson damping scheme. In the calculation of adsorption energies, an equilibrium method was applied to reduce basis set overlap error (BSSE), and the binding energy was calculated using the following equation:

[0191] E coor =E AB +E BSSE -E A -E B (1),

[0192] Where E coorIt is the BSSE-related adsorption energy, E AB E A and E B These are the electron energies of the entire system, part A, and part B, respectively. EBSSE is the correlation energy calculated using the balance method.

[0193] An implicit solvation model was used in the calculations to reflect the solution environment. The relative permittivity (εr) and refractive index (nD) of DMSO and DMF were defined in the conductor-like polarized continuum model (CPCM). The εr of DVS was calculated through a loop of DFT calculations and molecular dynamics (MD) simulations. First, the geometry and electronic structure of DVS were calculated in the implicit solvation model, where εr equals 47 and nD equals 1.48 (DFT step). Then, MD calculations were performed in GROMACS (version 2021.3) using the optimized structure and RESP2 charge. Atomic interactions were parameterized by the generating AMBER force field. The εr of the current state was then obtained through the GROMACS toolkit (MD step). The obtained εr can be used again in the DFT step to obtain a new structure and charge, which can then be used in the MD step to calculate a new εr. The loop of DFT and MD steps can stop when the εr output from two consecutive MD steps is equal. Figure 9 As shown, after 9 iterations, the calculated εr of DVS is obtained (9.76).

[0194] To investigate the dynamic processes in the pre-nucleation stage of perovskite precursor solutions, we performed approximately 20 ps ab initio molecular dynamics (AIMD) simulations using the CP2K software package (version 7.1) within the framework of density functional theory. The simulations were conducted in an isothermal-isobaric ensemble (NPT), with the temperature and pressure of the simulation system controlled using a Nose-Hoover thermostat and a barostat. We used two different solution environments (DMF / DMSO and DMF / DVS), each containing 7 Pb fractions. 2+ 20 copies of I - 1 copy of Cs + 1 part Br - , 6 copies of FA + Two molecular dynamics simulations were performed on the perovskite precursor in 12 DMF and 12 DMSO or 12 DVS samples. The molecular orbitals of the valence electrons were extended to the DZVP-MOLOPT-SR-GTH basis set, while the nuclear electrons were described using the Goedecker-Teter-Hutter (GTH) pseudopotential method. A plane wave density cutoff of 560 Ry was used. Long-range van der Waals interactions were described using the DFT-D3 method. The radial distribution function (RDF) of the Pb-I pair was calculated in VMD software.

[0195] Performance testing

[0196] 1. Properties of divinyl sulfone

[0197] First, the crosslinking initiator DVS was incorporated into the perovskite precursor solution and mixed with the solvent DMF at an appropriate volume ratio (0-20%, v:v). A conventional solvent system (DMF / DMSO = 5:1, v:v) was used for comparison. It should be noted that the crystallization kinetics of the perovskite film are determined not only by the boiling point, viscosity, and vapor pressure of the solvent system, but also by the coordination chemistry within the perovskite ink and the degree of influence of intermediate phase transitions.

[0198] Donor number (DN) is a quantitative measure of the Lewis basicity of a solvent, which evaluates its coordination interaction with Lewis acids (e.g., PbI₂). To investigate precursor chemistry in DVS-based solvent systems, the following steps are first taken... 23 Na2N nuclear magnetic resonance (NMR) spectroscopy was used to examine the densities (DN) of the DVS. For ease of study, a range of common organic solvents with reported DN values ​​were selected (Table 1). Appropriate amounts of NaClO4 were dissolved in these solvents to prepare 0.2 M solutions. From the perspective of… 23 The DN extracted from the linear fitting of the Na NMR shift was 17.3 kcal / mol. Figure 1 b、 Figure 6 , Figure 34 (Table 1) is much lower than that of commonly used aprotic organic solvents (e.g., DMSO).

[0199] Therefore, DVS is a low Lewis basic solvent, and it exhibits a weak coordination interaction with PbI2. Figure 7 In contrast, there is a strong interaction between DVS and ammonium iodide (e.g., FAI). We dissolved FAI in DVS to obtain a clear solution, but with a different color compared to the DVS solvent. Figure 7 When X-ray diffraction (XRD) spectral analysis was performed on the wet film using FAI in DVS solution, in addition to the characteristic peaks of the FAI powder, we also observed new diffraction peaks at 2θ = 12.78° and 14.19°. Figure 8 This may indicate a new solvated phase based on FAI-DVS. 1 The H NMR results also confirmed this chemical interaction. Figure 1 c). For pure FAI solution, the hydrogen chemical shifts were located at 7.854 ppm and 8.748 ppm, while in FAI / DVS solution, we observed significant shifts and splits in the hydrogen signal at 7.845 ppm, 8.631 ppm, and 8.666 ppm. This implies different chemical environments and different levels of DVS and FAI. + Strong chemical interactions between them.

[0200] To further elucidate the solute-solvent interaction, we used DMF, DMSO, and DVS to investigate the interaction between FA and solute. + The adsorption energy was calculated using density functional theory (DFT). Figure 9-10 and Figure 35 (See Table 2 in the table, and also the detailed calculation section). Compared to these current standard solvents, such as... Figure 1 As shown in d, in the case of DVS, FA + It exhibits the highest adsorption energy, which is in excellent agreement with our experimental results. Ab initio molecular dynamics (MD) was also performed to understand the solvation effects in the pre-nucleation stage of the perovskite precursor solution. MD simulations of approximately 20 ps were conducted to evaluate the evolution of the precursor-solvent mixture in two co-solvent systems (DMF / DMSO and DMF / DVS, see the detailed calculation section). Figure 2 As shown in a, Pb was found. 2+ and ammonium cation (FA) + and MA + Both are highly coordinated with oxygen atoms in DMSO, resulting in the formation of individual small Pb-I clusters in the DMF / DMSO system. However, in the DMF / DVS system, larger Pb-I clusters of edge-sharing iodopeptides were found to begin forming during MD simulations. Figure 2 a and Figure 11 This is also expected due to the weak bonding (low DN) between DVS and PbI2. These Pb-I clusters can act as nucleation centers to further promote the nucleation of perovskite nanocrystals. One of the main insights from this MD simulation is that solvent-solute interactions (e.g., DMF-DVS) can be tuned to have a direct impact on subsequent perovskite nucleation and crystallization kinetics, as will be discussed below.

[0201] 2. Crystallization kinetics of intermediate complexes and perovskite formation

[0202] To provide a comprehensive understanding of the influence of the precursor solution with pre-embedded DVS on the crystallization kinetics of perovskite, time-resolved UV-vis absorption spectra during the antisolvent-assisted spin coating process were analyzed. Figure 2 b shows the change in two-dimensional pseudo-color absorption intensity mapping with spin-coating time. Chlorobenzene (CB) was dropped onto the surface of the perovskite semi-wet film during spin-coating (at 25 s), and the sample from the DVS-based perovskite ink (DMF / DVS = 5:1, v:v) showed much faster nucleation kinetics than the sample from the DMSO-based ink (DMF:DMSO = 5:1, v:v). Figure 12The results were in excellent agreement with those from MD simulations. The cast perovskite film was then treated with gly to trigger copolymerization at the perovskite surface and GB during thermal annealing. The growth rate of the perovskite crystals during this process was quantitatively measured using the same technique. Figure 2 c shows the pseudo-color mapping of the in-situ UV-Vis absorption spectrum as a function of annealing time. The first derivative of the absorbance at 450 nm with respect to time was calculated, and the average growth rate of the perovskite crystals was calculated to be 0.073 s⁻¹ and 0.061 s⁻¹ for the control sample and the DVS-gly-based perovskite film, respectively. -1 ( Figure 13 ).

[0203] A detailed diagnosis of the phase transitions occurring during the thermal annealing process was performed using in-situ XRD spectroscopy between the control sample and the DVS-gly-based sample. For the as-cast control sample, in addition to the characteristic diffraction peaks of cubic FAPbI3 at 2θ = 14.01°, 19.88°, 24.39°, and 28.24° (corresponding to the (001), (011), (111), and (002) planes), we also observed signal-dependent solvates ( ) at 2θ < 10°. Figure 14 a). For comparison, the perovskite film based on as-cast DVS exhibits two distinct diffraction peaks at 2θ = 11.51° and 24.05°, which gradually disappear with thermal annealing. Figure 2 d, 2e and Figure 14 b). This signal may be attributed to the FAI-DVS solvate, confirming the coexistence of cubic perovskite nanocrystals and other FA-based intermediate complexes in the DVS-based sample. The XRD intensity of the perovskite main peak at 2θ = 14.01° was extracted as a function of annealing time, as shown in the figure. Figure 2 As shown in f, the perovskite crystal growth of the DVS-gly-based samples is significantly delayed, mainly due to the thermal energy required for dissociation of intermediates and recrystallization of the cubic perovskite phase, as well as for induced copolymerization. It is well known that delayed crystal growth is beneficial for forming high-quality perovskite films with better crystallinity, more dominant grain orientation, and lower defect density.

[0204] 3. Crosslinking and defect passivation

[0205] The crosslinking reaction between the pre-intercalated initiator (DVS) and the post-treated nucleophile (gly) was confirmed by Fourier transform infrared spectroscopy (FTIR) and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In FTIR, the crosslinking reaction was observed at 1610 cm⁻¹. -1 The DVS characteristic signal of the CC stretching vibration with νC=C at 1275cm decreases after thermal annealing, while a signal corresponding to the stretching vibration at 1275cm appears. -1 and 830cm-1 The obvious peak of COC stretching vibration ( Figure 3 a). This result confirms the high reactivity in the nucleophile-mediated oxa-Michael addition reaction between DVS and gly ( Figure 15 It should be noted that this addition reaction is the only way to achieve controlled copolymerization to form a large network structure. Furthermore, S=O at 1310 cm⁻¹ -1 and 1132cm -1 The characteristic peaks at this location were observed in both the as-cast and post-processed samples, confirming the presence of the DVS-gly copolymer in the final perovskite after heat annealing. Figure 16 Further MALDI-TOF-MS was performed to examine the crosslinking reaction, which confirmed the presence of several fragments in the DVS-gly network. Figure 3 b), and Figure 45 Showing Figure 3 MALDI-TOF-MS data of some segments in the DVS-gly network in b.

[0206] Following controlled copolymerization and perovskite crystal growth, the control sample, DVS, and DVS-gly-based perovskite films showed the same XRD patterns, and no low-dimensional perovskite or non-perovskite was detected. Figure 18 a) corresponds to the characteristic diffraction peaks of cubic FAPbI3, which may indicate that the DVS-gly copolymer scaffold is distributed on the perovskite surface and at GB. Among them, the perovskite film based on DVS-gly exhibits the clearest XRD pattern, with its (100) full width at half maximum (FWHM) decreasing from 0.231° in the control sample to 0.193°, indicating better crystallinity. Figure 18 b). Top-view scanning electron microscope (SEM) images of the perovskite film based on DVS-gly show uniform and dense grains with slightly enlarged GB (glyphics). Figure 19 This confirms that the DVS-gly scaffold is primarily constructed at the perovskite GB site during thermal annealing.

[0207] As is well known, lattice mismatch primarily stems from unfavorable phase transitions and perovskite grain expansion, which induce residual strain and intrinsic defects in the final perovskite film, ultimately accelerating perovskite degradation. Here, depth-correlated grazing incidence X-ray diffraction (GI-XRD) in 2θ-Sin2ψ mode was performed to identify lattice mismatch, and the evolution of residual strain across the perovskite film was analyzed at different grazing incidence angles. Figure 3 (c and 3d). Nearly equal depth-dependent XRD patterns show that the film has the same cubic phase structure at every depth. By changing the appropriate instrument angle ( Figure 36Table 3) selects two typical regions (50 nm near the perovskite surface and 200 nm in the bulk). The (012) plane at 2θ = 31.6° is characteristic of strain analysis due to its high multiplicity. In this method, this plane is usually used to obtain more grain information and mitigate the influence of orientation on the linear relationship of 2θ-Sin2ψ. For the control sample, it was observed that as the instrument tilt angle ψ increases, the (012) peak shifts significantly to a smaller 2θ, indicating that the crystal plane distance d (012) The increase in tensile strain is therefore borne in the near-surface region. Figure 3 c). In contrast, the position of the (012) peak of the DVS-gly-based perovskite remained almost unchanged, indicating that the soft properties of the DVS-gly copolymer scaffold can effectively reduce the non-uniform distribution of residual tensile strain in the near-surface region. Figure 3 d). The same function was observed in the bulk region of the DVS-gly sample. Figure 20 (ab) This means that the copolymer network can penetrate the entire thickness of the perovskite film. Further in-depth elemental analysis using X-ray photoelectron spectroscopy (XPS) confirmed that the DVS-gly copolymer is uniformly distributed throughout the perovskite film, exhibiting constant characteristic signals of S and O elements within a 500s etching period. Figure 3 e). These results mean that our strategy provides comprehensive protection on perovskite surfaces and at GB.

[0208] Steady-state and time-resolved photoluminescence (TRPL) spectroscopy was performed to explore charge recombination behavior in the perovskite film. Compared to the control perovskite film (809 nm), the DVS-gly-based perovskite on the glass substrate showed a more pronounced and slightly blue-shifted PL peak (805 nm), which is an indication of a decrease in the density of trapped states (tDOS) near the band tail. Figure 21 The TRPL decay spectrum was fitted using a double exponential function, and the fitting parameters are summarized in Table 4. Figure 37 It should be noted that the excitation fluence in our study was very low (636.2 nm, ≤5 nJ / cm). 2 Compared to the trapped state, it generates only a much lower free carrier density (2.4 × 10⁻⁶). 14 cm -3(far below the trap density). Under these conditions, TRPL decay primarily responds to trap-assisted recombination behavior in the bulk perovskite. Compared to the control sample (782.88 ns), the DVS-based and DVS-gly-based samples showed significantly extended average lifetimes (4091.66 ns and 4682.63 ns, respectively), indicating that this strategy significantly reduces non-radiative recombination through refined crystallization operations and effective passivation via the copolymer network. Figure 3 f).

[0209] 4. Molecular weight and polydispersity of polymers embedded in perovskite layers

[0210] By using optimized conditions of the crosslinking initiator DVS (DVS:DMF = 7%, v:v), the degree of copolymerization of the oxa-Michael addition reaction mediated by the nucleophile was precisely controlled by optimizing the molar ratio of gly to DVS (from 4.3 to 64 mol%).

[0211] Figure 17 and Figure 36 Table 3 summarizes the molecular weights of the crosslinked products (DVS-gly) determined by gel permeation chromatography at different molar ratios of gly to DVS (from 4.3 to 64 mol%). At 4.3 mol%, a crosslinked product with a very low molecular weight (Mn = 12,849, Mw = 20,556) is produced, resulting in a high polydispersity index (PDI = Mw / Mn = 1.6). Post-treatment with low concentrations of gly controls the crosslinking reaction to a low degree, resulting in small-sized but heterogeneous copolymers. At 32 mol%, a product with a much higher molecular weight (Mn = 110,415, Mw = 129,829) and a low PDI (1.176) is produced. These results indicate that post-treatment with moderate concentrations of gly induces a large and uniform crosslinked scaffold, which can provide superior moisture resistance in perovskites, release residual tensile strain near the surface, and suppress deep defects in the bulk. Increasing the gly molar ratio further to 64 mol% saturated the crosslinking reaction, as the limitation here stemmed from the reaction sites of the DVS. A slightly increased molecular weight (Mn = 120,808, Mw = 139,021) and a similar PDI (1.151) were obtained compared to the 32 mol% sample. However, post-treatment with excess gly on the cast perovskite film may induce FAI defects, thus disrupting the subsequent fine crystal growth process and consequently harming the overall crystal quality of the perovskite.

[0212] Compared to the widely reported uncontrolled polymerization induced by spontaneous monomer feeding, the asynchronous crosslinking strategy in this paper is a controllable reaction process.

[0213] 4. Device performance

[0214] Conventional nip PSCs were fabricated and assembled into FTO / TiO2 / SnO2 QDs / perovskite / spirocyclic-OMeTAD / Au structures, using perovskite ink mixed with an appropriate amount of DVS (0 to 20%, v:v, percentage relative to the main solvent DMF). The work function of the corresponding perovskite film was examined using ultraviolet photoelectroluminescence spectroscopy (UPS), such as... Figure 22 As shown, these samples exhibit a decreasing trend in work function (-4.513, -4.629, and -4.691 eV for the control sample, the DVS-based perovskite film, and the DVS-gly-based perovskite film, respectively), which may be related to the negatively charged iodine gap (Ii). - This is related to the reduction of defects. Figure 23 a shows the JV curves of the best-performing device under different volume ratios of DVS and DMF, and Figure 23 b shows representative JV curves of the DVS-gly-based device under forward and reverse scanning, respectively. Figure 38 Table 5 summarizes their photovoltaic characteristics. As the volumetric DVS ratio increases from 0 to 20%, V... OC The value showed an increasing trend from 1.200V to 1.229V. Meanwhile, JSC remained almost constant at approximately 25.2 mA cm⁻¹. -2 This is very consistent with the integral value from the external quantum efficiency (EQE) spectrum. Figure 4 b, less than 3% mismatch). Devices from inks with 7% DVS offer the highest efficiency, with a maximum PCE of 25.08%. Figure 4 a and Figure 25-26 As shown, after copolymerization with gly post-processing, the efficiency of the DVS-gly-based device increased significantly to 25.22% (certified 24.63%). Figure 24 JV curves were plotted for different gly concentrations (gly to DVS molar ratio from 0 to 64 mol%).

[0215] Furthermore, these devices have demonstrated a maximum V1.229. OC ( Figure 4 c). Based on the first derivative of the EQE spectrum, the photovoltaic bandgap (Eg) of the FA-dominated perovskite used in this invention is... IP The value is calculated to be 1.53 eV. Figure 27 To the best of our knowledge, 1.229VV OC This is the highest value reported in this bandgap of perovskites, and the corresponding V OC The loss (0.301V) is the lowest among all perovskite systems. Figure 39 (See Table 6 in the table). It is worth noting that the V of our device...OC The theoretical V was achieved OC 97.5% of the limit, such as Figure 4 As shown in d. This strategy has also been validated on pin structure devices based on different perovskite compositions, providing a maximum PCE of 25.98% with enhanced V. OC ( Figure 28 ad and Figure 40 (See Table 7). When the device area was increased, we achieved a micro-module (3 sub-cells, 3.6*3.6cm). 2 Substrate, Figure 29 The maximum PCE is 21.75%.

[0216] By employing a quantization-dominated composite mechanism, we revealed the Vg in DVS-gly-based devices using an electroluminescence method. OC The increase in efficiency. When the PSC operates as a light-emitting diode (LED) under forward bias conditions, we measured the external quantum efficiency (EQE) of electroluminescence. EL ()( Figure 4 e and Figure 30 ab). Nonradiative recombination loss (ΔV) OC ,nr) can be obtained from EQE when the injection current density is equal to JSC. EL Derived. Compared with the control device (EQE) EL =1.28%, ΔV OC Compared to the DVS-gly device (nr = 113mV), the DVS-gly device exhibits a significant EQE enhancement of 13.11% at an injection current density equal to JSC. EL ΔV corresponds to 52.5mV. OC ,nr, and V of the JV test OC The defects are consistent. This result indicates that hybrid asynchronous crosslinking significantly inhibits nonradiative recombination at the perovskite surface and GB, which dominates the Vo of DVS-gly-based devices. OC Enhance.

[0217] Further thermal conductivity spectroscopy (TAS) was performed to quantitatively estimate the frequency range from 10 6 Energy distribution of trapped state density (tDOS) under AC voltage conditions reduced from Hz to 100Hz. Compared with the control device (Nt = 8.33 × 10⁻⁶). 16 cm -3 In comparison, DVS-gly-based devices exhibit a much lower trap density (Nt = 5.09 × 10⁻⁶). 16 cm -3 ()( Figure 4 f). It is well known that deep defects (>0.35 eV) on the perovskite surface and at GB are primarily considered to be nonradiative recombination centers, which affects the V of the PSC.OC It is clearly detrimental. The DVS-gly strategy not only manipulates the fine crystallization process through a favorable intermediate-dominated transformation to provide high-quality perovskite crystals, but also effectively mitigates these intrinsic defects via controlled copolymerization at the perovskite surface and GB. The strategy in the application largely synergistically eliminates intrinsic deep defects and V OC The value was pushed to near the radiation limit.

[0218] To further investigate the charge transport / recombination behavior in PSCs, we performed electrochemical impedance spectroscopy (EIS). Figure 32 a and 32b show the control sample and the DVS-gly based device at 10 6 Nyquist plots for AC bias frequencies from Hz to 100Hz. Equivalent circuits simulating charge transfer and recombination are shown in this atlas, where R... S It is the series resistance of the device, and R rec It is the recombination resistance in the bulk perovskite, which is inversely proportional to the recombination rate of photogenerated carriers.

[0219] The DVS-gly device exhibits a lower Ri than the control device. S This is highly correlated with the enhanced fill factor (FF) measured by the JV curve. Figure 32 c). More importantly, the higher R-value of DVS-gly devices rec This is the main factor that reduces the recombination rate of photogenerated carriers in bulk perovskites. Figure 32 d), which is related to the enhanced V as previously described. OC Consistent.

[0220] To further clarify V OC Analysis of loss, quasi-Fermi level splitting (QFLS) derived from photoluminescence (PL), such as Figure 31 As shown. First, the radiation limit of the open-circuit voltage (V) oc,rad It is determined by the following equation:

[0221]

[0222] Where h is Planck's constant (6.626 × 10⁻⁶). -34 J·s), c is the speed of light (3.0 × 10⁻⁶). 8 (m / s). E is the photon energy, typically measured in electron volts (eV). k B This is the Boltzmann constant, with a value of 1.380649 × 10⁻⁶. -23 J / K. T is absolute temperature, typically taken as 300K at room temperature. φ AM1,5G(E) represents the spectrum of standard AM1.5G solar radiation, and EQE(E) is the external quantum efficiency. φ bb (E) represents the spectrum of blackbody radiation at temperature T = 300 K. After calculation, we obtain 1.42 × 10⁻⁶. -20 mA / cm 2 Dark radiation recombination current (J 0,rad ), and V of 1.264V. OC,rad ,like Figure 31 As shown in a.

[0223] Based on the measured photoluminescence quantum yield (PLQY, 13.24% for the control sample and 28.53% for the DVS-gly-based sample), the quasi-Fermi level split (QFLS) was determined by the following equation:

[0224] QFLS=qV OC，rad +k B Tln(PLQY) (4).

[0225] Combine QFLS with the extracted qV OC,rad and the qV of the measured device OC In combination, we elucidate the low V under our strategy. OC The origin of the loss (see) Figure 43 Table 10 in the table). According to qV OC,rad The difference between and QFLS (Δ(V) OC.rad -QFLS) resulted in a significant reduction in energy loss, from 52 meV to 32 meV. QFLS analysis led to the conclusion that the lowest recorded V... OC The loss originates primarily from the effective elimination of nonradiative recombination at the perovskite surface and grain boundaries via the obtained DVS-gly network.

[0226] 5. Moisture resistance of the perovskite layer and device stability

[0227] Besides device performance, long-term stability under various aging conditions (especially long-term operational stability) is crucial for the future commercialization of PSC technology. The DVS-gly copolymerization strategy provides excellent moisture resistance to the perovskite film through internal encapsulation. Figure 5 (a and 5b). Compared to the control perovskite film sample that immediately turned yellow, the DVS-gly-protected perovskite film remained black even after 180 s in water. Unencapsulated DVS-gly-based perovskite devices also exhibited significantly improved stability under direct water immersion. Figure 41 Table 8 in the table. Figure 44Table 11 shows the changes in photovoltaic parameters of the unencapsulated device immersed in water over time. The unencapsulated DVS-gly-based perovskite device also exhibited significantly improved stability under direct water immersion conditions, maintaining more than 93% of its initial efficiency after 180 s of immersion, compared to the short lifetime of 79% for the control device after 33 s.

[0228] For long-term stability, the PCE evolution of the control sample and the DVS-gly-based device was monitored under elevated temperature (ISOS-L-3: 65±5℃, 50±5% RH, PTAA-based nip device) and room temperature (ISOS-L-1: 30±5℃, 60±5% RH, spiro-OMeTAD-based nip device) conditions, under MPP tracking and continuous standard sunlight intensity illumination. The DVS-gly-based device maintained over 98% and 90% of its initial PCE after 1350 h at 65℃ and 1800 h at 30℃, respectively, significantly outperforming the control device. Figure 5 c and 5d). Furthermore, the thermal stability of the PSC in darkness (ISOS-D-2I, 85±5℃, N2) was evaluated based on different HTL values, as shown below. Figure 5 e and Figure 33 As shown in Figure a, the PTAA-based device exhibits longer thermal stability than the spiro-OMeTAD, primarily due to the absence of metal ion dopants. The PTAA-based DVS-gly device retains over 95% of its initial PCE after 1560 h, superior to the control device (which retains only 64%), mainly attributed to the reduced tDOS at the perovskite surface and GB. The DVS-gly device retains 98% of its initial PCE within 2300 h at ambient conditions (25±5℃, 20±5% RH). Figure 33 Enhanced shelf stability was also observed under the conditions shown in b). It is well known that shallow defects (with low migration activation energies) on the perovskite surface and at grain boundaries initiate the infiltration of moisture and oxygen into the perovskite film, thereby accelerating PSC degradation. This strategy effectively mitigates shallow defects and provides excellent moisture resistance, which explains the enhanced stability under different aging conditions.

[0229] The disclosed experimental data are intended to establish the feasibility and reproducibility of the claimed process under representative conditions. The selected materials and process parameters reflect the desired results and are consistent with standard practice in the field. The focus of this disclosure is to demonstrate the feasibility of the process under the specific conditions described. While the experimental data provided emphasizes specific conditions, the process is not intended to be limited to these embodiments. The methods described herein are adaptable to a range of conditions and variations in composition can be explored to optimize the process for a particular application. The selection of the parameters is based on their practical relevance and consistency with the objectives of the invention.

Claims

1. A polymer-intercalated perovskite layer comprising a crosslinked polymer matrix and a perovskite compound, wherein the crosslinked polymer matrix comprises a first repeating unit represented by -CH2CH2SO2CH2CH2- and a second repeating unit represented by a polyol group, and the perovskite compound is represented by Formula 1: (A + ) y [(A’ + ) 1-x (A” + ) x ] 1-y (M 2+ )(X - )3 1 Where x is a value in the range of 0-0.99, and y is a value in the range of 0.01-0.99; M 2+ It is Pb 2+ Sn 2+ Or Ge 2+ ; A + It is Cs + or Rb + ; A' + It is H(C=NH2)NH2 + ; A” + It is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + ;and X - It is Cl - ,Br - or I - One or more of them.

2. The polymer-intercalated perovskite layer of claim 1, wherein the polyol group comprises diol group, triol group, tetraol group or a mixture thereof.

3. The polymer-intercalated perovskite layer of claim 1, wherein the polyol group comprises ethylene glycol, propylene glycol, glycerol, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, bis(trimethylolpropane), diethylene glycol, dipropylene glycol, ethoxylated pentaerythritol, sorbitol, or a mixture thereof.

4. The polymer-intercalated perovskite layer of claim 1, wherein M 2+ It is Pb 2+ A + It is Cs + And A” + It is CH3NH3 + .

5. The polymer-intercalated perovskite layer of claim 1, wherein the perovskite compound comprises (Cs) + ) y [(H(C=NH2)NH2 + ) 1-x (CH3NH3 + ) x ] 1-y (Pb 2+ )[(I - ) 1-z (Br - ) z )]3, where each of x, y and z is an independent value ranging from 0.01 to 0.

99.

6. The polymer-intercalated perovskite layer of claim 1, wherein the polyol group is a glycerol group.

7. The polymer-embedded perovskite layer of claim 1, wherein each of x and y is independently a value ranging from 0.01 to 0.

1.

8. The polymer-intercalated perovskite layer of claim 1, wherein the crosslinked polymer matrix has a weight-average molecular weight in the range of 20,000 to 140,000.

9. The polymer-embedded perovskite layer of claim 1, wherein the molar ratio of the second repeating unit to the first repeating unit is 4-64:

100.

10. A method for producing a polymer-intercalated perovskite layer as claimed in claim 1, wherein the method comprises: A perovskite precursor solution is provided, the solution comprising one or more metal salts, each independently represented by the formula MX2, three or more salts, each independently represented by the formula AZ, A'Z, or A”Z, a crosslinking initiator divinyl sulfone, and a solvent, wherein M is Pb. 2+ Sn 2+ Or Ge 2+ A is Cs + or Rb + A' is H(C=NH2)NH2 + "A" is CH3NH3 + CH3CH2NH3 + Or Me(C=NH2)NH2 + X is Cl independently in each case. - ,Br - or I - And Z is Cl independently in each case. - ,Br - or I - ; The perovskite precursor solution is contacted with a polyol to form a crosslinking precursor solution; and The crosslinking precursor solution is annealed to form the perovskite layer.

11. The method of claim 10, wherein the perovskite precursor solution comprises (Cs) + (I) - ), (H(C=NH2)NH2 + (I) - (CH3NH3) + (Br) - (CH3NH3) + (Cl) - (Pb) 2+ (Br) - )2 and (Pb 2+ (I) - )2.

12. The method of claim 10, wherein the solvent comprises dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), N,N'-dimethylacrylurea (DMPU), or a mixture thereof.

13. The method of claim 10, wherein the volume ratio of divinyl sulfone to the solvent is 1-20:

100.

14. The method of claim 10, wherein the one or more metal salts have a concentration of 0.2 M to 1.5 M in the perovskite precursor solution.

15. The method of claim 10, wherein the molar ratio of the polyol to divinyl sulfone is 4-64:

100.

16. The method of claim 10, wherein the crosslinking precursor solution is annealed at a temperature of 100-120°C.

17. An optoelectronic device comprising the perovskite layer as described in claim 1.

18. The optoelectronic device of claim 17, wherein the optoelectronic device is a perovskite solar cell (PSC), a perovskite light-emitting diode, a perovskite laser, or a perovskite photodetector.

19. The optoelectronic device of claim 18, wherein the open-circuit voltage of the perovskite solar cell is 1.162-1.347V.

20. The optoelectronic device of claim 18, wherein the photoelectric conversion efficiency of the perovskite solar cell is 17.78-25.98%.

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