Passivated a / m / x material

Abstract

This invention provides a photovoltaic device comprising a passivated A / M / X material, wherein the passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent, wherein the crystalline A / M / X material comprises formula [A]. a [M] b [X] c The invention relates to a compound wherein: [A] comprises one or more A cations; [M] comprises one or more M cations, wherein the M cation is a metal or quasi-metal cation; [X] comprises one or more X anions; a is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and wherein the passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety, and (a) does not comprise an amine moiety, or (b) comprises an amine moiety, wherein the amine moiety is a secondary amine, a tertiary amine, or a quaternary amine, or the passivating agent comprises a dimer or polymer of the organic compound. The invention also provides the use of the passivated A / M / X material as defined above as a sensitizer in a photovoltaic device. The invention further relates to a method for producing a passivated A / M / X material, and then (a) producing a photovoltaic device comprising the passivated A / M / X material, or (b) using the passivated A / M / X material as a sensitizer in a photovoltaic device.

Description

Technical Field

[0001] This invention relates to a photovoltaic device comprising a passivated A / M / X material. The invention also relates to the use of the passivated A / M / X material as a sensitizer in a photovoltaic device. Furthermore, the invention relates to a method for producing the passivated A / M / X material, and then (a) producing a photovoltaic device comprising the passivated A / M / X material, or (b) using the passivated A / M / X material as a sensitizer in a photovoltaic device. Background Technology

[0002] Hybrid organic-inorganic metal halide perovskites are widely recognized as one of the most promising emerging semiconductor materials for optoelectronic applications due to their excellent properties, including tunable band gaps, high absorption coefficients, and long carrier diffusion lengths. (See Saliba, M, et al.) Perovskite Solar Cells: From the Atomic Level to Film Quality and Device Performance De Wolf, S. et al. Organometallic halide perovskites: Sharp optical absorption edge and its relation to photovoltaic performance ;and Lim, J., et al., Elucidating the long-range charge carrier mobility in metal halide perovskite thin films .

[0003] Although metal halide perovskites are considered "defect-tolerant," they still require careful growth and "defect passivation strategies" to achieve maximum efficiency and exhibit improved long-term operational stability in optoelectronic devices. Non-radiative defect-mediated charge carrier recombination can be suppressed by modifying perovskites with molecular compounds that bind to or interact with different crystal sites on the perovskite surface (see Noel, NK, et al.). Enhanced Photoluminescence and Solar Cell Performance via Lewis Base Passivation of Organic–Inorganic Lead Halide Perovskites ; and Snaith, HJ, and others, Photovoltaic device comprising a metal halide perovskite and a passivating agent This "molecular passivation" strategy has been widely adopted and is crucial for achieving contemporary record-breaking photo-to-electric conversion efficiency (PCE) in triiodide perovskites (see Jiang, Q. et al.). Surface passivation of perovskite film for efficient solar cells ; and Park, J., and others, Controlled growth of perovskite layers with volatile alkylammonium chlorides ).

[0004] Perovskites, which have shown great promise in providing phase-stable single-junction and tandem multi-junction solar cells, have not benefited from most molecular passivation strategies and instead exhibit severe photovoltage defects when integrated into solar cells.

[0005] The quality of perovskite light absorbers is typically evaluated using photoluminescence quantum yield (PLQY). A higher PLQY value indicates a lower nonradiative recombination rate. Several methods can be employed when focusing on passivating isolated perovskite films or nanocrystals. These include using small-molecule Lewis acids or bases and nanocrystal growth ligands (such as trioctylphosphine oxide and oleic acid). Nanocrystal growth ligands can lead to near-uniform internal luminescence efficiencies in both nanocrystals and polycrystalline films (see deQuilettes, DW et al.). Photoluminescence Lifetimes Exceeding 8 μs and Quantum Yields Exceeding 30% in Hybrid Perovskite Thin Films by Ligand Passivation However, the relatively large organic molecules required for stable organic passivation ligands can also inhibit charge carrier transport in the film and have not yet been demonstrated in high-performance solar cells. As an alternative to molecular passivation, growing thin “shells” of metal oxides or metal hydroxides around perovskite nanocrystals has proven effective in improving both luminescent efficiency and material stability (see Guggisberg, D. et al.). Colloidal CsPbX3 Nanocrystals with Thin Metal Oxide Gel Coatings However, thicker “insulating” metal (hydroxide) oxide coatings suppress charge transport, and some of the best passivation methods exhibiting excellent PLQY have not yet been shown to be compatible with integration into devices to achieve near-radiative-limited high efficiency or photovoltaic (PV) parameters. Following the metal (hydroxide) oxide approach applied to polycrystalline thin films, recent studies have shown that passivating the top surface of perovskites with (3-aminopropyl)trimethoxysilane (APTMS) can significantly reduce nonradiative recombination, resulting in one of the highest PLQYs to date for mixed-cation lead mixed-anion thin-film perovskites (see Jariwala, S. et al.). Reducing Surface Recombination Velocity of Methylammonium-Free Mixed-Cation Mixed-Halide Perovskites via Surface Passivation ; and Pothoof, J. et al. Surface Passivation Suppresses Local Ion Motion in Halide Perovskites In the same study, no functional solar cells were reported (Jariwala, S. et al.), while in subsequent studies, the open-circuit voltage (V) was... OC The improvement in (Shi, Y) is far lower than what the PLQY data indicate. et al., (3-Aminopropyl)trimethoxysilane Surface Passivation Improves Perovskite Solar Cell Performance by Reducing Surface Recombination Velocity ).

[0006] There is still a great need to develop passivation strategies to achieve efficient and stable photovoltaic devices. Summary of the Invention

[0007] This invention stems from the discovery that using specific passivating agents to produce passivated A / M / X materials can reduce the defect density of A / M / X materials, and that when these passivated A / M / X materials are used in photovoltaic devices, they can significantly improve long-term operational stability. Devices formed using passivated A / M / X materials can, among other things, provide high-voltage, high-efficiency perovskite solar cells with a wide range of compositions and band gaps. Furthermore, materials and solar cells incorporating passivated A / M / X materials are highly stable under high temperatures and simulated sunlight.

[0008] Therefore, in a first aspect, the present invention provides a photovoltaic device comprising passivated A / M / X material. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0009] In a second aspect, the present invention provides the use of passivated A / M / X materials as sensitizers in photovoltaic devices. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0010] In a third aspect, the present invention provides a method for producing passivated A / M / X materials. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: To produce photovoltaic devices that incorporate passivated A / M / X materials.

[0011] In a fourth aspect, the present invention provides a method for producing passivated A / M / X materials. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: Passivated A / M / X materials are used as sensitizers in photovoltaic devices. Attached Figure Description

[0012] Figure 1The diagram illustrates silane molecules, their preparation, and photoelectric properties. a) Structures of the following aminosilane (AS) molecules: ((3-aminopropyl)trimethoxysilane (APTMS), trimethoxy(propyl)silane (PTMS), trimethoxy[3-(methylamino)propyl]silane (MAPTMS), (N,N-dimethylaminopropyl)trimethoxysilane (DMAPTMS), [3-(2-aminoethylamino)propyl]trimethoxysilane (AEAPTMS), and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane [(AE)2APTMS]). b) Schematic diagram of a positive intrinsic negative solar cell architecture, where ETL is the electron transport layer, HTL is the hole transport layer, TE is the top electrode, BE is the bottom electrode, and TCO is a transparent conductive oxide. c) Illustration of the passivation molecules based on vapor-phase deposition: i) Selected from... Figure 1 a) Load the AS molecules into a culture dish; ii) Heat the culture dish containing the passivated molecules at 100°C for a short time (i.e., a few minutes) until most of the molecules vaporize; iii) Place the grown perovskite film sample in the culture dish for tens of seconds to a few minutes; d) Fabricate and use on a TCO glass substrate. Figure 1 a) Photographs of the molecularly treated and untreated perovskite films (Ref). e) and f) with Figure 1 Molecular treatment and untreated I are shown in Figure a. 90 Br 10 The photoluminescence quantum yield (PLQY) and THz mobility (f) of perovskite films.

[0013] Figure 2 It shows aminosilane molecules and untreated I 60 Br 40 PLQY.

[0014] Figure 3 Displays I with and without AEAPTMS processing 90 Br 10 I 77 Br 23 and I 60 Br 40 PLQY is composed of perovskite.

[0015] Figure 4 The results show that when AEAPTMS treatment is performed only on perovskite, on top of the HTL / perovskite stack, or between perovskite and ETL (i.e., perovskite / ETL), and without AEAPTM treatment, I 60 Br 40 a) PLQY and b) corresponding quasi-Fermi level splitting (QFLS). All treatments were performed on the top surface of the perovskite.

[0016] Figure 5 This shows the I values ​​for different processing durations, with and without AEAPTMS treatment. 60 Br 40 PLQY was measured.

[0017] Figure 6 The image shows I with and without aminosilane molecule treatment. 90 Br 10 a) optical density, b) reflectance and c) transmittance.

[0018] Figure 7 Showing the two sets of reference I 90 Br 10 THz conductivity measurements were performed.

[0019] Figure 8 The results show the effects of I when treated with different aminosilane molecules. 90 Br 10 THz conductivity measurements were performed.

[0020] Figure 9 The results show the effects of I treated with and without aminosilane molecules. 90 Br 10 SEM measurements were performed.

[0021] Figure 10 The figure shows I when treated with MAPTMS molecules. 90 Br 10 A two-dimensional (2D) perovskite phase was formed on the surface. The fitted lattice parameters were based on a monolayer Ruddlesden-Popper phase with the Pbca space group. Based on grazing incidence wide-angle X-ray scattering (GIWAXS) data, the fitted data showed that both peaks originated from a family facet with a high orientation (001).

[0022] Figure 11Optimized structures of silane surface interactions are shown. a) Side view of the structures simulated using DFT (density functional theory) and ab initio molecular dynamics (AIMD) techniques for the interactions of aminosilanes PTMS, APTMS, MAPTMS, and AEAPTMS with Pb / I-terminated (001)FAPbI3 surfaces. The PbI6 octahedron is highlighted to indicate that the major structural relaxation occurs mostly at the top layer. b) Variations in charge density distribution around all species involved in silane surface binding; prominent charge accumulation (yellow) and depletion (blue) regions indicate N-Pb and O-Pb interactions. c) Binding energies of aminosilanes on pristine and iodide Frenkel defect surfaces. d) Schematic diagram showing the perovskite surface with undercoordinated Pb cations adjacent to iodide vacancies and the binding of AEAPTMS molecules through N-Pb and O-Pb bonds. For clarity, FA is omitted here. + cation.

[0023] Figure 12 shows the surface treatments of I after various aminosilane treatments. 90 Br 10 Current density and voltage characterization were performed for: a) PTMS, b) APTMS, c) MAPTMS, d) DMAPTMS, e) AEAPTMS, and f) (AE)2APTMS.

[0024] Figure 13 shows the characterization of perovskite solar cells. a), b), and c) are shown using I0. 90 Br 10 (a)I 77 Br 23 (b)I 60 Br 40 (c) The absorbent has a pore size of 0.25 cm. 2 The current density and voltage characteristics of representative AEAPTMS-treated perovskite solar cells are shown, where FB-SC represents the scan direction from forward bias (FB) to short circuit (SC) conditions, and SC-FB is the opposite. Illustrations a)-c) summarize the key PV performance parameters. d) Based on I 90 Br 10 I 77 Br 23 and I 60 Br 40 The representative large area of ​​1cm 2 The current density and voltage characteristics of the battery processed by AEAPTMS. e) shows the corresponding maximum power point tracking (MPPT) efficiency (η) over 120 seconds.

[0025] Figure 14 The images show I treated with a) AEAPTMS molecules and untreated I.90 Br 10 EQE spectrum (solid line, where at AM1.5 (100 mW cm⁻¹)). -2 (a) Integrating the photocurrent over the solar spectrum and the corresponding first derivative of EQE (dashed line, making the extracted bandgap value 1.60 eV). c) The corresponding η values ​​of the AEAPTMS-based cell and reference cell measured over a 120-second time period. MPPT .

[0026] Figure 15 The images show I treated with a) AEAPTMS molecules and untreated I. 77 Br 23 EQE spectrum (solid line, where at AM1.5 (100 mW cm⁻¹)). -2 (a) Integrating the photocurrent over the solar spectrum and the corresponding first derivative of EQE (dashed line, making the extracted bandgap value 1.67 eV). c) The corresponding η values ​​of the AEAPTMS-based cell and reference cell measured over a 120-second time period. MPPT .

[0027] Figure 16 The images show I treated with a) AEAPTMS molecules and untreated I. 60 Br 40 EQE spectrum (solid line, where at AM1.5 (100 mW cm⁻¹)). -2 (a) Integrating the photocurrent over the solar spectrum and the corresponding first derivative of EQE (dashed line, making the extracted bandgap value 1.77 eV). c) The corresponding η values ​​of the AEAPTMS-based cell and reference cell measured over a 120-second time period. MPPT .

[0028] Figure 17 The results show whether the molecules were treated with or untreated using AEAPTMS (i.e.,...). Figure 17 The "ref" in the text) 90 Br 10 (1.60eV, 26 batteries), I 77 Br 23 (1.67eV, 15 batteries) and I 60 Br 40 (1.77 eV, 18 cells) 0.25 cm⁻¹ perovskite 2 Solar cells, V obtained from SC-FB and FB-SC scans OC The statistical results.

[0029] Figure 18 The results show whether the molecules were treated with or untreated using AEAPTMS (i.e.,...). Figure 18The "ref" in the text) 90 Br 10 (1.60eV, 26 batteries), I 77 Br 23 (1.67eV, 15 batteries) and I 60 Br 40 (1.77 eV, 18 cells) 0.25 cm⁻¹ perovskite 2 Solar cells, J obtained from SC-FB and FB-SC scans SC The statistical results.

[0030] Figure 19 The results show whether the molecules were treated with or untreated using AEAPTMS (i.e.,...). Figure 19 The "ref" in the text) 90 Br 10 (1.60eV, 26 batteries), I 77 Br 23 (1.67eV, 15 batteries) and I 60 Br 40 (1.77 eV, 18 cells) 0.25 cm⁻¹ perovskite 2 Statistical results of FF obtained from SC-FB and FB-SC scans of solar cells.

[0031] Figure 20 The results show whether the molecules were treated with or untreated using AEAPTMS (i.e.,...). Figure 20 The "ref" in the text) 90 Br 10 (1.60eV, 26 batteries), I 77 Br 23 (1.67eV, 15 batteries) and I 60 Br 40 (1.77 eV, 18 cells) 0.25 cm⁻¹ perovskite 2 Statistical results of PCE obtained from SC-FB and FB-SC scans of solar cells.

[0032] Figure 21 The image shows 1-cm with and without AEAPTMS molecular treatment. 2 The EQE spectrum of the battery (solid line, where at AM1.5 (100mW cm⁻¹)) -2 (Integrating the photocurrent over the solar spectrum) and the corresponding first derivative of EQE (dashed line, making the extracted bandgap values ​​a) 1.60 eV, b) 1.67 eV and c) 1.77 eV).

[0033] Figure 22 shows the operational stability and aging characterization. a) AEAPTMS packaged components aged in laboratory ambient air with a relative humidity of 50-60%, at 85°C, under open-circuit conditions and full-spectrum simulated sunlight. 90 Br 10 Battery and Reference (ref) I 90 Br 10 Evolution of the average maximum power point (MPP) of cells (including six AEAPTMS-based cells and five ref cells) (with corresponding standard deviations presented as band plots). MPP for each cell was tracked for 120 seconds at different aging stages. Data sets including several solar cells with different degradation pathways (i.e., light immersion and aging) are explicitly shown. b)(a) Evolution of the normalized MPP for each cell used and recorded. For the champion cell, the time (T0) taken to reach 95% of its initial MPP. 95，冠军 (a) Approximately 1600 hours. (b) and (c) Before aging (0h) and after aging for 600h under the conditions described in (a), the total area is 0.25-cm². 2 (c) and reference (d) I processed by AEAPTMS 90 Br 10 The PL-derived QFLS plot of the battery. e) and f) correspond to the luminescence-derived charge collection mass (Q) of the AEAPTMS-processed (e) and reference (f) batteries calculated in (c) and (d), respectively. col Figures g and h) show QFLS(g) and QFLS(g) as violin diagrams. col The statistical results in (h) are given, where for all batteries recorded in (b), the median, interquartile range, and 1.5 × interquartile range are represented as points, boxes, and lines, respectively. Each QFLS and Q col The figure covers an area of ​​5.38mm × 4.67mm.

[0034] Figure 23 The AEAPTMS-treated encapsulated I-type aluminum alloy was shown to have undergone aging in laboratory ambient air at 85°C under open-circuit conditions and full-spectrum simulated sunlight at a relative humidity of 50-60%. 90 Br 10 Battery and ref I 90 Br 10 The average V of the batteries (including six AEAPTMS-based batteries and five ref batteries) OC The evolution (the corresponding standard deviation is in the form of a band chart).

[0035] Figure 24 The AEAPTMS-treated encapsulated I-type aluminum alloy was shown to have undergone aging in laboratory ambient air at 85°C under open-circuit conditions and full-spectrum simulated sunlight at a relative humidity of 50-60%.90 Br 10 Battery and ref I 90 Br 10 The average J of the batteries (including six AEAPTMS-based batteries and five ref batteries) SC The evolution (the corresponding standard deviation is in the form of a band chart).

[0036] Figure 25 The AEAPTMS-treated encapsulated I-type aluminum alloy was shown to have undergone aging in laboratory ambient air at 85°C under open-circuit conditions and full-spectrum simulated sunlight at a relative humidity of 50-60%. 90 Br 10 Battery and ref I 90 Br 10 The evolution of the average FF of the batteries (including six AEAPTMS-based batteries and five ref batteries) (the corresponding standard deviation is presented in the form of a band plot).

[0037] Figure 26 The evolution of the EQE spectrum before and after aging in ambient air with a relative humidity of 50-60% in the laboratory at 85°C, under open-circuit conditions and full-spectrum simulated sunlight, is shown, with the EQE spectrum at AM1.5 (100 mW cm⁻¹) being the most significant. -2 Integrating the photocurrent over the solar spectrum, and I 90 Br 10 Batteries treated with (a) and without (b) AEAPTMS molecules.

[0038] Figure 27 It shows a total area of ​​0.25 cm. 2 a) Processed by AEAPTMS and b) ref I 90 Br 10 (b) QFLS plots of the battery before aging (0h) and after different aging time periods. Each image covers an area of ​​5.38mm × 4.67mm.

[0039] Figure 28 It shows a total area of ​​0.25 cm. 2 a) Processed by AEAPTMS and b) ref I 90 Br 10 Q values ​​of the battery before aging (0h) and after different aging periods. col Figure. Each image covers an area of ​​5.38mm × 4.67mm.

[0040] Figure 29 The current density and voltage characteristics of a set of pin perovskite solar cells are shown, including those treated with APTMS and those not treated (i.e., reference).

[0041] Figure 30 The use of evaporation of C is shown. 60 0.25cm with and without BCP treatment and AEAPTMS treatment 2 I 90 Br 10 The solar cells were characterized by a) current density and voltage, and b) the corresponding η over a 120-second time period. MPPT In c) and d), the EQE spectra of the cells with and without AEAPTMS molecular treatment are shown (solid lines, where at AM 1.5 (100 mW cm⁻¹)). -2 (Integrating the photocurrent over the solar spectrum) and the first derivative of the corresponding EQE (dashed line, making the extracted bandgap value 1.67eV).

[0042] Figure 31 Three-dimensional (3D) crystallographic characterization of the perovskite film is shown. Reference and aminosilane-treated I₂ films were prepared on ITO glass substrates. 90 Br 10 XRD series of perovskite films.

[0043] Figure 32 The electron density of states in AEAPTMS-treated perovskite is shown. The electron density of states on the perovskite surface with iodide Frenkel defects is shown before and after interaction with AEAPTMS molecules. A small increase in the band gap from 1.03 eV to 1.15 eV is found due to AEAPTMS surface bonding. This broadening of surface states implies a surface passivation effect. After interaction with AEAPTMS, the trap-like states below the valence band edge disappear, again demonstrating the effective passivating effect of AEAPTMS in eliminating these trap states and iodine vacancy defects through strong surface bonding.

[0044] Figure 33 PCE bandgap and V were shown. OC - Comparison of bandgap literature data. Data are presented using different symbols based on their effective pixel area: squares represent pixel areas <0.1cm². 2 The circle represents a pixel area of ​​0.1 to 0.3 cm. 2 Between; a triangle represents a pixel area equal to 1.0 cm². 2 The dashed lines represent percentages of detailed margin limits (e.g., 90%, 80%, etc.). Our representative 0.25-cm band gaps are 1.6 eV, 1.67 eV, and 1.77 eV. 2 and 1-cm 2The batteries are labeled red (left frame), green (middle frame), and blue (right frame), and circled with dashed lines. All data was extracted from reverse scans performed on the respective battery (pin configuration), as described by Jacobsson, TJ, et al. An open-access database and analysis tool for perovskite solar cells based on the FAIR data principles As reported.

[0045] Figure 34 Displayed I processed by AEAPTMS 60 Br 40 Battery characteristics. a) Photograph of the solar cell design used in this study. b) 1-cm shown in (a). 2 I processed by AEAPTMS 60 Br 40 The corresponding current density and voltage characteristics of the battery. c) and d) The corresponding EQE obtained under voltage scan operation between 0 and 4V. EL (c) and via 17mA cm -2 The current density injected into the same cell (b) obtained a 600-second recorded EQE. EL (d). The illustrations in (c) and (d) show the battery at 17 mAcm. -2 Illumination at current density and η for 120 seconds MPPT The corresponding photos.

[0046] Figure 35 It showed I 90 Br 10 Operational stability of solar cells. a) Aging of encapsulated AEAPTMS-treated cells under open-circuit conditions and full-spectrum simulated sunlight in laboratory ambient air with a relative humidity of 50-60% at 85°C. 90 Br 10 Battery and ref I 90 Br 10 Evolution of the average PCE of the cells (including 6 AEAPTMS-based cells and 5 ref cells) (the corresponding standard deviations are presented in band plot form). Data sets including several solar cells with different degradation pathways (i.e., light immersion and aging) are explicitly shown. b)(a) Evolution of the normalized PCE of the individual cells used and recorded. For the champion cell, the time (T) taken to reach 95% of its initial MPP. 95，冠军 It takes approximately 1440 hours.

[0047] Figure 36 Operational stability and aging characterization are demonstrated. a) AEAPTMS packaged products aged in laboratory ambient air with a relative humidity of 50-60%, at 85°C, under open-circuit conditions and full-spectrum simulated sunlight. 90 Br10 Battery and Reference (ref) I 90 Br 10 Evolution of the average maximum power point (MPP) of the cells (including 6 AEAPTMS-based cells and 5 ref cells) (with corresponding standard deviations presented as band plots). MPP for each cell was tracked for 120 seconds at different aging stages. Data sets including several solar cells with different degradation pathways (i.e., light immersion and aging) are explicitly shown. b)(a) Evolution of the normalized MPP for each cell used and recorded. For the champion cell, the time (T0) taken to reach 95% of its initial MPP. 95，冠军 It takes approximately 1600 hours. Detailed Implementation

[0048] The term "crystallization" as used in this article refers to crystalline compounds, which are compounds with an extended 3D crystal structure. Crystalline compounds are typically in crystalline form, or, in the case of polycrystalline compounds, microcrystals (i.e., multiple crystals with a particle size of less than or equal to 10 μm). These crystals often form a layer together. Crystalline materials can have crystals of any size. When crystals have one or more dimensions in the range of 1 nm to 1000 nm, they can be described as nanocrystals.

[0049] The term "organic cation" refers to a cation that contains carbon. Cations can contain other elements; for example, a cation can contain hydrogen, nitrogen, or oxygen.

[0050] As used in this article, the term "crystalline A / M / X material" refers to a material with a crystalline structure containing one or more A ions, one or more M ions, and one or more X ions. A and M ions are cations. X ions are anions. A / M / X materials typically do not contain any other types of ions. As used herein, the term "perovskite" refers to a material having a three-dimensional crystal structure associated with the three-dimensional crystal structure of CaTiO3, or a material comprising a layer having a structure associated with the CaTiO3 structure. The structure of CaTiO3 can be represented by the formula AMX3, where A and M are cations of different sizes, and X is an anion. In the unit cell, the A cation is located at (0,0,0), the M cation at (1 / 2, 1 / 2, 1 / 2), and the X anion at (1 / 2, 1 / 2, 0). The A cation is typically larger than the M cation. Those skilled in the art will understand that variations in A, M, and X, resulting in different ion sizes, can cause the perovskite material's structure to become distorted away from the structure adopted by CaTiO3, leading to a distorted structure with lower symmetry. If the material comprises a layer having a structure associated with the CaTiO3 structure, the symmetry will also be lower. Materials comprising perovskite material layers are well known. For example, materials with a K2NiF4-type structure comprise perovskite material layers. Those skilled in the art will understand that perovskite materials can be represented by the formula [A][M][X]3, where [A] is at least one cation, [M] is at least one cation, and [X] is at least one anion. When a perovskite contains more than one A cation, different A cations can be distributed at A sites in an ordered or disordered manner. When a perovskite contains more than one M cation, different M cations can be distributed at B sites in an ordered or disordered manner. When a perovskite contains more than one X anion, different X anions can be distributed at X sites in an ordered or disordered manner. The symmetry of perovskites containing more than one A cation, more than one M cation, or more than one X cation will be lower than that of CaTiO3. For layered perovskites, the stoichiometric ratio can vary among A, M, and X ions. As an example, if the ionic radius of the A cation is too large to be housed within a 3D perovskite structure, a [A]2[M][X]4 structure can be used. The term "perovskite" also includes A / M / X materials employing the Ruddleson-Popper phase. The Ruddleson-Popper phase refers to a perovskite with a mixture of layered and 3D components. This perovskite can be produced using A... n-1 A'2M n X 3n+1 The crystal structure of a perovskite, where A and A' are distinct cations, and n is an integer from 1 to 8 or from 2 to 6. The term "mixed 2D and 3D" perovskite is used to refer to perovskites containing both AMX3 and A'. n-1 A'2M n X 3n+1 Perovskite films with two perovskite phase regions or domains.

[0051] The term “metal halide perovskite” as used in this article refers to a perovskite containing at least one metal cation and at least one halide anion. The term “mixed halide perovskite” as used in this article refers to perovskite containing at least two types of halide anions.

[0052] The term “mixed-cation perovskite” as used in this article refers to perovskite containing at least two types of A cations.

[0053] The term “mixed metal perovskite” as used in this article refers to perovskites containing at least two types of M cations.

[0054] The term “organic-inorganic metal halide perovskite” as used in this article refers to a metal halide perovskite containing at least one organic cation.

[0055] As used in this document, the terms "set on" or "is set on" refer to making a component available on another component or placing a component on top of another component. This can mean making a first component directly available on a second component, placing a first component directly on top of a second component, or having a third component between the first and second components. For example, if a first layer is set on a second layer, this includes cases where a third layer exists between the first and second layers. Generally, "set on" means placing a component directly on top of another component.

[0056] Similarly, the terms "set between" or "is set between" as used herein refer to making a (first) component available between two other (second and third) components or placing a (first) component between two other (second and third) components. This may mean making the first component available directly between the second and third components, or placing the first component directly between the second and third components, or having other components between the first and second components and / or between the first and third components. For example, if the first layer is set between the second and third layers, this includes the possibility of an intermediate fourth layer between the first and second layers, and an intermediate fifth layer between the first and third layers. However, "set between" generally refers to placing a (first) component directly between two other (second and third) components or making the (first) component available directly between two other (second and third) components.

[0057] As used herein, the term "layer" refers to any structure that is substantially layered in form (e.g., extending substantially along two perpendicular directions, but with limitation on its extension along a third perpendicular direction). The thickness of a layer can vary with its extent. Typically, the thickness of a layer is approximately constant. The "thickness" of a layer as used herein refers to the average thickness of the layer. The thickness of a layer can be readily measured, for example, by using microscopy, such as electron microscopy of membrane cross-sections, or by surface profilometry, such as using a stylus profilometer.

[0058] As used herein, the term "band gap" refers to the energy difference between the top of the valence band and the bottom of the conduction band in a material. Those skilled in the art can readily measure the band gap of semiconductors (including perovskites) using well-known procedures that do not require excessive experimentation. For example, the band gap of a semiconductor can be estimated by constructing a photovoltaic diode or solar cell from the semiconductor and determining the photovoltaic spectrum. Alternatively, the band gap can be estimated by measuring the optical absorption spectrum using transmission spectrophotometry or photothermal deflection spectroscopy. The band gap can be determined by plotting a Tauc diagram, as described in Tauc, J., Grigorovici, R. and Vancu, A. Optical Properties and Electronic Structure of Amorphous Germanium. Phys. Status Solidi 15, 627–637 (1966), where the square of the product of the absorption coefficient and the photon energy is plotted on the Y-axis, the photon energy on the x-axis, and the linear intercept of the absorption edge with the x-axis gives the optical band gap of the semiconductor. Alternatively, the optical bandgap can be estimated by taking the starting point of the incident photon-to-electron conversion efficiency, as Barkhouse et al. Device characteristics of a 10.1% hydrazineprocessed Cu2ZnSn (Se,S)4 solar cell As stated above.

[0059] As used herein, the term "semiconductor" or "semiconductor material" refers to a material whose conductivity is between that of a conductor and a dielectric. A semiconductor can be an n-type semiconductor, a p-type semiconductor, or an intrinsic (i) semiconductor. A semiconductor can have a band gap of 0.5 to 3.5 eV, for example, 0.5 to 2.5 eV or 1.0 to 2.0 eV (when measured at 300 K).

[0060] As used herein, the term "n-type region" refers to a region of one or more electron transport (i.e., n-type) materials. Similarly, the term "n-type layer" refers to a layer of electron transport (i.e., n-type) materials. Electron transport (i.e., n-type) materials can be a single electron transport compound or element, or a mixture of two or more electron transport compounds or elements. Electron transport compounds or elements can be undoped or doped with one or more doping elements.

[0061] As used herein, the term "p-type region" refers to a region of one or more hole-transporting (i.e., p-type) materials. Similarly, the term "p-type layer" refers to a layer of hole-transporting (i.e., p-type) materials. Hole-transporting (i.e., p-type) materials can be a single hole-transporting compound or element, or a mixture of two or more hole-transporting compounds or elements. Hole-transporting compounds or elements can be undoped or doped with one or more doping elements.

[0062] As used herein, the term "electrode material" refers to any material suitable for use in an electrode. The electrode material will have high electrical conductivity. The term "electrode" as used herein refers to a region or layer composed of, or substantially composed of, electrode material.

[0063] As used herein, the term "passivation" refers to the suppression of non-radiative defect-mediated charge carrier recombination in A / M / X materials. Specifically, as used herein, passivation is achieved by modifying A / M / X materials with molecular compounds that bind to or interact with different sites on the A / M / X material surface. These interacting sites on the A / M / X material surface can be lattice sites exposed on the surface, or defect sites such as vacancies or interstitials, as well as long-range crystal defects such as step dislocations and addition atoms.

[0064] The term "passivating agent" as used in this article refers to the molecular compound used to passivate A / M / X materials.

[0065] As used herein, “alkyl” is a substituted or unsubstituted straight-chain or branched saturated group, typically a substituted or unsubstituted straight-chain saturated group, more typically an unsubstituted straight-chain saturated group. C1-C 20 Alkyl groups are unsubstituted or substituted straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms. Typically, they are C1-C2. 10 Alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, or C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, or C1-C4 alkyl, such as methyl, ethyl, isopropyl, n-propyl, tert-butyl, sec-butyl or n-butyl.

[0066] When an alkyl group is substituted, it typically carries one or more substituents selected from the following: substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted aryl (as defined herein), cyano, amino, C1-C 10 Alkylamino, di(C1-C) 10 Alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamido, hydroxyl, oxo, halogen, carboxyl, ester, acyl, acyloxy C1-C 20 Alkoxy, aryloxy, haloalkyl, sulfonic acid, mercapto (i.e., thiol, -SH), C1-C 10 Alkylthio, arylthio, sulfonyl, phosphoric acid, phosphate ester, phosphonic acid, and phosphonate ester. Examples of substituted alkyl groups include haloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, and alkylaryl. The term alkylaryl as used herein refers to C1-C64. 20Alkyl groups, wherein at least one hydrogen atom has been replaced by an aryl group. Examples of such groups include, but are not limited to, benzyl (phenylmethyl, PhCH2-), diphenylmethyl (Ph2CH-), triphenylmethyl (triphenylmethyl, Ph3C-), phenethyl (phenylethyl, Ph-CH2CH2-), styryl (Ph-CH=CH-), and cinnamyl (Ph-CH=CH-CH2-).

[0067] As described below, alkyl groups, such as C1-C 20 The alkyl group may optionally be interrupted by a secondary, tertiary, or quaternary amine moiety as defined below. That is, the secondary, tertiary, or quaternary amine moiety may interrupt the carbon chain of the alkyl group such that the nitrogen atom of the secondary, tertiary, or quaternary amine moiety is bonded to two different carbon atoms within the carbon chain of the alkyl group. The alkyl group may be interrupted more than once by multiple secondary, tertiary, or quaternary amine moiety moietyes, each interrupting the alkyl group at a different point along the carbon chain (i.e., between different pairs of carbon atoms in the carbon chain). This is particularly true when the alkyl group is an organic group bonded to the silicon atom of the silane moiety of an organic compound of the passivating agent described herein, such as the organic group R in an organic compound of formula (I) herein. Furthermore or alternatively, such an alkyl group, for example, C1-C 20 Alkyl groups may be substituted with one or more primary, secondary, tertiary, or quaternary amines as defined below.

[0068] Alternatively, the alkyl group may not be interrupted by the secondary, tertiary, or quaternary amine portion. In other words, the carbon chain of the alkyl group may be uninterrupted. This is typically the case when the alkyl group is not an organic group of the silicon atom of the silane portion of the organic compound bonded to the passivating agent described herein, for example when the alkyl group is not the organic group R in the organic compound of formula (I) herein.

[0069] Typically, substituted alkyl groups have one, two, or three substituents, for example, one or two substituents.

[0070] As used herein, “aryl” is a substituted or unsubstituted monocyclic or bicyclic aromatic group that typically contains 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, in the ring moiety. Examples include phenyl, naphthyl, indenyl, and indenyl. The aryl group can be unsubstituted or substituted. When an aryl group as defined above is substituted, it typically carries one or more substituents selected from: unsubstituted C1-C6 alkyl (forming an aralkyl group), unsubstituted aryl, cyano, amino, C1-C6 alkyl, ... 10 Alkylamino, di(C1-C) 10 Alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamino, hydroxyl, halogen, carboxyl, ester, acyl, acyloxy, C1-C 20 Alkoxy, aryloxy, haloalkyl, mercapto (i.e., thiol, -SH), C1-C10 Alkylthio, arylthio, sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid and phosphonate ester, and sulfonyl. Typically, it carries 0, 1, 2, or 3 substituents. The substituted aryl group can be substituted at two positions by a single C1-C6 alkylene group, or by a bidentate group represented by the formula -X-(C1-C6)alkylene or -X-(C1-C6)alkylene-X-, where X is selected from O, S, and NR, and R is H, aryl, or C1-C6 alkyl. Therefore, the substituted aryl group can be an aryl group fused with a cycloalkyl or heterocyclic group. The ring atom of the aryl group can include one or more heteroatoms (such as in a heteroaryl). This aryl group (heteroaryl) is a substituted or unsubstituted monocyclic or bicyclic heteroaryl group that typically contains 6 to 10 atoms in the ring moiety, including one or more heteroatoms. It is typically a 5- or 6-membered ring containing at least one heteroatom selected from O, S, N, P, Se, and Si. It can contain, for example, 1, 2, or 3 heteroatoms. Examples of heteroaryl groups include thiophenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, pyrazolyl, pyrroleyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolinyl, and isoquinolinyl. Heteroaryl groups can be unsubstituted or substituted, as described above for aryl groups. Typically, they have 0, 1, 2, or 3 substituents.

[0071] As used herein, the term "cycloalkyl" refers to a saturated or partially unsaturated cyclic hydrocarbon group. A cycloalkyl group can be C10 or C20. 3-10 cycloalkyl, C 3-8 cycloalkyl or C 3-6 Cycloalkyl. C 3-8 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclohex-1,3-dienyl, cycloheptyl, and cyclooctyl. 3-6 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0072] As used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon group containing one or more double bonds. An alkenyl group can be C... 2-20 alkenyl, C 2-14 alkenyl, C 2-10 alkenyl, C 2-6 alkenyl or C 2-4 Alkenyl. C 2-10 Examples of alkenyl groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. 2-6 Examples of alkenyl groups are vinyl, propenyl, butenyl, pentenyl, or hexenyl. 2-4Examples of alkenyl groups are vinyl, isopropenyl, n-propenyl, sec-butenyl, or n-butenyl. Alkenyl groups typically contain one or two double bonds.

[0073] As used in this article, the term "alkynyl" refers to a straight-chain or branched hydrocarbon group containing one or more triple bonds. The alkynyl group can be C... 2-20 alkynyl group, C 2-14 alkynyl group, C 2-10 alkynyl group, C 2-6 alkynyl or C 2-4 Alkynyl group. C 2-10 Examples of alkynyl groups are ethynyl, propynyl, butynyl, penynyl, hexynyl, hepynyl, octyynyl, nonynyl, or decynyl. 2-6 Examples of alkynyl groups are ethynyl, propynyl, butynyl, pentynyl, or hexynyl. Alynyl groups typically contain one or two triple bonds.

[0074] Unless otherwise stated, the term "substituted" as used herein in the context of substituted organic groups refers to an organic group having one or more substituents selected from: C 1-10 Alkyl, aryl (as defined herein), cyano, amino, nitro, C 1-10 Alkylamino, di(C 1-10 ) alkylamino, arylamino, diarylamino, aryl (C 1-10 ) alkylamino, amide, acylamino, hydroxyl, oxo, halogen, carboxyl, ester, acyl, acyloxy, C 1-10 Alkyloxy, aryloxy, halogenated (C 1-10 ) alkyl, sulfonic acid, thiol, C 1-10 Alkylthio, arylthio, sulfonyl, phosphoric acid, phosphate ester, phosphonic acid, and phosphonate ester. Examples of substituted alkyl groups include haloalkyl, perhaloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, and alkylaryl. When a group is substituted, it can have one, two, or three substituents. For example, a substituted group can have one or two substituents.

[0075] The term "halide" as used in this article refers to the single-charged anion of an element in Group VIII of the periodic table. "Halides" include fluorides, chlorides, bromides, and iodides.

[0076] As used herein, the term "halogen" refers to a halogen atom. Exemplary halogen species include fluorine, chlorine, bromine, and iodine species.

[0077] As used herein, the term hydroxyl represents the group with the formula -OH.

[0078] As used herein, the term thiol represents the group of the formula -SH.

[0079] As used herein, the term acyl denotes a group of the formula -C(=O)R, where R is an acyl substituent, such as a substituted or unsubstituted C. 1-20 Alkyl, or substituted or unsubstituted aryl. Examples of acyl groups include, but are not limited to, -C(=O)CH3 (acetyl), -C(=O)CH2CH3 (propionyl), -C(=O)C(CH3)3 (tert-butyryl) and -C(=O)Ph (benzoyl, phenone).

[0080] As used herein, the term acyloxy (or ester) denotes a group of the formula -OC(=O)R, where R is an acyloxy substituent, such as a substituted or unsubstituted C. 1-20 Alkyl, or substituted or unsubstituted aryl, usually C 1-6 Alkyl groups. Examples of acyl groups include, but are not limited to, -OC(=O)CH3 (acetoxy), -OC(=O)CH2CH3, -OC(=O)C(CH3)3, -OC(=O)Ph and -OC(=O)CH2Ph.

[0081] As used herein, the term ester (or carboxylate, carboxylic acidester, or oxycarbonyl) represents a group of the formula -C(=O)OR, where R is an ester substituent, such as a substituted or unsubstituted C. 1-20 Alkyl, or substituted or unsubstituted aryl (usually phenyl). Examples of ester groups include, but are not limited to, -C(=O)OCH3, -C(=O)OCH2CH3, -C(=O)C(CH3)3 and -C(=O)OPh.

[0082] As used herein, the terms “carboxy,” “carboxyl,” and “carboxylic acid” each denote a group of the formula -C(=O)OH or -COOH. As those skilled in the art will understand, carboxylic acid groups can be in protonated and deprotonated forms (e.g., -C(=O)OH and -C(=O)O). - ) and salt forms (e.g., -C(=O)O) - X + , where X + It exists as a monovalent cation.

[0083] C 1-10 The alkylthio group is the C atom attached to the sulfur atom. 1-10 Alkyl, preferably C 1-6 Alkyl group. Aryl thio group is an aryl group attached to a sulfur atom, preferably phenyl. An example of an aryl thio group is -SPh.

[0084] C 1-10 An alkoxy group is a substituted or unsubstituted C atom attached to an oxygen atom.1-10 Alkyl group. C 1-6 An alkoxy group is a substituted or unsubstituted C atom attached to an oxygen atom. 1-6 Alkyl group. C 1-4 An alkoxy group is a substituted or unsubstituted carbon atom attached to an oxygen atom. 1-4 Alkyl group. The C... 1-20 C 1-10 C 1-6 and C 1-4 Alkyl groups may optionally be terminated as defined herein. C 1-4 Examples of alkoxy groups include -OMe (methoxy), -OEt (ethoxy), -O(nPr) (n-propoxy), -O(iPr) (isopropoxy), -O(nBu) (n-butoxy), -O(sBu) (sec-butoxy), -O(iBu) (isobutoxy), and -O(tBu) (tert-butoxy). 1-20 Other examples of alkoxy groups are -O (adamantyl), -O-CH2-adamantyl, and -O-CH2-CH2-adamantyl.

[0085] An aryl group is a substituted or unsubstituted aryl group attached to an oxygen atom as defined herein. An example of an aryl group is -OPh (phenoxy group).

[0086] As used herein, the amino group is a group of formula -NR2, where each R is a substituent. R is typically selected from hydrogen, alkyl, alkenyl, cycloalkyl, or aryl, where alkyl, alkenyl, cycloalkyl, and aryl are each as defined herein. Typically, each R is selected from hydrogen, C... 1-10 Alkyl, C 2-10 alkenyl and C 3-10 Cycloalkyl. Preferably, each R is selected from hydrogen, C… 1-6 Alkyl, C 2-6 alkenyl and C 3-6 Cycloalkyl. More preferably, each R is selected from hydrogen and C. 1-6 Alkyl group. Most preferably, each R is hydrogen.

[0087] Typical amino groups are alkylamino groups, which are groups of the formula -NR2, wherein at least one R is an alkyl group as defined herein. C 1-6 Alkylamino is one of them where at least one R is C 1-6 Alkyl amino groups of alkyl groups.

[0088] As used herein, an imino group is a group of the formula R2C=N- or -C(R)=NR, where each R is a substituent. That is, an imino group is a group containing a C=N moiety, which is located at or attached to the C atom of the N atom in the C=N bond. R is as defined herein: that is, R is generally selected from hydrogen, alkyl, alkenyl, cycloalkyl, or aryl, where each of alkyl, alkenyl, cycloalkyl, and aryl is as defined herein. Typically, each R is selected from hydrogen, C... 1-10 Alkyl, C 2-10 alkenyl and C 3-10 Cycloalkyl. Preferably, each R is selected from hydrogen, C… 1-6 Alkyl, C 2-6 alkenyl and C 3-6 Cycloalkyl. More preferably, each R is selected from hydrogen and C. 1-6 alkyl.

[0089] Typical imino groups are alkylimino groups, which are groups of the formula R2C=N- or -C(R)=NR, wherein at least one R is an alkyl group as defined herein. 1-6 Alkylimino is an alkylimino in which the R substituent contains 1 to 6 carbon atoms.

[0090] As used herein, the term "ether" refers to an oxygen atom substituted by two alkyl groups as defined herein. The alkyl groups may be optionally substituted and may be the same or different.

[0091] As used herein, the term "ammonium ion" refers to an organic cation containing quaternary nitrogen. An ammonium cation is an organic cation of formula R... 1 R 2 R 3 R 4 N + The cation. R 1 R 2 R 3 and R 4 It is a substituent. R 1 R 2 R 3 and R 4 Each is typically selected independently from hydrogen, or optionally from substituted alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, and amino groups; the optional substituents are preferably amino or imino substituents. Typically, R 1 R 2 R 3 and R 4 Each is independently selected from hydrogen, and optionally from substituted C. 1-10 Alkyl, C 2-10 alkenyl, C 3-10 cycloalkyl, C 3-10 cycloalkyl, C 6-12 Aryl and C1-6 Amino group; if present, the optional substituent is preferably amino; particularly preferred is C. 1-6 Amino group. Preferably, R 1 R 2 R 3 and R 4 Each is independently selected from hydrogen and unsubstituted C. 1-10 Alkyl, C 2-10 alkenyl, C 3-10 cycloalkyl, C 3-10 cycloalkyl, C 6-12 Aryl and C 1-6 Amino. In a particularly preferred embodiment, R 1 R 2 R 3 and R 4 Independently selected from hydrogen and C 1-10 Alkyl, C 2-10 alkenyl and C 1-6 Amino group. More preferably, R 1 R 2 R 3 and R 4 Independently selected from hydrogen and C 1-6 Alkyl, C 2-6 alkenyl and C 1-6 Amino.

[0092] As used herein, the term "iminium" is expressed as (R... 1 R 2 C=NR 3 R 4 ) + Organic cations, of which R 1 R 2 R 3 and R 4 As defined with respect to ammonium cations. Therefore, in a particularly preferred embodiment of an imine cation, R 1 R 2 R 3 and R 4 Independently selected from hydrogen and C 1-10 Alkyl, C 2-10 alkenyl and C 1-6 Amino. In a further preferred embodiment of the imine cation, R 1 R 2 R 3 and R 4 Independently selected from hydrogen and C 1-6 Alkyl, C 2-6 alkenyl and C 1-6 Amino group. Typically, the imine cation is formamidinium, i.e., R...1 It is NH2, and R 2 R 3 and R 4 Both are H.

[0093] As used herein, the term "sensitizer" refers to a material capable of photoinduced charge generation, photoemission, or electroemission. Typically, sensitizers are also capable of transporting charge (holes or electrons). For example, when the sensitizer is the A / M / X material, it is typically also capable of transporting charge.

[0094] This invention provides a photovoltaic device comprising passivated A / M / X material. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0095] The term "silane moiety" as used in this article refers to the moiety containing four substituents R. sil The silicon atom portion. The four R atoms in the silane moiety. sil Each substituent can be independently selected from inorganic groups, such as H, OH, and halogens; and organic groups, such as alkyl, aryl, alkoxy, acyl, ester, and acyloxy groups, each of which can be unsubstituted or substituted. Sometimes, the four R groups... sil One or more of the substituents contain another silane moiety. For example, R sil The basic body can be replaced by OSiR. Sil The 3' group. Typically, the four R's of the silane moiety... sil Each substituent is independently an H or an organic group; more typically, each R...sil These are organic groups. For example, the four R groups in the silane moiety. sil The substituents can each be independently selected from alkoxy and alkyl groups, and the alkoxy and alkyl groups can each be unsubstituted or substituted.

[0096] In this invention, R in the silane portion sil Substituents can be groups that, together with the silicon atoms to which they are bonded, constitute an organic compound containing a silane moiety acting as a passivating agent. Any primary, secondary, tertiary, or quaternary amine moiety present in the organic compound can be an R group of the silane moiety. sil Part of the substituent.

[0097] As used herein, “amine moiety” refers to the portion in which a nitrogen atom is bonded to at least one group other than hydrogen, which is a primary amine, secondary amine, tertiary amine, or quaternary amine as defined below. Each group in the amine moiety other than hydrogen is typically an organic group, such as an alkyl or aryl group, which may be unsubstituted or substituted.

[0098] As used herein, "primary amine" refers to a portion in which nitrogen is bonded to a group other than hydrogen and two hydrogen atoms, or, if the primary amine portion is protonated, to three hydrogen atoms. Therefore, the primary amine portion has the formula RNH2 or RNH3. + In this system, R is a group other than hydrogen. The group other than hydrogen is usually an organic group, such as an alkyl or aryl group, which can be unsubstituted or substituted.

[0099] As used herein, "secondary amine" refers to the portion in which nitrogen is bonded to two groups other than hydrogen and one hydrogen atom, or, if the secondary amine moiety is protonated, to two hydrogen atoms. Therefore, the secondary amine moiety has the formula R₂NH or R₂NH₂. + In this amine moiety, R is a group other than hydrogen. These groups are typically organic groups, such as alkyl or aryl groups, which can be unsubstituted or substituted. Two groups other than hydrogen may optionally bond to each other to form a ring with the nitrogen from the secondary amine moiety (but this is not usually the case).

[0100] As used herein, "tertiary amine" refers to the portion in which nitrogen is bonded to three groups other than hydrogen and not to a hydrogen atom, or, if the tertiary amine moiety is protonated, to a hydrogen atom. Therefore, the tertiary amine moiety has the formula R3N or R3NH. + In this amine moiety, R is a group other than hydrogen. These groups are typically organic groups, such as alkyl or aryl groups, which may be unsubstituted or substituted. Any one of the three groups other than hydrogen may optionally bond to another group other than hydrogen, forming a ring together with the nitrogen from the tertiary amine moiety.

[0101] The term "quaternary ammonium" as used in this article refers to the cationic moiety in which nitrogen is bonded to four groups other than hydrogen. Therefore, the quaternary ammonium moiety has the formula R4N. + In this amine moiety, R is a group other than hydrogen. These groups are typically organic groups, such as alkyl or aryl groups, which may be unsubstituted or substituted. Any one of the four groups other than hydrogen may optionally bond to another group other than hydrogen, forming a ring together with the nitrogen from the tertiary amine moiety.

[0102] In this invention, one or more groups other than hydrogen in the primary, secondary, tertiary, or quaternary amine moiety can be groups that, together with the nitrogen atom to which they are bonded and any hydrogen atom to said nitrogen atom, constitute an organic compound containing a silane moiety. The silane moiety can be a part of said groups other than hydrogen.

[0103] As described above, the passivating agent of the present invention comprises an organic compound. Typically, the organic compound comprises a silane moiety and an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. The organic compound may comprise a silane moiety and multiple amine moieties, wherein at least one of the amine moieties is a secondary, tertiary, or quaternary amine. The organic compound may comprise a silane moiety and two to five amine moieties, for example, two, three, four, or five amine moieties, wherein at least one of the amine moieties is a secondary, tertiary, or quaternary amine. Typically, when the organic compound comprises multiple amine moieties and at least one of the amine moieties is a secondary, tertiary, or quaternary amine, there are also cases where at least one of the amine moieties is a primary amine. Typically, when the organic compound comprises multiple amine moieties, at least one of the amine moieties is a primary amine, and the other amine moieties are each independently selected from secondary, tertiary, and quaternary amines. Preferably, one of the amine moieties is a primary amine, and the other amine moieties are each secondary amines.

[0104] Typically, when an organic compound contains an amine moiety, the organic compound contains an organic group bonded to a silicon atom of a silane moiety, wherein each of the amine moieties is present in the organic group. In this embodiment, the organic group is typically C 1-20 Alkyl groups, wherein each amine moiety, which is a secondary, tertiary, or quaternary amine, can interrupt C. 1-20 The carbon chain of an alkyl group, or present as a substituent at C10. 1-20 On an alkyl group, and wherein any amine moiety of a primary amine exists as a substituent at C. 1-20 On alkyl groups. The C 1-20 Alkyl groups can be, for example, C10. 1-10 Alkyl group. C 1-20 Alkyl (or C) 1-10Alkyl groups can be either otherwise unsubstituted or substituted. In other words, apart from any amine moiety present on the alkyl group as a substituent, the alkyl group can be unsubstituted (“otherwise unsubstituted”) or substituted (“otherwise substituted”). For example, organic groups (typically referred to as C...) 1-20 Or C 1-10 Alkyl groups can also be selected from thiols, C 1-10 One or more groups of alkylthio, arylthio, carboxyl, pyridyl, and bipyridyl can be substituted. Therefore, in addition to any amine moiety present as a substituent on the alkyl group, the alkyl group can also be selected from thiols, C... 1-10 One or more groups of alkylthio, arylthio, carboxyl, pyridyl, and bipyridyl are substituted.

[0105] Organic compounds can be, for example, according to formula (I) (I) in: R is the organic group; and E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted C 1-10 Alkyl, unsubstituted or substituted aryl, unsubstituted or substituted acyl, unsubstituted or substituted ester, unsubstituted or substituted acyloxy, hydroxyl and halogen.

[0106] Typically, in compounds of formula (I), the group R is C 1-20 Alkyl groups, wherein each amine moiety, which is a secondary, tertiary, or quaternary amine, can interrupt C. 1-20 The carbon chain of an alkyl group may exist as a substituent at C1. 1-20 On an alkyl group, and wherein any amine moiety of a primary amine exists as a substituent at C. 1-20 On an alkyl group, and wherein C 1-20 The alkyl group is either unsubstituted or substituted (e.g., as mentioned above, it can be selected from thiols, C...). 1-10 (Substitution with one or more groups of alkylthio, arylthio, carboxyl, pyridyl, and bipyridyl). Typically, in compounds of formula (I), group R is C. 1-10 Alkyl groups, wherein each amine moiety, which is a secondary, tertiary, or quaternary amine, can interrupt C. 1-10 The carbon chain of an alkyl group may exist as a substituent at C1. 1-10 On an alkyl group, and wherein any amine moiety of a primary amine exists as a substituent at C. 1-10 On an alkyl group, and wherein C 1-10 The alkyl group is either unsubstituted or substituted (e.g., it may be additionally selected from thiols, C...).1-10 (Substitution with one or more groups of alkylthio, arylthio, carboxyl, pyridyl, and bipyridyl).

[0107] Typically, E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted C 1-10 Alkyl groups, unsubstituted or substituted aryl groups, and unsubstituted or substituted aryl groups. Group E 1 E 2 and E 3 Typically, it is unsubstituted or substituted C 1-10 Alkoxy groups, such as unsubstituted C4 groups 1-10 Alkoxy group. E group 1 E 2 and E 3 It can be, for example, unsubstituted or substituted C. 1-6 Alkoxy, or unsubstituted or substituted C 1-4 Alkyl groups. Typically, these alkoxy groups are unsubstituted. E 1 E 2 and E 3 It can be selected independently, for example, from ethoxy and methoxy. For example, E 1 E 2 and E 3 Each can be a methoxy group.

[0108] Typically, organic compounds have formula (II). (II) in: E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted C 1-10 Alkyl, unsubstituted or substituted aryl, unsubstituted or substituted acyl, unsubstituted or substituted ester, unsubstituted or substituted acyloxy, hydroxyl and halogen; q is 0 or an integer from 1 to 5; Each m is an independent integer from 1 to 5; Each n is independently 0 or 1; p is 0 or an integer from 1 to 5; G is NR 1 2 or CR 1 3; Each R 1 Independently, it is H, or unsubstituted or substituted C. 1-6Alkyl (and usually H or unsubstituted C) 1-6 Alkyl groups, such as H, methyl, or ethyl groups); Where each n is 0 and G is NR 1 2, or when q is 0 and G is NR 1 2, then at least one R 1 The group is an unsubstituted or substituted C 1-6 alkyl.

[0109] Typically, in compounds of formula (II), E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted C 1-10 Alkyl groups, unsubstituted or substituted aryl groups, and unsubstituted or substituted aryl groups. Group E 1 E 2 and E 3 Typically, it is unsubstituted or substituted C 1-10 Alkoxy groups, such as unsubstituted C4 groups 1-10 Alkoxy group. E group 1 E 2 and E 3 It can be, for example, unsubstituted or substituted C. 1-6 Alkoxy, or unsubstituted or substituted C 1-4 Alkyl groups. Typically, these alkoxy groups are unsubstituted. E 1 E 2 and E 3 It can be selected independently, for example, from ethoxy and methoxy.

[0110] Typically, E 1 E 2 and E 3 At least one of them is a methoxy group. Preferably, E 1 E 2 and E 3 At least two of them are methoxyl groups. More preferably, E 1 E 2 and E 3 They are all methoxyl groups.

[0111] Typically, in compounds of formula (II), when G is NR 1 2. If q is not 0, then p is not 0. Typically, in compounds of formula (II), G is NR. 1 2.

[0112] Typically, in compounds of formula (II), each R 1 Independently, it is H or methyl. Preferably, each R 1It's H.

[0113] Typically, in compounds of formula (II), q is 0, 1, or 2. Typically, q is 1 or 2. Alternatively, q is 0. For example, q can be 0. Alternatively, q can be 1. Alternatively, q can be 2.

[0114] Typically, in the compounds of formula (II), q is an integer from 1 to 5, each m is independently 1, 2 or 3, and each n is 1. Preferably, q is 1 or 2, each m is 2, and each n is 1.

[0115] Typically, in compounds of formula (II), p is an integer from 1 to 5. For example, p is usually 1. However, p is also usually 2. In other typical cases, p is 3. p can be, for example, 4. In other cases, p can be 5. However, p is usually 1, 2, 3, or 4. Preferably, p is 1, 2, or 3.

[0116] In this invention, the organic compounds are preferably selected from: (i) PTMS ; (ii) MAPTMS ; (iii) DMAPTMS ; (iv) AEAPTMS ; And (v)(AE)2APTMS .

[0117] More preferably, the organic compound is selected from (ii) MAPTMS, (iii) DMAPTMS, (iv) AEAPTMS and (v) (AE)2APTMS.

[0118] Typically, the organic compounds are selected from AEAPTMS and (AE)2APTMS.

[0119] Organic compounds are typically AEAPTMS. However, the typical organic compound is (AE)2APTMS.

[0120] Passivating agents may include dimers or polymers of organic compounds. The dimer of the organic compound may comprise (i) a first monomer unit, wherein the first monomer unit is an organic compound as defined above, provided that the silicon atom of the silane portion of the first monomer unit is replaced by a linking atom or group; and (ii) a second monomer unit, wherein the second monomer unit is an organic compound as defined above, provided that the silicon atom of the silane portion of the second monomer unit is replaced by a linking atom or group, wherein the linking atom or group is covalently bonded to the silicon atom of the silane portion of the first monomer unit and covalently bonded to the silicon atom of the silane portion of the second monomer unit to link the first monomer unit to the second monomer unit.

[0121] The first monomer unit can be an organic compound of formula (I) or formula (II) as defined above, provided that the E of the first monomer unit is... 1 E 2 and E 3 One of them is the connecting atom or group, and the second monomer unit can be an organic compound of formula (I) or formula (II) as defined above, provided that the E of the second monomer unit is... 1 E 2 and E 3 One of them is the connecting atom or group.

[0122] Dimers can have the following formula (Ia): (Ia) Where L is the connecting atom or group, and each R, E 1 and E 2 Independently as defined above. (As defined above, each R is an organic group, wherein each of the amine moieties is present in the organic group.) Dimers can, for example, have formula (IIa):

[0123] (IIa) Where L is the connecting atom or group, and each G, p, n, m, q, E 1 and E 2 Independently as defined above. In dimers of formula (Ia) or (IIa), the linking atom or group is usually the linking atom.

[0124] Typically, L is a connecting atom, such as a divalent atom, such as an oxygen atom, a sulfur atom, or a selenium atom. Usually, when L is a connecting atom, the connecting atom is an oxygen atom.

[0125] L can be a linking group, such as an unsubstituted or substituted alkylene, or an unsubstituted or substituted arylene, or a group -OQ-, OQO-, -QQ-, or -QQQ-, where O is an oxygen atom and each Q is an unsubstituted or substituted alkylene, or an unsubstituted or substituted arylene. Typically, the alkylene or each alkylene is an unsubstituted or substituted C1-C6 alkylene, more typically an unsubstituted C1-C6 alkylene, such as butylene, propylene, or ethylene. Those skilled in the art will understand that an arylene is a divalent aryl group, wherein the aryl group is as defined above. An arylene can be, for example, an unsubstituted or substituted phenylene, such as an unsubstituted phenylene.

[0126] Polymers of organic compounds may comprise monomer units that are organic compounds as defined above, provided that the silicon atom of the silane moiety is replaced by at least one linking atom or group, wherein the linking atom or group, or each linking atom or group, is covalently bonded to the silicon atom and also covalently bonded to the silane atom of the silane moiety of another monomer unit in the polymer. The monomer unit is typically an organic compound of formula (I) or formula (II) as defined above, provided that E... 1 E 2 and E 3 At least one of them is the connecting atom or group, typically wherein E 1 E 2 and E 3 Both of these are the connecting atoms or groups. Each connecting atom or group can be further defined above for dimers of formulas (Ia) and (IIa). Typically, each connecting atom or group is a connecting atom, such as an oxygen atom.

[0127] Typically, the polymeric units of organic compounds contain the monomeric unit of formula (Ib): (Ib) Where L is the connecting atom or group, and R and E 1 As defined above. (As defined above, R is an organic group, wherein each of the amine moieties is present in the organic group.) Typically, the polymer contains at least three monomer units of formula (Ib), for example, 3 to 1000, or 3 to 100, for example, 3 to 50, or 1 to 20, for example, 3 to 10, or 2 to 5 monomer units of formula (Ib).

[0128] Typically, for example, polymers of organic compounds contain monomer units of formula (IIb): (IIb) Wherein L is the connecting atom or group, and G, p, n, m, q and E1 are as described above. Typically, the polymer contains at least three monomer units of formula (IIb), for example 3 to 1000, or 3 to 100, for example 3 to 50, or 3 to 20, for example 3 to 10, or 3 to 5 monomer units of formula (IIb).

[0129] Typically, polymer inclusion (Ic) structures are: (Ic) Where each L is the connecting atom or group, and each R and E 1 Independently as defined above, and z is an integer of at least 3. (As defined above, each R is an organic group, wherein each of the amine moieties is present in the organic group.) The integer z can be, for example, 3 to 1000, or 3 to 100, such as 3 to 50, or 3 to 20, such as 3 to 10, or 3 to 5.

[0130] Typically, for example, the polymer inclusion formula (IIc) structure: (IIc) Where each L is the connecting atom or group, and each G, p, n, m, q, and E 1 Independently as defined above, and z is an integer of at least 3. The integer z can be, for example, 3 to 1000, 3 to 100, or, for example, 3 to 50, or 3 to 20, or, for example, 3 to 10, or 3 to 5.

[0131] In this invention, the passivating agent can be disposed on the surface of the crystalline A / M / X material.

[0132] Photovoltaic devices may include layers containing passivated A / M / X materials. The layer containing passivated A / M / X material may include (i) a crystalline A / M / X material layer and (ii) a passivating agent. The passivating agent may be disposed on the surface of the crystalline A / M / X material layer. The passivating agent may penetrate into the crystalline A / M / X material layer to a depth beyond the surface of the crystalline A / M / X material layer. The passivating agent may, for example, be disposed on the surface of the crystalline A / M / X material layer and penetrate into the crystalline A / M / X material layer to a depth below the surface. This depth may be, for example, at most about 140 nm, or at most about 120 nm, or at most about 100 nm, or at most about 80 nm. The depth may, for example, be from about 10 nm to about 140 nm, for example, from about 20 nm to about 120 nm, or from about 30 nm to about 100 nm, or from about 40 nm to about 90 nm. Typically, the depth is about 70 nm.

[0133] The layer containing passivated A / M / X material may include (i) a crystalline A / M / X material layer and (ii) a passivating agent layer disposed on the surface of the crystalline A / M / X material layer. A layer containing passivated A / M / X material can be substantially composed of passivated A / M / X material. A layer comprising passivated A / M / X material may include a crystalline A / M / X material layer and the passivating agent permeated into the surface of the crystalline A / M / X material layer. The passivating agent may permeate into the surface of the crystalline A / M / X material layer. It may permeate into the surface of the crystalline A / M / X material layer up to a certain distance beyond the surface. The passivating agent may, for example, permeate into the surface of the crystalline A / M / X material layer up to about 140 nm (meaning up to about 140 nm beyond the surface), or up to about 120 nm, or up to about 100 nm, or up to about 80 nm. Typically, the passivating agent permeates into the surface of the crystalline A / M / X material layer up to about 70 nm. The passivating agent may, for example, permeate into the surface of the crystalline A / M / X material layer from about 10 nm to about 140 nm, for example, from about 20 nm to about 120 nm, or from about 30 nm to about 100 nm, or from about 40 nm to about 90 nm, for example, from about 70 nm.

[0134] The layer containing passivated A / M / X material may include passivated A / M / X material particles. Each passivated A / M / X material particle may include (a) crystalline A / M / X material particles and (b) the passivating agent disposed on the surface of the crystalline A / M / X material.

[0135] The thickness of the layer containing the passivated A / M / X material can be from about 10 nm to about 100 μm, or from about 10 nm to about 10 μm, or from about 100 nm to about 1000 nm.

[0136] When a photovoltaic device includes a layer comprising a passivated A / M / X material, the device may include a photoactive region comprising an n-type region comprising at least one n-type layer, a p-type region comprising at least one p-type layer, and a passivated A / M / X material layer disposed between the n-type region and the p-type region. Typically, the photoactive region is disposed between a first electrode and a second electrode.

[0137] The first electrode may include a metal (e.g., silver, gold, aluminum, copper, molybdenum, or tungsten), an organic conductive material (such as PEDOT:PSS), or a transparent conductive oxide (e.g., fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), zinc-doped indium oxide (IZO), or tin-doped indium oxide (ITO)). However, typically, the first electrode is a transparent electrode. Therefore, the first electrode typically comprises a transparent conductive oxide, preferably FTO, ITO, IZO, or AZO. Typically, the first electrode is tin-doped indium oxide (ITO). The thickness of the first electrode layer is typically from 10 nm to 1000 nm, and more typically from 40 nm to 400 nm.

[0138] The second electrode can be as defined above for the first electrode. For example, the second electrode can include a metal (e.g., silver, gold, aluminum, or tungsten), an organic conductive material (such as PEDOT:PSS), or a transparent conductive oxide (e.g., fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), zinc-doped indium oxide (IZO), or tin-doped indium oxide (ITO)). However, typically, the second electrode comprises or is substantially composed of a metal, such as an elemental metal (in which case the first electrode is typically a transparent electrode, as described above). Examples of metals that can comprise or are substantially composed of the second electrode material include silver, gold, copper, molybdenum, aluminum, platinum, palladium, or tungsten. The second electrode can be arranged by vacuum evaporation. The thickness of the second electrode material layer is typically from about 10 nm to about 1000 nm, preferably from about 50 nm to about 150 nm.

[0139] The second electrode may optionally include a further layer comprising a metal (e.g., Cr) or a metal oxide (e.g., Cr₂O₃), typically a layer comprising Cr or a mixture of chromium and chromium(III) oxide (Cr / Cr₂O₃). The thickness of this further layer is typically between 1 nm and 10 nm.

[0140] Typically, the second electrode comprises a gold layer and a chromium layer. Optionally, the thickness of the gold layer can be from about 50 nm to about 150 nm. Optionally, the thickness of the chromium layer can be from about 1 nm to about 10 nm.

[0141] Examples of electron transport (n-type) materials are known to those skilled in the art. Suitable n-type materials can be organic or inorganic. Suitable inorganic n-type materials can be selected from metal oxides, metal sulfides, metal selenides, metal tellurides, perovskites, amorphous Si, n-type group IV semiconductors, n-type group III-V semiconductors, n-type group II-VI semiconductors, n-type group I-VII semiconductors, n-type group IV-VI semiconductors, n-type group V-VI semiconductors, and n-type group II-V semiconductors, any of which may be doped or undoped. More typically, n-type materials are selected from metal oxides, metal sulfides, metal selenides, and metal tellurides.

[0142] Therefore, the n-type layer may comprise an inorganic material selected from oxides of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or oxides of mixtures of two or more of these metals. For example, the n-type layer may comprise TiO2, SnO2, ZnO, Nb2O5, Ta2O5, WO3, W2O5, In2O3, Ga2O3, Nd2O3, PbO, or CdO.

[0143] Other suitable n-type materials that may be used include sulfides of cadmium, tin, copper, or zinc, including sulfides of mixtures of two or more of the aforementioned metals. For example, the sulfide may be FeS2, CdS, ZnS, SnS, BiS, SbS, or Cu2ZnSnS4. The n-type layer may, for example, comprise a selenide of cadmium, zinc, indium, or gallium, or a selenide of a mixture of two or more of said metals; or a telluride of cadmium, zinc, cadmium, or tin, or a telluride of a mixture of two or more said metals. For example, the selenide may be Cu(In,Ga)Se2. Typically, the telluride is a telluride of cadmium, zinc, cadmium, or tin. For example, the telluride may be CdTe.

[0144] The n-type layer may, for example, comprise an inorganic material selected from the following: oxides of titanium (e.g., TiO2), tin (e.g., SnO2), zinc (e.g., ZnO), niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, cadmium, or oxides of mixtures of two or more of the aforementioned metals; sulfides of cadmium, tin, copper, zinc, or sulfides of mixtures of two or more of the aforementioned metals; selenides of cadmium, zinc, indium, gallium, or selenides of mixtures of two or more of the aforementioned metals; or tellurides of cadmium, zinc, cadmium, or tin, or tellurides of mixtures of two or more of the aforementioned metals.

[0145] For example, if they are n-doped, other examples of suitable n-type materials include group IV element or compound semiconductors; amorphous silicon; group III-V semiconductors (e.g., gallium arsenide); group II-VI semiconductors (e.g., cadmium selenide); group I-VII semiconductors (e.g., cuprous chloride); group IV-VI semiconductors (e.g., lead selenide); group V-VI semiconductors (e.g., bismuth telluride); and group II-V semiconductors (e.g., cadmium arsenide). Other n-type materials can also be used, including organic and polymeric electron transport materials and electrolytes. Suitable examples include, but are not limited to, fullerenes or fullerene derivatives (e.g., C). 60 C 70 , phenyl-C 61 methyl butyrate (PCBM, also referred to herein as PC) 61 BM), PC 71 BM (i.e., phenyl C) 71 Methyl butyrate), bis[C] 60 ]BM (i.e., double-C 60 Methyl butyrate) and 1′,1′′,4′,4′′-tetrahydro-bis[1,4]methylenenaphthalo[1,2,2′,3′,56,60:2′′,3′′][5,6]fullerene-C 60 (ICBA)); organic electron transport materials including perylene or its derivatives; poly{[N,NO-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboxyimide)-2,6-diyl]-alt-5,50-(2,20-bithiophene)} (P(NDI2OD-T2)); or copper bath (BCP).

[0146] Typically, n-type materials are methyl phenyl-C61-butyrate (PCBM) or C... 60 Typically, when using PCBMs, they are deposited as a solution phase. Typically, when using C... 60 At that time, it was deposited in the gas phase through vacuum evaporation.

[0147] Typically, BCP is used as an additional n-type material in n-type layers. Therefore, PCBMs are often used in combination with BCPs, or C... 60 Use in combination with BCP.

[0148] Examples of hole-transporting (p-type) materials are known to those skilled in the art. P-type materials can be a single p-type compound or element, or a mixture of two or more p-type compounds or elements, and can be undoped or doped with one or more doping elements.

[0149] p-type materials can include inorganic or organic p-type materials. For example, p-type materials can be organic p-type materials.

[0150] Suitable p-type materials can be selected from polymers or molecular transporters. Examples of p-type materials include, for instance, spiro-OMeTAD (2,2′,7,7′-tetra-(N,N-di-p-methoxyaniline)9,9′-spirodifluorene), P3HT (poly(3-hexylthiophene)), PCPDTBT (poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl]]), PVK (poly(N-vinylcarbazole)), HTM-TFSI (1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide), Li-TFSI (lithium bis(trifluoromethanesulfonyl)imide), and spiro-OMETAD. + -Bis(trifluoromethanesulfonyl)imine - (spiro(TFSI)2), tBP (tert-butylpyridine), m-MTDATA (4,4′,4′′-tris(methylphenylamino)triphenylamine), MeOTPD (N,N,N′,N′-tetra(4-methoxyphenyl)-benzidine), BP2T (5,5′-bis(biphenyl-4-yl)-2,2′-bithiophene), Di-NPB (N,N′-bis-[(l-naphthyl)-N,N′-diphenyl]-1,l′-biphenyl)-4,4′-diamine), α-NPB (N,N′-bis(naphthyl-1-yl)-N,N′-diphenyl-benzidine), TNATA (4,4′,4′′-tris(N-(naphthyl-2-yl)-N-aniline)triphenylamine), BPAP F (9,9-bis[4-(N,N-bisphenyl-4-yl-amino)phenyl]-9H-fluorene), spiro-NPB (N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9′-spirobis[9H-fluorene]-2,7-diamine), 4P-TPD (4,4-bis(N,N-diphenylamino)-tetraphenyl), polyTPD (i.e., poly[N,N′-bis(4-butylphenyl)-N,N]-bisphenylbenzidine]), Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid), PTAA (i.e., poly(triarylamine), also known as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]), or PEDOT:PSS. p-type materials may include carbon nanotubes. Typically, p-type materials are selected from spiro-OMeTAD, P3HT, PCPDTBT, polyTPD, Me-4PACz, spiro(TFSI)2, and PVK. In one embodiment, the p-type material is Me-4PACz.

[0151] Suitable p-type materials also include molecular hole transporters, polymeric hole transporters, and copolymeric hole transporters. P-type materials can be, for example, molecular hole transport materials comprising one or more of the following polymers or copolymers: thiophene, phenelenyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrole, ethoxydithiophene, amino, triphenylamino, carbazole, ethylenedioxythiophene, dioxythiophene, or fluorene.

[0152] p-type materials can be doped, for example with tert-butylpyridine and LiTFSI. Doping can increase the hole density of p-type materials. For example, p-type materials can be doped with NOBF4 (nitroso tetrafluoroborate) or 1,3,4,5,7,8-hexafluorotetracyanonaphthoquinone dimethyl ether (F6TCNNQ) to increase the hole density.

[0153] Hole transport materials (p-type materials) can be solid-state inorganic hole transport materials. For example, a p-type layer can contain inorganic hole transporters, including oxides of nickel (e.g., NiO), vanadium, copper, or molybdenum; CuI, CuBr, CuSCN, Cu2O, CuO, or CIS; perovskite; amorphous silicon; p-type group IV semiconductors, p-type group III-V semiconductors, p-type group II-VI semiconductors, p-type group I-VII semiconductors, p-type group IV-VI semiconductors, p-type group V-VI semiconductors, and p-type group II-V semiconductors, wherein the inorganic material may be doped or undoped. The p-type layer can be a dense layer of the inorganic hole transporter.

[0154] p-type materials can be inorganic p-type materials, such as materials including: oxides of nickel, vanadium, copper, or molybdenum; CuI, CuBr, CuSCN, Cu2O, CuO, or CIS; amorphous silicon; p-type group IV semiconductors, p-type group III-V semiconductors, p-type group II-VI semiconductors, p-type group I-VII semiconductors, p-type group IV-VI semiconductors, p-type group V-VI semiconductors, and p-type group II-V semiconductors, wherein the inorganic material may be doped or undoped. p-type materials may, for example, include inorganic hole transporters selected from CuI, CuBr, CuSCN, Cu2O, CuO, and CIS.

[0155] Typically, the hole transport (p-type) material layer is a solid-state inorganic hole transport material, including oxides of nickel, vanadium, copper, or molybdenum. The solid-state inorganic hole transport material usually exists in the form of a dense layer. For example, the solid-state inorganic hole transport material may include nickel oxide. For instance, optoelectronic devices may include a dense nickel oxide layer. A layer containing crystalline A / M / X materials can be disposed, for example, directly on the hole transport (p-type) material layer, such as on a layer containing solid-state inorganic hole transport materials (including nickel oxide), preferably on a dense nickel oxide layer.

[0156] However, typically, p-type regions contain Me-4PACz.

[0157] Typically, the p-type region contains Me-4PACz, and the n-type region contains phenyl-C. 61 -Methyl butyrate (PCBM) or C 60 Typically, an n-type region also contains a BCP. Therefore, an n-type region can contain a PCBM and a BCP, or a C 60 And BCP.

[0158] The device of the present invention comprises a passivated A / M / X material, which includes a passivating agent and a crystalline A / M / X material. The crystalline A / M / X material is typically a semiconductor. The crystalline A / M / X material comprises formula [A]. a [M] b [X] c A compound wherein: [A] comprises one or more A cations; [M] comprises one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] comprises one or more X anions; a is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18. a is typically a number from 1 to 4, b is typically a number from 1 to 3, and c is typically a number from 1 to 8.

[0159] Each of a, b, and c can be an integer or not. For example, in a compound employing a structure with vacancies, such that the lattice is not fully filled, a, b, or c may not be integers. In the production of A / M / X materials, providing very good control over their stoichiometry is straightforward, thus easily forming structures where a, b, or c are not integers (e.g., structures with vacancies in one or more of the A, M, or X sites) and structures where a, b, and c are all integers. Therefore, in some embodiments, one or more of a, b, and c are non-integer values. For example, one of a, b, and c may be a non-integer value. In one embodiment, a is a non-integer value. In another embodiment, b is a non-integer value. In yet another embodiment, c is a non-integer value.

[0160] In other implementations, each of a, b, and c is an integer value. Thus, in some implementations, a is an integer from 1 to 6; b is an integer from 1 to 6; and c is an integer from 1 to 18. a is typically an integer from 1 to 4, b is typically an integer from 1 to 3, and c is typically an integer from 1 to 8.

[0161] In formula [A] a [M] b [X] c In compounds, typically: [A] contains one or more A cations, which may be selected, for example, from alkali metal cations or organic monovalent cations; [M] comprises one or more M cations, wherein the M cations are metal or near-metal cations selected from the following: Pd 4+ W 4+ Re 4+ Os 4+ Ir 4+ Pt 4+ Sn 4+ Pb 4+ 、Ge 4+ Te 4+ Bi 3+ Sb 3+ Ca 2+ 、Sr 2+ Cd 2+ Cu 2+ Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd 2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ and Eu 2+ Sn is preferred 2+ Pb 2+ 、Ge 2+ and Ni 2+ Pb is particularly preferred. 2+ and Sn 2+ ; [X] contains one or more X anions, said X anions are selected from halogen anions (e.g., Cl-). - ,Br - and I - ), O 2- S 2- Se 2- and Te 2- ; 'a' is a number from 1 to 4; b is a number from 1 to 3; and c is a number from 1 to 8.

[0162] Preferably, formula [A] a [M] b [X] c The compounds include perovskites. Formula [A] a [M] b [X] cThe compounds typically include metal halide perovskites, such as organic-inorganic metal halide perovskites.

[0163] [M] cation [M] comprises one or more M cations, wherein the M cations are metal or quasi-metal cations. [M] may comprise two or more different M cations. [M] may comprise one or more monovalent cations, one or more divalent cations, one or more trivalent cations, or one or more tetravalent cations.

[0164] Typically, one or more M cations are selected from Ca 2+ 、Sr 2+ Cd 2+ Cu 2+ Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd 2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ Eu 2+ Bi 3+ Sb 3+ Pd 4+ W 4+ Re 4+ Os 4+ Ir 4+ Pt 4+ Sn 4+ Pb 4+ 、Ge 4+ Or Te 4+ Preferably, the one or more M cations are selected from Cu. 2+ Pb 2+ 、Ge 2+ or Sn 2+ .

[0165] Typically, [M] contains one or more metal or near-metal divalent cations. For example, each M cation can be selected from Ca... 2+ 、Sr 2+ Cd 2+ Cu 2+ Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd 2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ and Eu2+ Sn is preferred 2+ Pb 2+ Cu 2 + 、Ge 2+ and Ni 2+ Sn is preferred 2+ and Pb 2+ In some embodiments, [M] comprises two different M cations, typically said cation is Sn. 2+ and Pb 2+ .

[0166] [A] cation and [X] anion Generally, the one or more A cations are monovalent cations. [A] typically contains one or more A cations, which can be organic and / or inorganic monovalent cations. For example, [A] may contain at least two A cations, which can be organic and / or inorganic monovalent cations. Therefore, formula [A] a [M] b [X] c The compound can be a mixed cationic perovskite. [A] may contain at least one A cation that is an organic cation and at least one A cation that is an inorganic cation. [A] may contain at least two cations that are both organic A cations. [A] may contain at least two A cations that are both inorganic cations.

[0167] When species A is an inorganic monovalent cation, A is usually an alkali metal monovalent cation (i.e., a monovalent cation of a metal located in Group 1 of the periodic table), such as Li. + Na + K + 、Rb + Cs + For example, Cs + or Rb + For example, Cs + Typically, [A] contains at least one organic monovalent cation. When A is an organic monovalent cation, A is typically an ammonium cation, such as methylammonium ion, or an imine cation, such as formamidinium ion.

[0168] Each type of A cation can be selected from: alkali metal cations, such as Li + Na + K + 、Rb + Cs + ;Formula [R1R2R3R4N] + The cations, wherein R1, R2, R3, and R4 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C6-12 Aryl group, and at least one of R1, R2, R3, and R4 is not hydrogen; formula [R5R6N=CH-NR7R8] + The cations, wherein R5, R6, R7, and R8 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl; and C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 cycloalkylimine ion, C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 The cycloalkylimine ions are each unsubstituted or selected from amino, C 1-6 Alkylamino, imino, C 1-6 Alkylimino, C 1-6 Alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6-12 One or more substituents of the aryl group are substituted.

[0169] Preferably, each A cation is selected from Cs. + 、Rb + methylammonium ion [(CH3NH3)] + ], Ethylammonium ion [(CHCH2NH3) + ], Propylammonium ion [(CH3CH2CH2NH3) + ], Butylammonium ion [(CH3CH2CH2CH2NH3) + ], Pentylammonium ion [(CH3CH2CH2CH2CH2NH3) + Hexylammonium ion [(CH3CH2CH2CH2CH2CH2NH3)] + [Heptylammonium ion [(CH3CH2CH2CH2CH2CH2CH2NH3)] + Octylammonium ion [(CH3CH2CH2CH2CH2CH2CH2CH2NH3)] + Tetramethylammonium ion [(N(CH3)4)] + Formamidinium ion [(H2N-C(H)=NH2)] + ]、1-Aminoethyl-1-imine ion [(H2N–C(CH3)=NH2) +] and guanidine ions [(H2N-C(NH2)=NH2) + (guanidinium).

[0170] [A] typically contains one, two, or three monovalent A cations. [A] may contain a single cation selected from methylammonium ions [(CH3NH3)] + ], Ethylammonium ion [(CHCH2NH3) + ], Propylammonium ion [(CH3CH2CH2NH3) + Dimethylammonium ion [(CH3)2NH + Tetramethylammonium ion [(N(CH3)4)] + Formamidinium ion [(H2N-C(H)=NH2)] + ]、1-Aminoethyl-1-imine ion [(H2N–C(CH3)=NH2) + ], guanidinium ion [(H2N-C(NH2)=NH2) + ]、Cs + and Rb + For example, [A] can be contained as a methylammonium ion [(CH3NH3)]. + A single cation.

[0171] Alternatively, [A] may contain two cations selected from this group, such as Cs. + and formamidinium ion [(H2N-C(H)=NH2)] + ], or for example, Cs + and Rb + Or, for example, methylammonium ion [(CH3NH3)] + ] and formamidinium ion [(H2N-C(H)=NH2) + ].

[0172] [X] contains one or more X anions. Typically, [X] contains one or more halide anions, i.e., selected from F... - ,Br - Cl - and I - The anions of [X]. Typically, each X anion is a halide ion. [X] usually contains one, two, or three X anions, which are usually selected from Br. - Cl - and I - .

[0173] X can include two or more different X anions. Typically, [X] contains two or more different halide anions. [X] can be composed, for example, of two X anions, such as Cl and Br, or Br and I, or Cl and I. Therefore, formula [A]a [M] b [X] c Compounds typically include mixed perovskites. When [A] contains one or more organic cations, formula [A]... a [M] b [X] c The compounds can be organic-inorganic metal halide perovskites.

[0174] Typically, the one or more A cations are monovalent cations, the one or more M cations are divalent cations, and the one or more X anions are one or more halide anions.

[0175] Typically, [A] comprises at least two different A cations as described herein, and [X] comprises at least two different X anions as described herein. In some embodiments, [A] comprises at least three different A cations as described herein, and [X] comprises at least two different X anions as described herein.

[0176] Formula [A] a [M] b [X] c Compounds - More Details Typically, a=1, b=1, and c=3. Therefore, equation [A]... a [M] b [X] c The compound can be a compound of formula [A][M][X]3, wherein [A], [M], and [X] are as described herein. Typically, crystalline A / M / X materials include perovskites of formula (I): [A][M][X]3(I) Wherein: [A] contains one or more A cations, wherein the A cations are monovalent cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal divalent cations; [X] contains one or more anions, wherein the anions are halide anions.

[0177] In some embodiments, the perovskite of formula (I) comprises a single A cation, a single M cation, and a single X anion. That is, the perovskite is the perovskite of formula (IA): AMX3 (IA) Wherein A, M, and X are as defined above. In a preferred embodiment, A is selected from (CH3NH3). + (CH3CH2NH3) + (CH3CH2NH3) + (CH3CH2CH2NH3)+ (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M is Pb 2+ or Sn 2+ And X is selected from Br - Cl - and I - .

[0178] For example, crystalline A / M / X materials may include or are substantially composed of materials selected from APbI3, APbBr 、 APbCl3, ASnI3, ASnBr3 and ASnCl3 are perovskite compounds of formula (IA), wherein A is the cation described herein.

[0179] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IA) selected from the following: CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3SnI3, CH3NH3SnBr3, CH3NH3SnCl3, CsPbI3, CsPbBr3, CsPbCl3, CsSnI3, CsSnBr3, CsSnCl3 (H2N–C(H)=NH2)PbI3, (H2N–C(H)=NH2)PbBr3, (H2N–C(H)=NH2)PbCl3, (H2N–C(H)=NH2)SnI3, (H2N–C(H)=NH2)SnBr3 and (H2N–C(H)=NH2)SnCl3, especially CH3NH3PbI3 or CH3NH3PbBr3, preferably CH3NH3PbI3.

[0180] In one implementation, the perovskite is a perovskite of formula (IB): [A I x A II 1-x MX3 (IB) Where A I and A II As defined above regarding A, where M and X are as defined above, and where X is greater than 0 and less than 1. In a preferred embodiment, A I and A II Each is selected from (CH3NH3) + (CH3CH2NH3) +(CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M is Pb 2+ or Sn 2+ And X is selected from Br - Cl - and I - A I and A II For example, they could be (H2N–C(H)=NH2) + and Cs + Or they could be (CH3NH3) respectively. + and (H2N-C(H)=NH2) + Alternatively, they can be Cs respectively. + and Rb + Preferably, A I and A II They are (H2N–C(H)=NH2) + and Cs + .

[0181] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IB) selected from the following: (Cs x Rb 1-x PbBr3, (Cs) x Rb 1-x PbCl3, (Cs) x Rb 1-x PbI3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x PbCl3, [(CH3NH3)] x (H2N–C(H)=NH2) 1-x PbBr3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x PbI 、 [(CH3NH3) x Cs 1-x PbCl3, [(CH3NH3)] x Cs 1-x PbBr3、[(CH3NH3) x Cs1-x PbI3, [(H2N–C(H)=NH2) x Cs 1-x PbCl3, [(H2N–C(H)=NH2) x Cs 1-x PbBr3, [(H2N–C(H)=NH2) x Cs 1-x PbI3, [(CH3NH3) x (H2N–C(H)=NH2) 1-x SnCl3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x SnBr3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x SnI3、 [(CH3NH3) x Cs 1-x SnCl3、[(CH3NH3) x Cs 1-x SnBr3、[(CH3NH3) x Cs 1-x SnI3、[(H2N–C(H)=NH2) x Cs 1-x SnCl3, [(H2N–C(H)=NH2) x Cs 1-x SnBr3 and [(H2N–C(H)=NH2) x Cs 1-x SnI3, where x is greater than 0 and less than 1, for example, x can be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0182] In one embodiment, the perovskite is a perovskite compound of formula (IC): AM[X I y X II 1-y ]3 (IC) Where A and M are as defined above, and X I and X II As defined above with respect to X, where y is greater than 0 and less than 1. In a preferred embodiment, A is selected from (CH3NH3). + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) +(H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M is Pb 2 and Sn 2+ And X I and X II Each selected from Br - Cl - and I - .

[0183] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IC) selected from the following: APb[Br y I 1-y 3. APb[Br] y Cl 1-y ]3. APb[I y Cl 1-y 3. ASn[Br y I 1-y 3. ASn[Br y Cl 1-y ]3、ASn[I y Cl 1-y ]3, where y is greater than 0 and less than 1, and where A is the cation described herein. y can be from 0.01 to 0.99. For example, y can be from 0.05 to 0.95, or from 0.1 to 0.9.

[0184] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IC) selected from the following: CH3NH3Pb[Br y I 1-y 3. CH3NH3Pb[Br y Cl 1-y ]3、CH3NH3Pb[I y Cl 1-y 3. CH3NH3Sn[Br y I 1-y 3. CH3NH3Sn[Br y Cl 1-y ]3、CH3NH3Sn[I y Cl 1-y 3. CsPb[Br] y I 1-y 3. CsPb[Br] y Cl 1-y 3. CsPb[I yCl 1-y 3. CsSn[Br y I 1-y 3. CsSn[Br y Cl 1-y ]3、CsSn[I y Cl 1-y 3. (H2N–C(H)=NH2)Pb[Br] y I 1-y 3. (H2N–C(H)=NH2)Pb[Br] y Cl 1-y ]3、(H2N–C(H)=NH2)Pb[I y Cl 1-y 3. (H2N–C(H)=NH2)Sn[Br y I 1-y 3. (H2N–C(H)=NH2)Sn[Br y Cl 1-y ]3 and (H2N–C(H)=NH2)Sn[I y Cl 1-y ]3, where y is greater than 0 and less than 1, for example, y can be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0185] In a preferred embodiment, the perovskite is a perovskite of formula (ID): [A I x A II 1-x ]M[X I y X II 1-y ]3 (ID) Where A I and A II As defined above regarding A, M is as defined above, and X... I and X II As defined above regarding X, where both X and y are greater than 0 and less than 1. In a preferred embodiment, A I and A II Each is selected from (CH3NH3) + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs+ and Rb + Preferably, A I and A II They are (H2N–C(H)=NH2) + and Cs + M is Pb 2+ or Sn 2+ And X I and X II Each selected from Br - Cl - and I - .

[0186] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (ID) selected from the following: (Cs x Rb 1-x )Pb(Br y Cl 1-y 3. (Cs) x Rb 1-x )Pb(Br y I 1-y )3 and (Cs x Rb 1-x Pb(Cl) y I 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x Pb[Br] y I 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x Pb[Br] y Cl 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x ]Pb[I y Cl 1-y 3. [(CH3NH3)] x Cs 1-x Pb[Br] y I 1-y 3. [(CH3NH3)] x Cs 1-x Pb[Br] y Cl 1-y 3. [(CH3NH3)] x Cs 1-x ]Pb[I y Cl 1-y 3. [(H2N–C(H)=NH2)] x Cs1-x Pb[Br] y I 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x Pb[Br] y Cl 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x ]Pb[I y Cl 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x Sn[Br] y I 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x Sn[Br] y Cl 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x Sn[I y Cl 1-y 3. [(CH3NH3)] x Cs 1-x Sn[Br] y I 1-y 3. [(CH3NH3)] x Cs 1-x Sn[Br] y Cl 1-y 3. [(CH3NH3)] x Cs 1-x Sn[I y Cl 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x Sn[Br] y I 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x Sn[Br] y Cl 1-y ]3 and [(H2N–C(H)=NH2) x Cs 1-x Sn[I y Cl 1-y ]3, where both X and y are greater than 0 and less than 1. For example, both x and y can be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0187] In one implementation, the perovskite is a perovskite of formula (IE): A[M I z M II 1-z X3 (IE) Where M I and M II As defined above with respect to M, A and X are as defined above, and z is greater than 0 and less than 1. In a preferred embodiment, A is selected from (CH3NH3). + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M I It is Pb 2+ And M II It is Sn 2+ And X I and X II Each selected from Br - Cl - and I - .

[0188] For example, crystalline A / M / X materials may comprise or consist essentially of perovskite compounds selected from the following formula (IE): CH3NH3[Pb z Sn 1-z Cl3, CH3NH3[Pb z Sn 1-z ]Br3、CH3NH3[Pb z Sn 1-z I3、Cs[Pb z Sn 1-z Cl3, Cs[Pb] z Sn 1-z ]Br3、Cs[Pb z Sn 1-z I3、(H2N–C(H)=NH2)[Pb z Sn 1-z Cl3、(H2N–C(H)=NH2)[Pb z Sn 1-z ]Br3 and (H2N–C(H)=NH2)[Pb z Sn 1-z]I3, where z is greater than 0 and less than 1, for example z can be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0189] In one implementation, the perovskite is a perovskite of formula (IF): [A I x A II 1-x ][M I z M II 1-z X3 (IF) Where A I and A II As defined above regarding A, M I and M II As defined above regarding M, and X as defined above, where both x and z are greater than 0 and less than 1. In a preferred embodiment, A I and A II Each is selected from (CH3NH3) + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M I It is Pb 2+ And M II It is Sn 2+ ; and X is selected from Br - Cl - and I - A I and A II For example, they could be (H2N–C(H)=NH2) + and Cs + Or they could be (CH3NH3) respectively. + and (H2N–C(H)=NH2) + Alternatively, they can be Cs respectively. + and Rb + .

[0190] For example, crystalline A / M / X materials may comprise or consist substantially of perovskite compounds of formula (IF) selected from the following: [(CH3NH3)] x(H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z Cl3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z Br3、[(CH3NH3) x (H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z I3、[(CH3NH3) x Cs 1-x ][Pb z Sn 1-z Cl3、[(CH3NH3) x Cs 1-x ][Pb z Sn 1-z Br3、[(CH3NH3) x Cs 1-x ][Pb z Sn 1-z I3、[(H2N–C(H)=NH2) x Cs 1-x ][Pb z Sn 1-z Cl3、[(H2N–C(H)=NH2) x Cs 1-x ][Pb z Sn 1-z ]Br3、[(H2N–C(H)=NH2) x Cs 1-x ][Pb z Sn 1-z ]I3, where x and z are both greater than 0 and less than 1. For example, x and z can each be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0191] In one embodiment, the perovskite is a perovskite compound of formula (IG): A[M I z M II 1-z ][X I y X II 1-y ]3 (IG) Where A is as defined above, M I and M II As defined above regarding M, and XI and X II As defined above with respect to X, where both y and z are greater than 0 and less than 1. In a preferred embodiment, A is selected from (CH3NH3). + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M I It is Pb 2+ And M II It is Sn 2+ And X I and X II Each selected from Br - Cl - and I - .

[0192] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IG) selected from the following: A[Pb z Sn 1-z ][Br y I 1-y 3. A[Pb] z Sn 1-z ][Br y Cl 1-y 3. A[Pb] z Sn 1-z ][I y Cl 1-y ]3, wherein y and z are both greater than 0 and less than 1, and wherein A is the cation described herein. y and z can each be from 0.01 to 0.99. For example, y and z can each be from 0.05 to 0.95, or from 0.1 to 0.9.

[0193] For example, crystalline A / M / X materials may include or consist essentially of perovskite compounds of formula (IG) selected from the following: CH3NH3[Pb z Sn 1-z ][Br y I 1-y 3. CH3NH3[Pb z Sn 1-z ][Br y Cl 1-y 3. CH3NH3[Pbz Sn 1-z ][I y Cl 1-y 3. Cs[Pb] z Sn 1-z ][Br y I 1-y 3. Cs[Pb] z Sn 1-z ][Br y Cl 1-y 3. Cs[Pb] z Sn 1-z ][I y Cl 1-y 3. (H2N–C(H)=NH2)[Pb z Sn 1-z ][Br y I 1-y 3. (H2N–C(H)=NH2)[Pb z Sn 1-z ][Br y Cl 1-y ]3 and (H2N–C(H)=NH2)[Pb z Sn 1-z ][I y Cl 1-y ]3, where y and z are both greater than 0 and less than 1. For example, y and z can each be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0194] In a preferred embodiment, the perovskite is a perovskite of formula (IH): [A I x A II 1-x ][M I z M II 1-z ][X I y X II 1-y ]3 (IH) Where A I and A II As defined above regarding A, M I and M II As defined above regarding M, X I and X II As defined above with respect to X, where x, y, and z are each greater than 0 and less than 1. In a preferred embodiment, A I and A II Each is selected from (CH3NH3)+ (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (H2N–C(H)=NH2) + (H2N–C(CH3)=NH2) + (H2N–C(NH2)=NH2) + Cs + and Rb + M I It is Pb 2+ And M II It is Sn 2+ And X I and X II Each selected from Br - Cl - and I - .

[0195] For example, crystalline A / M / X materials may comprise or consist essentially of perovskite compounds of formula (IH) selected from the following: [(CH3NH3)] x (H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z ][Br y I 1-y 3. [(CH3NH3)] x (H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z ][Br y Cl 1-y 3. (CH3NH3) x (H2N–C(H)=NH2) 1-x ][Pb z Sn 1-z ][I y Cl 1-y 3. [(CH3NH3)] x Cs 1-x ][Pb z Sn 1-z ][Br y I 1-y 3. [(CH3NH3)] x Cs 1-x ][Pb z Sn 1-z ][Br y Cl 1-y 3. [(CH3NH3)] x Cs1-x ][Pb z Sn 1-z ][I y Cl 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x ][Pb z Sn 1-z ][Br y I 1-y 3. [(H2N–C(H)=NH2)] x Cs 1-x ][Pb z Sn 1-z ][Br y Cl 1-y ]3 and [(H2N–C(H)=NH2) x Cs 1-x ][Pb z Sn 1-z ][I y Cl 1-y ]3, where x, y and z are each greater than 0 and less than 1. For example, x, y and z can each be 0.01 to 0.99, or 0.05 to 0.95, or 0.1 to 0.9.

[0196] In one embodiment, a=2, b=1, and c=4. In this embodiment, the crystalline A / M / X material comprises a compound of formula (II) (“2D layered perovskite”): [A]2[M][X]4(II) Wherein: [A] comprises one or more A cations, wherein the A cations are monovalent cations; [M] comprises one or more M cations, wherein the M cations are metal or quasi-metal divalent cations; and [X] comprises one or more X anions, wherein the X anions are halide anions. In this embodiment, the A and M cations and the X anion are as defined above.

[0197] In another embodiment, a=2, b=1, and c=6. In this embodiment, the crystalline A / M / X material may in this case comprise a hexahalometalate of formula (III): [A]2[M][X]6(III) Wherein: [A] contains one or more A cations, wherein the A cations are monovalent cations; [M] contains one or more M cations, wherein the M cations are metallic or quasi-metallic tetravalent cations; and [X] contains one or more X anions, wherein the X anions are halide anions.

[0198] In a preferred embodiment, the hexahalometalate of formula (III) can be a mixed monovalent cationic hexahalometalate. In the mixed monovalent cationic hexahalometalate, [A] comprises at least two monocations A, wherein the A cations are monovalent cations; [M] comprises at least one M cation, wherein the M cation is a metallic or near-metallic tetravalent cation (and typically [M] comprises a single M cation, wherein the M cation is a metallic or near-metallic tetravalent cation); and [X] comprises at least one X anion, wherein the X anion is a halide anion (and typically [X] comprises a single halide anion or two types of halide anions). In the mixed metallic hexahalometalate, [A] comprises at least one monovalent cation (typically [A] is a single monovalent cation or two types of monovalent cations); [M] comprises at least two metallic or near-metallic tetravalent cations (e.g., Ge). 4+ and Sn 4 + [X] contains at least one halide anion (and typically [X] is a single halide anion or two types of halide anions). In mixed halide hexahalometalates, [A] contains at least one monovalent cation (typically [A] is a single monovalent cation or two single types of monovalent cations); [M] contains at least one metal or metalloid tetravalent cation (typically [M] is a single metal tetravalent cation); [X] contains at least two halide anions, such as Br₂. - and Cl - , or Br - and I - .

[0199] [A] may contain at least one A monovalent cation selected from any suitable monovalent cation (such as those described herein for perovskites). In the case of hexahalometalates, each A cation is typically selected from Li. + Na + K + 、Rb + Cs + NH4 + And monovalent organic cations. Monovalent organic cations are organic cations carrying a single positive charge, for example, with a molecular weight not exceeding 500 g / mol. For example, [A] can be selected from Li + Na + K + 、Rb + Cs + NH4 + A single A cation, and a monovalent organic cation. [A] preferably comprises at least one A cation, said A cation being selected from Rb. + Cs + NH4 +And monovalent organic cations. For example, [A] can be a monovalent cation selected from Li. + Na + K + 、Rb + Cs + and NH4 + [A] is a single inorganic monovalent A cation. In another embodiment, [A] can be at least one monovalent organic A cation. For example, [A] can be a single monovalent organic A cation. In one embodiment, [A] is (CH3NH3). + In another embodiment, [A] is (H2N–C(H)=NH2). + .

[0200] Preferably, [A] comprises two or more types of A cations. [A] can be a single monovalent A cation, or actually two monovalent A cations. Each monovalent A cation is independently selected from K. + 、Rb + Cs + NH4 + (CH3NH3) + (CH3CH2NH3) + (CH3CH2CH2NH3) + (N(CH3)4) + (N(CH2CH3)4) + (N(CH2CH2CH3)4) + (H2N–C(H)=NH2) + and (H2N–C(CH3)=NH2) + .

[0201] [M] may contain one or more M cations selected from suitable metallic or metalloid tetravalent cations. Metals include elements from groups 3 to 12 of the periodic table, as well as Ga, In, Tl, Sn, Pb, Bi, and Po. Metalloids include Si, Ge, As, Sb, and Te. For example, [M] may contain at least one M cation, which is a metallic or metalloid tetravalent cation selected from: Ti 4+ V 4+ Mn 4+ Fe 4+ Co 4+ Zr 4+ 、Nb 4+ Mo 4+ Ru 4+ ,Rh 4+ Pd 4+ Hf 4+ Ta 4+ W4+ Re 4+ Os 4+ Ir 4+ Pt 4+ Sn 4+ Pb 4+ Po 4+ Si 4+ 、Ge 4+ and Te 4+ Typically, [M] contains selections from Pd. 4+ W 4+ Re 4+ Os 4+ Ir 4+ Pt 4+ Sn 4+ Pb 4+ 、Ge 4+ and Te 4+ At least one tetravalent cation of metal or metalloid. For example, [M] may be selected from Pd. 4+ W 4+ Re 4+ Os 4+ Ir 4+ Pt 4+ Sn 4+ Pb 4+ 、Ge 4+ and Te 4+ A single metal or metalloid tetravalent cation.

[0202] Typically, [M] contains at least one M cation, said M cation being selected from Sn. 4+ Te 4+ 、Ge 4+ and Re 4+ The [M] is a tetravalent cation of metal or metalloid nature. In one embodiment, [M] comprises at least one M cation, said M cation being selected from Pb. 4+ Sn 4+ Te 4+ 、Ge 4+ and Re 4+ A metallic or near-metallic tetravalent cation. For example, [M] may contain an M cation, which is selected from Pb. 4+ Sn 4+ Te 4+ and Ge 4+ At least one tetravalent cation of metal or metalloid. Preferably, [M] contains at least one tetravalent cation selected from Sn. 4+ Te 4+ and Ge 4+At least one tetravalent cation of metal or metalloid. As described above, the hexahalometalate compound can be a mixed metal or a single metal hexahalometalate. Preferably, the hexahalometalate compound is a single metal hexahalometalate compound. More preferably, [M] is selected from Sn. 4+ Te 4+ and Ge 4+ A single metallic or near-metallic tetravalent cation. For example, [M] could be a Te 4+ A single metal or metalloid tetravalent cation. For example, [M] could be a Ge 4+ A single metal or metalloid tetravalent cation. Most preferably, [M] is Sn. 4+ A single metal or metalloid tetravalent cation.

[0203] [X] may contain at least one X anion, wherein the X anion is a halide anion. Therefore, [X] contains elements selected from F... - Cl - ,Br - and I - At least one halide anion. Typically, [X] contains a halide anion selected from Cl. - ,Br - and I - At least one halide anion. The hexahalometalate compound can be a mixed hexahalometalate or a single hexahalometalate. If the hexahalometalate is mixed, [X] contains a component selected from F. - Cl - ,Br - and I - Two, three, or four halogen anions. Typically, in mixed halogen compounds, [X] contains halogens selected from F. - Cl - ,Br - and I - Two types of halogen anions.

[0204] In some embodiments, [A] is a single monovalent cation, and [M] is a single metallic or near-metallic tetravalent cation. Therefore, crystalline A / M / X materials can, for example, include hexahalometalate compounds of formula (IIIA). A2M[X]6 (IIIA) Wherein: A is a monovalent cation; M is a metallic or near-metallic tetravalent cation; and [X] is at least one halide anion. [X] may be selected from F - Cl - ,Br - and I - Preferably selected from Cl - ,Br - and I -One, two, or three halide anions. In formula (IIIA), [X] is preferably selected from Cl. - ,Br - and I - One or two halogen anions.

[0205] Crystalline A / M / X materials may, for example, comprise or consist substantially of hexahalometalate compounds of formula (IIIB). A2MX 6-y X′ y (IIIB) Wherein: A is a monovalent cation (i.e., the second cation); M is a metallic or near-metallic tetravalent cation (i.e., the first cation); X and X′ are each independently a (different) halide anion (i.e., two second anions); and y is 0 to 6. When y is 0 or 6, the hexahalometalate compound is a single halogen compound. When y is 0.01 to 5.99, the compound is a mixed halide hexahalometalate compound. When the compound is a mixed halogen compound, y can be 0.05 to 5.95. For example, y can be 1.00 to 5.00.

[0206] Hexahalometalate compounds can be, for example, A2SnF 6-y Cl y A2SnF 6-y Br y A2SnF 6-y I y 、A2SnCl 6-y Br y 、A2SnCl 6-y I y 、A2SnBr 6-y I y A2TeF 6-y Cl y A2TeF 6-y Br y A2TeF 6-y I y A2TeCl 6-y Br y A2TeCl 6-y I y A2TeBr 6-y I y A2GeF 6-y Cl y A2GeF 6-y Br y A2GeF 6-y I y 、A2GeCl 6-y Br y 、A2GeCl6-y I y 、A2GeBr 6-y I y A2ReF 6-y Cl y A2ReF 6-y Br y A2ReF 6-y I y 、A2ReCl 6-y Br y 、A2ReCl 6-y I y or A2ReBr 6-y I y Where: A is K + 、Rb + Cs + 、(R 1 NH3) + 、(NR 2 4) + or (H2N–C(R) 1 =NH2) + , where R 1 It is H, substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted aryl, R 2 Is it substituted or unsubstituted C? 1-10 Alkyl group; and y is 0 to 6. Optionally, y is 0.01 to 5.99. If the hexahalometalate compound is a mixed halogen compound, then y is typically 1.00 to 5.00. A can be as defined above. For example, A can be Cs + NH4 + (CH3NH3) + (CH3CH2NH3) + (N(CH3)4) + (N(CH2CH3)4) + (H2N–C(H)=NH2) + Or (H2N–C(CH3)=NH2) + For example, Cs + NH4 + Or (CH3NH3) + .

[0207] Hexahalometalate compounds can typically be A2SnF 6-y Cl y A2SnF 6-y Br y A2SnF 6-y I y 、A2SnCl 6-y Bry 、A2SnCl 6-y I y or A2SnBr 6-y I y Where: A is K + 、Rb + Cs + 、(R 1 NH3) + 、(NR 2 4) + or (H2N–C(R) 1 =NH2) + , or A as defined in this paper, where R 1 It is H, substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted aryl, or R 2 Is it substituted or unsubstituted C? 1-10 Alkyl group; and y is 0 to 6.

[0208] In another embodiment, the hexahalometalate compound is A2GeF. 6-y Cl y A2GeF 6-y Br y A2GeF 6-y I y 、A2GeCl 6-y Br y 、A2GeCl 6-y I y or A2GeBr 6-y I y Where: A is K + 、Rb + Cs + 、(R 1 NH3) + 、(NR 2 4) + or (H2N–C(R) 1 =NH2) + , or A as defined in this paper, where R 1 It is H, substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted aryl, or R 2 Is it substituted or unsubstituted C? 1-10 Alkyl group; and y is 0 to 6.

[0209] Hexahalometalate compounds can be, for example, A2TeF 6-y Cl y A2TeF 6-y Br y A2TeF 6-y Iy A2TeCl 6-y Br y A2TeCl 6-y I y or A2TeBr 6-y I y Where: A is K + 、Rb + Cs + 、(R 1 NH3) + 、(NR 2 4) + or (H2N–C(R) 1 =NH2) + , or A as defined in this paper, where R 1 It is H, substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted aryl, or R 2 Is it substituted or unsubstituted C? 1-10 Alkyl; and y is 0 to 6, or y as defined herein.

[0210] Typically, y will be between 1.50 and 2.50. For example, y can be between 1.80 and 2.20. This may occur if the compound is produced using two equivalents of AX′ and one equivalent of MX4, as described below.

[0211] In some embodiments, all ions are either single anions or cations. Therefore, crystalline A / M / X materials may comprise or consist substantially of hexahalometalate compounds of formula (IIIC). A2MX6 (IIIC) Wherein: A is a monovalent cation; M is a metallic or near-metallic tetravalent cation; and X is a halide anion. A, M, and X can be defined as in this paper.

[0212] The hexahalometalate compound can be A2SnF6, A2SnCl6, A2SnBr6, A2SnI6, A2TeF6, A2TeCl6, A2TeBr6, A2TeI6, A2GeF6, A2GeCl6, A2GeBr6, A2GeI6, A2ReF6, A2ReCl6, A2ReBr6, or A2ReI6, where: A is K + 、Rb + Cs + 、(R 1 NH3) + 、(NR 2 4) + or (H2N–C(R) 1 =NH2) + , where R 1It is H, substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted aryl, and R 2 Is it substituted or unsubstituted C? 1-10 Alkyl group. A can be as defined herein.

[0213] Preferably, the hexahalometalate compound is Cs₂SnI₆, Cs₂SnBr₆, or Cs₂SnBr₆. 6-y I y Cs2SnCl 6-y I y Cs2SnCl 6-y Br y , (CH3NH3)2SnI6, (CH3NH3)2SnBr6, (CH3NH3)2SnBr 6-y I y (CH3NH3)2SnCl 6-y I y (CH3NH3)2SnCl 6-y Br y , (H2N–C(H)=NH2)2SnI6, (H2N–C(H)=NH2)2SnBr6, (H2N–C(H)=NH2)2SnBr 6- y I y (H2N–C(H)=NH2)2SnCl 6-y I y Or (H2N–C(H)=NH2)2SnCl 6-y Br y Where y is from 0.01 to 5.99. For example, hexahalometallic acid salts can be (CH3NH3)2SnI6, (CH3NH3)2SnBr6, (CH3NH3)2SnCl6, (H2N–C(H)=NH2)2SnI6, (H2N–C(H)=NH2)2SnBr6, or (H2N–C(H)=NH2)2SnCl6. Hexahalometallic acid salts can be Cs2SnI6, Cs2SnBr6, Cs2SnCl 6-y Br y 、(CH3NH3)2SnI6、(CH3NH3)2SnBr6、or(H2N–C(H)=NH2)2SnI6。

[0214] Crystalline A / M / X materials may include bismuth or antimony halide metal acids. For example, crystalline A / M / X materials may include halide metal acid salt compounds comprising: (i) one or more monovalent cations ([A]) or one or more divalent cations ([B]); (ii) one or more metallic or near-metallic trivalent cations ([M]); and (iii) one or more halide anions ([X]). The compound may be a compound of the following formula: BBiX5, B2BiX7, or B3BiX9, wherein B is (H3NCH2NH3). 2+ (H3N(CH2)2NH3) 2+ (H3N(CH2)3NH3) 2+ (H3N(CH2)4NH3) 2+ (H3N(CH2)5NH3) 2+ (H3N(CH2)6NH3) 2+ (H3N(CH2)7NH3) 2+ (H3N(CH2)8NH3) 2+ Or (H3N–C6H4–NH3) 2+ And X is I – ,Br – or Cl – Preferred I – .

[0215] In yet another embodiment, the crystalline A / M / X material can be a double perovskite. Such compounds are defined in WO 2017 / 037448, the entire contents of which are incorporated herein by reference. Typically, the compound is a double perovskite compound of formula (IV): [A]2[B + [B] 3+ [X]6 (IV); Wherein: as defined herein, [A] includes one or more A cations that are monovalent cations; [B] + ] and [B 3+ [M] is equivalent to [M], where M includes one or more M cations that are monovalent cations and one or more M cations that are trivalent cations; and [X] includes one or more X anions that are halide anions.

[0216] [B + The monovalent cation, M, is typically selected from metal and metalloid monovalent cations. Preferably, the monovalent cation, M, or M, is selected from Li. + Na + K + 、Rb + Cs + Cu+ Ag + Au + and Hg + More preferably, one or more M cations that are monovalent cations are selected from Cu. + Ag + and Au + Most preferably, one or more M cations that are monovalent cations are selected from Ag. + and Au + For example, [B] + ] can be Ag + A monovalent cation, or [B + ] could be Au + A monovalent cation.

[0217] [B 3+ The trivalent cations included in the [ ] are typically selected from metal and metalloid trivalent cations. Preferably, the trivalent cations included in the [ ] are selected from Bi. 3+ Sb 3+ Cr 3+ Fe 3+ Co 3+ Ga 3+ As 3+ Ru 3+ ,Rh 3+ In 3+ Ir 3+ and Au 3+ More preferably, one or more M cations that are trivalent cations are selected from Bi. 3+ and Sb 3+ For example, [B] 3+ ] can be for Bi 3+ A trivalent cation, or [B 3+ ] can be Sb 3+ Bismuth is a trivalent cation. Compared to heavy metals such as lead, bismuth is relatively less toxic.

[0218] In some implementations, in ([B + The M cations, which are monovalent cations, in []) are selected from Cu. + Ag + and Au + , and in ([B 3+ The M1 cation, which is a trivalent cation, is selected from Bi1. 3+ and Sb 3+ .

[0219] An example of a double perovskite is Cs2BiAgBr6.

[0220] Typically, when the compound is a bis-perovskite, it is a compound of formula (IVa): A2B + B 3+ [X]6 (IVa); Wherein: A cation is as defined herein; B cation is as defined herein. + It is an M cation that is a monovalent cation; as defined in this paper, B 3+ It is a trivalent cation M; and [X] includes one or more X anions that are halide anions, such as two or more halide anions, preferably a single halide anion.

[0221] In yet another embodiment, the compound can be a layered double perovskite compound of formula (V): [A]4[B + [B] 3+ [X]8 (V); Among them: [A], [B] + [B3] + [] and [X] are as defined above. In some embodiments, the layered double perovskite compound is a double perovskite compound of formula (Va): A4B + B 3+ [X]8 (Va); Wherein: A cation is as defined herein; B cation is as defined herein. + It is an M cation that is a monovalent cation; as defined in this paper, B 3+ It is a trivalent cation M; and [X] includes one or more X anions that are halide anions, such as two or more halide anions, preferably a single halide anion or two types of halide anions.

[0222] In yet another embodiment, the compound can be a compound of formula (VI): [A]4[M][X]6(VI; Wherein: [A], [M], and [X] are as defined above (e.g., with respect to compounds of formula (I) or (II)). However, preferably, the compound is not a compound of formula (VI). When the compound is a compound of formula (VI), it may preferably be a compound of formula (VIA). [A I A II ]4[M][X]6(VIA; That is, [A] comprises compounds containing two types of monovalent A cations. In other preferred embodiments, the compound of formula (VI) can be a compound of formula (VIB): [A]4[M][XI X II ]6 (VIB); That is, a compound of formula (VI) in which [X] contains two types of X anions. In other preferred embodiments, the compound of formula (VI) can be a compound of formula (VIC): [A I A II ]4[M][X I X II ]6 (VIC); That is, a compound of formula (VI) in which [A] contains two types of A monovalent cations and [X] contains two types of X anions. In formulas (VIa), (VIb) and (VIc), each of [A], [M] and [X] is as defined above (e.g., with respect to compounds of formula (I) or (II)).

[0223] In another embodiment, a=1, b=1, and c=4. In this embodiment, the crystalline A / M / X material may include a compound of formula (VII): [A][M][X]4 (VII) Wherein: [A] comprises one or more A cations that are monovalent cations; [M] comprises one or more M cations that are metallic or quasi-metallic trivalent cations; [X] comprises one or more X anions that are halide anions. The A monovalent cations and M trivalent cations are as defined herein. An exemplary compound of formula (VII) is AgBiI4.

[0224] It should be understood that the present invention also includes methods for producing variations of the above-described structures (I), (II), (III), (IV), (V), (VI) and (VII), wherein one or more of the associated values ​​of a, b and c are non-integer values.

[0225] Preferably, formula [A] a [M] b [X] c The compound is a compound of formula [A][M][X]3, a compound of formula [A]4[M][X]6, or a compound of formula [A]2[M][X]6. For example, in a preferred embodiment, formula [A] a [M] b [X] c The compounds are those of formula (I), such as those of formulas (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH), (IIIA), or (IIIB), (IIC), (VIA), (VIB), or (VIC). Typically, formula [A] is used. a [M]b [X] c The compound is a compound of formula (I), such as compounds of formula (IA), (IB), (IC), (ID), (IE), (IF), (IG), or (IH).

[0226] In some implementations, formula [A] a [M] b [X] c The compound is one in which [A] comprises two or more different A cations. For example, [A] may contain two or three types of A cations. In some embodiments, formula [A]... a [M] b [X] c The compound is one in which [X] comprises two or more different X anions. For example, [X] may contain two types of anions, such as halide anions. In some embodiments, formula [A] a [M] b [X] c The compound is one in which [M] contains two or more different M cations. For example, [X] can contain two types of anions, such as Sn. 2+ and Pb 2+ .

[0227] In one aspect of each of these implementations, formula [A] a [M] b [X] c A compound is a compound in which [A] contains two or more different A cations and [X] contains two or more different X anions. For example, [A] may contain two types of A cations and [X] may contain two types of X anions (e.g., two types of halide anions). [A] may contain three types of A cations and [X] may contain two types of X anions (e.g., two types of halide anions).

[0228] In one aspect of each of these implementations, formula [A] a [M] b [X] c The compound is one in which [A] contains two or more different A cations and [M] contains two or more different M cations. For example, [A] may contain two types of A cations, and [M] may contain two types of M cations (e.g., Sn). 2+ and Pb 2 + ). In one aspect of each of these implementations, formula [A]a [M] b [X] c The compound is one in which [X] contains two or more different X anions and [M] contains two or more different M cations. For example, [X] may contain two types of X anions (e.g., two types of halide anions), and [M] may contain two types of M cations (e.g., Sn). 2+ and Pb 2+ ). In one aspect of each of these implementations, formula [A] a [M] b [X] c The compound is one in which [A] contains two or more different A cations, [X] contains two or more different X anions, and [M] contains two or more different M cations. For example, [A] may contain two types of A cations, [X] may contain two types of X anions (such as two types of halide anions), and [M] may contain three types of M cations (such as Sn). 2+ and Pb 2+ ). Typically, formula [A] a [M] b [X] c The compound is a compound of formula [A][M][X]3, wherein [A], [M] and [X] are as defined above.

[0229] Typically, each type of A cation is selected from: alkali metal cations; formula [R1R2R3R4N] + The cations, wherein R1, R2, R3, and R4 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl group, and at least one of R1, R2, R3, and R4 is not hydrogen; formula [R5R6N=CH-NR7R8] + The cations, wherein R5, R6, R7, and R8 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl; and C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 cycloalkylimine ion, C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10cycloalkylammonium ions and C 3-10 The cycloalkylimine ions are each unsubstituted or selected from amino, C 1-6 Alkylamino, imino, C 1-6 Alkylimino, C 1-6 Alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6-12 One or more substituents of the aryl group are substituted. Typically, each A cation is selected from Cs. + 、Rb + Formamidinium ion, guanidine ion, methylammonium ion, ethylammonium ion, propylammonium ion, butylammonium ion, pentylammonium ion, hexylammonium ion, heptylammonium ion, and octylammonium ion, and preferably Cs + 、Rb + Formamidinium ion, guanidine ion, methylammonium ion and ethylammonium ion.

[0230] Typically, [X] contains two or more different X anions. Typically, the two or more different X anions are two or more different halide anions. Preferably, [X] contains Br and I.

[0231] Typically, [A] contains formamidinium ions. [A] also typically contains Cs. + Alternatively, [A] can be composed primarily of formamidinium ions.

[0232] Typically, [A] does not contain methylammonium ions. Alternatively, [A] consists of methylammonium ions and at least one A cation other than methylammonium ions, provided that the molar fraction of methylammonium ions in [A] is less than 15% of [A].

[0233] Typically, [M] contains selections from Ca 2+ 、Sr 2+ Cd 2+ Cu 2+ Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd 2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ and Eu 2+ The M cation. Typically, [M] contains a cation selected from Sn. 2+ Pb 2+ Cu 2+ 、Ge 2 and Ni 2+ Preferably selected from Sn 2+and Pb 2+ The M cation. Preferably, [M] comprises Pb. 2+ .

[0234] Typically, formula [A] a [M] b [X] c The compound is of formula [Cs] x (H2N–C(H)=NH2) 1-x ]Pb[I y Br 1-y Compounds of [3], wherein x is greater than 0 and less than 1, and y is greater than 0 and less than 1. Typically, x is from about 0.05 to about 0.5, for example from about 0.08 to about 0.3, or from about 0.1 to about 0.2. For example, x can be 0.13, 0.15, or 0.17. Typically, y is from about 0.3 to about 0.99, for example from about 0.4 to about 0.95, or from about 0.50 to about 0.92. For example, y can be 0.9, or 0.6, or 0.77.

[0235] Formula [A] a [M] b [X] c The compounds may include, for example, Cs. 0.13 FA 0.87 Pb(I 0.9 Br 0.1 3. Cs 0.15 FA 0.85 Pb(I 0.6 Br 0.4 )3 or Cs 0.17 FA 0.83 Pb(I 0.77 Br 0.23 )3, where FA is a formamidinium cation, (H2N–C(H)=NH2) + .

[0236] A photovoltaic device may, for example, include an n-type region comprising at least one n-type layer; a p-type region comprising at least one p-type layer; and a layer disposed between the n-type and p-type regions comprising the passivated A / M / X material. A photovoltaic device may, for example, include a photoactive region comprising an n-type region, a p-type region, and a layer disposed between the n-type and p-type regions comprising the passivated A / M / X material. The layer comprising the passivated A / M / X material may consist substantially of, or be composed of, a passivated A / M / X material. The layer comprising the passivated A / M / X material may, for example, comprise (or consist substantially of, or be composed of) a thin film of the passivated A / M / X material. Those skilled in the art will understand that an n-type layer is an electron transport (i.e., n-type) material layer, and a p-type layer is a hole transport (i.e., p-type) material layer. A wide range of n-type and p-type materials are known to those skilled in the art, for example, as described in WO 2020 / 012195, the entire contents of which are incorporated herein by reference. The n-type layer may, for example, contain titanium dioxide, methyl phenyl-C61-butyrate (PCBM), or C 60 The p-type layer may, for example, contain spiroOMeTAD (2,2′,7,7′-tetra-(N,N-di-p-methoxyaniline)9,9′-spirodifluorene) or Me-4PACz. The n-type layer may contain BCP and C. 60 Alternatively, methyl phenyl-C61-butyrate (PCBM) may be used. The photovoltaic device may also include a first electrode and a second electrode. The first electrode may contact the n-type region. The second electrode may contact the p-type region. Typically, the photoactive region is disposed between the first and second electrodes. The first and second electrodes may contain any suitable conductive material. The first electrode typically contains a transparent conductive oxide, such as FTO, ITO, or AZO, preferably ITO. The second electrode typically contains one or more metals, such as one or more metals selected from silver, gold, copper, aluminum, platinum, palladium, chromium, or tungsten. Typically, the second electrode contains gold and chromium. Each electrode may be formed as a monolayer or may be patterned.

[0237] Photovoltaic devices can be solar cells. Photovoltaic devices can be single-junction photovoltaic devices, such as single-junction solar cells.

[0238] Alternatively, the photovoltaic device can be a tandem junction or multijunction photovoltaic device, such as a tandem junction or multijunction solar cell. Therefore, the photovoltaic device may include a first electrode, a second electrode, and a photoactive region disposed between the first and second electrodes as defined above (i.e., including the n-type region, the p-type region, and the layer comprising passivated A / M / X material disposed between the n-type and p-type regions); and at least one other photoactive region. One or more other photoactive regions may (independently) be the same as or different from the photoactive regions defined above. At least one other photoactive region may be at least one other photoactive region used in conventional and known optoelectronic and photovoltaic devices. For example, at least one other photoactive region may include or be derived from a photoactive region of a crystalline silicon photovoltaic cell, or from a photoactive region of a conventional thin-film gallium arsenide, CIGS, CIS, or CZTSSe photovoltaic device. At least one other photoactive region may include or comprise a photoactive region containing a semiconductor layer. The semiconductor may, for example, include silicon, such as crystalline silicon. Semiconductors may include, for example, metal sulfide semiconductors or metal selenide semiconductors, such as copper zinc tin sulfide, copper zinc tin selenide, copper zinc tin selenide sulfide, copper indium gallium selenide, copper indium gallium diselenide, or copper indium selenide.

[0239] Applications of passivated A / M / X materials This invention also provides the use of passivated A / M / X materials as sensitizers in photovoltaic devices. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; a is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18. The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0240] The passivated A / M / X material can be any passivated A / M / X material as further defined anywhere in this document.

[0241] Method for producing passivated A / M / X materials The present invention also provides a method for producing passivated A / M / X materials, wherein the method further includes: producing a photovoltaic device comprising the passivated A / M / X material, or using the passivated A / M / X material as a sensitizer in a photovoltaic device.

[0242] Therefore, the present invention provides a method for producing passivated A / M / X materials. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; a is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18. The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: Production of photovoltaic devices including passivated A / M / X materials.

[0243] The present invention also provides a method for producing passivated A / M / X materials. The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; a is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18. The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: Passivated A / M / X materials are used as sensitizers in photovoltaic devices.

[0244] The passivated A / M / X material produced in these methods can be any passivated A / M / X material as defined anywhere in this document.

[0245] In the method described herein, the passivated A / M / X material can be in the form of a layer.

[0246] The method may include treating a layer containing the crystalline A / M / X material with the passivating agent, the layer containing the crystalline A / M / X material being disposed on a substrate. The layer containing the crystalline A / M / X material may first be produced by any suitable method for producing a layer (e.g., a thin film) of the crystalline A / M / X material on a substrate. Producing [A] on the substrate... a [M] b [X] c Methods for crystallizing A / M / X material layers of compounds are known in the art, and are described, for example, in WO 2020 / 109787, WO 2020 / 012193 and WO 2020 / 01195. Such methods typically involve exposing a substrate to the [A] material to be produced. a [M] b [X] c The compound contains one or more A cations, one or more M cations, and one or more X anions. Typically, the cations and anions correspond to the [A] to be produced. a [M] b [X]c The relative amounts of the same stoichiometric ratio of cations and anions are present in the compound. One or more A cations, one or more M cations, and one or more X anions may be present in one or more different phases selected from the gas phase and the solution phase. For example, such methods typically involve arranging a film-forming solution on a substrate, wherein the film-forming solution comprises a solvent, one or more A cations, one or more M cations, and one or more X anions. Alternatively, multiple solutions may be used, which together comprise the cations and anions in question. The arrangement here can be performed by spin coating or any other suitable solution deposition method. Typically, thermal annealing is performed afterward, for example at a temperature of 50 to 150°C, such as at about 100°C. Alternatively, such methods typically involve exposing the substrate to: a gas phase comprising one or more A cations, one or more M cations, and one or more X anions; or multiple gas phases together comprising one or more A cations, one or more M cations, and one or more X anions. Thermal annealing may then be performed, for example at a temperature of 50 to 150°C, such as at about 100°C.

[0247] As described above, the method of the present invention may include (i) treating the crystalline A / M / X material (which may optionally be in the form of a layer) with the passivating agent.

[0248] The step of treating the crystalline A / M / X material with the passivating agent may include vaporizing the passivating agent to generate a gaseous passivating agent, and treating the crystalline A / M / X material with the gaseous passivating agent. Vaporizing the passivating agent can be achieved by heating the passivating agent, for example at a temperature of 50 to 150°C, such as heating the passivating agent at about 100°C. The crystalline A / M / X material may be exposed to the generated vapor, for example for a period of time, such as 5 seconds to 5 minutes, such as 10 seconds to 2 minutes.

[0249] Alternatively, the step of treating the crystalline A / M / X material with the passivating agent may include preparing a solution of the passivating agent and treating the crystalline A / M / X material with the solution of the passivating agent. This treatment can be performed by spin coating or any other suitable solution deposition method.

[0250] Alternatively, the method may include (ii) producing the crystalline A / M / X material from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent. For example, the method may include producing a layer comprising the crystalline A / M / X material on a substrate in the presence of the passivating agent, the production comprising exposing the substrate to the one or more A cations, the one or more M cations, the one or more X anions, and the passivating agent. The one or more A cations, the one or more M cations, the one or more X anions, and the passivating agent may be present in one or more different phases selected from the gas phase and the solution phase. For example, one or more A cations, one or more M cations, one or more X anions, the passivating agent, and a solvent may be present in a film-forming solution, and the method may include disposing the film-forming solution on the substrate. Alternatively, multiple solutions may be used, which together comprise the discussed cations and anions and the passivating agent, and the method may include disposing each of the solutions on the substrate. This disposition may be performed by spin coating or any other suitable solution deposition method. Following this, thermal annealing can be performed, for example at a temperature of 50 to 150°C, such as at about 100°C. Alternatively, the method may include exposing the substrate to: a gas phase comprising one or more A cations, one or more M cations, one or more X anions, and the passivating agent; or multiple gas phases together comprising one or more A cations, one or more M cations, one or more X anions, and the passivating agent. Following this, thermal annealing can be performed, for example at a temperature of 50 to 150°C, such as at about 100°C.

[0251] The passivating agents used in the methods of this invention comprise, or are substantially composed of, organic compounds, or are composed of organic compounds containing a silane moiety and (a) not containing an amine moiety, or (b) containing an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. The organic compounds may be as further defined anywhere herein. Such organic compounds used herein as passivating agents are commercially available and / or can be synthesized by those skilled in the art using conventional methods. Dimers and polymers of such organic compounds as defined above can also be readily produced by conventional methods. Such dimers and polymers (e.g., of formula Ia, IIa, Ic, or IIc) may be produced prior to the methods described above for producing passivated A / M / X materials, or they may be formed in situ from the corresponding monomeric organic compounds (e.g., of formula I or II) during the methods for producing passivated A / M / X materials.

[0252] In the method of the present invention, the substrate may include a first charge transport region, the first charge transport region comprising at least one first charge transport material layer. The substrate may also include a first electrode. The method of the present invention may further include arranging a second charge transport region on a layer comprising the crystalline A / M / X material, the second charge transport region comprising at least one layer of a second charge transport material. The method may further include arranging a second electrode on the second charge transport region. Typically, the first charge transport region is a hole transport region and the first charge transport material is a hole transport material, and the second charge transport region is an electron transport region and the second charge transport material is an electron transport material. Alternatively, the first charge transport region may be an electron transport region and the first charge transport material may be an electron transport material, and the second charge transport region may be a hole transport region and the second charge transport material may be a hole transport material.

[0253] Hole transport (p-type) and electron transport (n-type) materials can be further defined above with respect to the device of the present invention, as can the first and second electrodes.

[0254] Significant advantages have been achieved for devices incorporating passivated A / M / X materials, such as photovoltaic devices. These advantages include, for example, improved device efficiency and stability.

[0255] The invention will be further described in the following embodiments.

[0256] Example 1. Method Precursor material preparation Lead iodide (PbI₂, 99.99%), lead bromide (PbBr₂, >98.0%), and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz, >99.0%) were purchased from TCI. Formamidinium iodide (FAI, >99.99%) was purchased from Dyenamo. Methyl [6,6]-phenyl-C61-butyrate (PC) 61 BM (>99.5%) was purchased from Solenne BV. BCP (98%) and Cesium iodide (CsI, 99.9%) were purchased from Alfa Aesar. Unless otherwise specified, all other materials and solvents were purchased from Sigma-Aldrich. All materials were used as is without further purification. To form a mixed cationic lead-anionic perovskite precursor solution, N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were mixed in an organic solvent system containing N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at a volume ratio of DMF:DMSO = 4:1, with precise stoichiometry [i.e., CsI] in relation to the mixed perovskite composition. x FA 1-x Pb(I1-y Br y (i) For a 1.6 eV battery, x = 0.13 and y = 0.10; (ii) For a 1.67 eV battery, x = 0.17 and y = 0.23; (iii) For a 1.77 eV battery, x = 0.15 and y = 4] CsI, FAI, PbI2 and PbBr2 were prepared in the corresponding manner. For the 1.6 eV battery and the 1.67 / 1.77 eV battery, the perovskite precursor concentrations were 1.41 M and 1.39 M, respectively. The perovskite precursor solutions were stirred overnight in a nitrogen-filled glove box and used without any further treatment.

[0257] Film deposition and solar cell manufacturing Tin-doped indium oxide (ITO) coated glass was cleaned in the following order using a series of ultrasonic cleaning baths with various solutions and solvents: 1) a deionized aqueous solution of 2% v / v Decon 90 cleaner; 2) deionized water; 3) acetone; and 4) isopropanol (approximately 10 minutes per step). After ultrasonic cleaning, the substrate was dried with compressed nitrogen and then treated with UV ozone for 20 minutes before use. Following the substrate cleaning procedure, Me-4PACz (0.5 mg / mL in ethanol) was deposited by dispensing a prepared organic solution onto the substrate rotating at 3000 rpm for 20 seconds. -1 Then, it was thermally annealed in ambient air at 130°C for 5 minutes. The perovskite layer was deposited using a spin coater in a nitrogen-filled glove box with the following process parameters: starting at 1000 rpm for 5 seconds (5-second ramp-up time from a standstill), then at 5000 rpm for 30 seconds (5-second ramp-up time from 1000 rpm). Before the end of the spin process, a solvent quenching method was used, with 200 μL of anisole dropped onto the spin-coated substrate 35 seconds after the start of the spin process. Then, thermal annealing (100°C for 50 minutes) was performed to form the perovskite layer. For PC-based... 61 BM's battery will use the prepared PC 61 BM solution (20 mg / mL in a mixed solvent of chlorobenzene, CB, and 1,2-dichlorobenzene, o-DCB) -1 The sample was dynamically rotated onto the perovskite layer at 2000 rpm for 20 seconds (CB:o-DCB volume ratio = 3:1). The sample was then annealed at 100 °C for 5 minutes. After cooling to room temperature, the prepared BCP solution (0.5 mg / mL in isopropanol) was applied. -1 Dynamically rotate to PC at 4000 rpm 61 Apply to the BM layer for 20 seconds, then perform a brief heat annealing treatment at 100°C for approximately 1 minute. PC 61 Both the BM and BCP layers are processed inside a nitrogen-filled glove box. For C-based...60 For devices, for 20-nm C 60 2-nm BCP deposition was performed, and the evaporation chamber was evacuated to 8×10⁻⁶. –7 and 2×10 –66 The base pressure is between mbar. The chamber walls are maintained at 17°C and the rotating substrate at 20°C by two separate coolers. High vacuum (5 × 10⁻⁶ mbar) is achieved by using a thermal evaporator (Nano 36, Kurt J. Lesker) placed in the ambient environment. -6 A solar cell is completed by thermally evaporating Cr (3.5 nm) and Au electrodes (100 nm) under a shadow mask at a temperature of mbar.

[0258] Solar cell characterization and stability testing In simulated sunlight (AM 1.5 irradiance generated by a Wavelabs SINUS-220 simulator) and darkness, current-voltage and maximum power point measurements were measured in the ambient environment using two Keithley 2400 Series source meters. The effective area of ​​the solar cell was shaded to 0.25 or 1 cm² within an opaque holder using black anodized metal apertures. 2 Scan from "reverse" (i.e., from "forward bias" to "short circuit"), then at 245 mV s. -1 A forward scan (i.e., from short-circuit to forward bias) was performed at a scan rate to acquire the current-voltage characteristics. Subsequently, a 120-second active maximum power point tracking measurement was performed using a gradient descent algorithm to obtain the maximum power point tracking efficiency. The intensity of the solar simulator was periodically set to match the short-circuit current density of the KG3-filtered Si reference photodiode (Fraunhofer ISE) to its 1-sun certified value. Before each batch of solar cell measurements, a local intensity measurement was performed by integrating the spectrum obtained from the solar simulator's internal spectrometer. By comparing this internal intensity measurement with the measurement obtained during calibration, the equivalent irradiance at the time of measurement was determined.

[0259] The perovskite solar cells were first coated with a thin layer of CYTOP™ (CTL-809M, AGC Chemicals), then dried under vacuum, and subsequently encapsulated in a nitrogen-filled glove box using a cover glass (LT cover, Lumtec) and UV adhesive (LT-U001, Lumtec). All encapsulated devices were then aged in a simulated full-spectrum AM 1.5 sunlight immersion chamber using an Atlas SUNTEST CPS+ (1500W air-cooled xenon lamp) at an irradiance of 77 mW cm⁻¹. -2Furthermore, no ultraviolet filters were used. All aging tests performed in this work were conducted under open-circuit conditions. For current-voltage characterization, samples were removed from the chamber and tested at different aging times according to the measurement protocol described herein. The aging chamber used to store the packaged samples was air-cooled and the temperature was controlled at 85°C (measured using a black standard temperature control unit). During aging, the relative humidity in the laboratory was monitored within the range of 50-60%.

[0260] Photoluminescence quantum yield Photoluminescent quantum yield (PLQY) measurements were performed using the de Mello method (de Mello, JC et al.). An improved experimental determination of external photoluminescence quantum efficiency The sample was photoexcited using a 532 nm CW laser diode (ThorLabs DJ532-10) coupled to an optical fiber and an integrating sphere. The laser intensity was adjusted to provide a photon flux equivalent to one solar equivalent, which, for this excitation wavelength and the band gap of the absorbing material studied in an earlier article, is approximately 56 mW / cm². -2 (Kirchartz, T. et al., Photoluminescence-Based Characterization of Halide Perovskites for Photovoltaics A second fiber runs from the output of the integrating sphere to the QEPro spectrometer (purchased from OceanOptics). The system is calibrated by illuminating the integrating sphere with a calibration halogen lamp (HL-3P-INT-CAL, OceanInsight) that has a specified spectral irradiance. Spectral correction coefficients are established to match the detector's spectral output to the lamp's calibrated spectral irradiance.

[0261] External quantum efficiency The external quantum efficiency (EQE) of the device was measured using a Fourier transform photocurrent spectroscopy system based on a Bruker Vertex 80V Fourier transform interferometer. The solar cell was shielded with a metal aperture, allowing the entire effective area to be illuminated by a halogen tungsten lamp. To determine the EQE, the photocurrent spectrum of the device under test was divided by the photocurrent spectrum of a calibrated Si reference cell (Newport) with a known EQE. Acquisition times for each photocurrent spectrum were ~60 seconds, and the measurements were taken under ambient conditions. To determine the equivalent short-circuit current density at 1 solar irradiance from the EQE measurements, the AM1.5 photon flux (…) was calculated. φ AM1.5 The overlap integral of the spectrum and EQE. Specifically, this is given by the following equation:

[0262] Where q is the elementary charge and λ is the wavelength.

[0263] Terahertz photoconductivity Using authors such as Ulatowski, A., etc., Revealing Ultrafast Charge-Carrier Thermalization in Tin-Iodide Perovskites through Novel Pump–Push–Probe Terahertz Spectroscopy. ACS Photonics 8, 2509-2518 (2021) The optically pumped terahertz (THz) probe technique described herein was used to measure optically induced time-resolved conductivity. The thin film was photoexcited using laser pulses from a Ti:Sapphire laser system (pulse duration 35 fs, center wavelength 800 nm, repetition rate 5 kHz; Spectra Physics MaiTai-Ascend-Spitfire regenerative amplifier). The frequency was then doubled to 400 nm using a BBO crystal. The excitation flux was controlled using a neutral density filter wheel. The time delay between the optical pump pulse and the probe THz pulse was adjusted using an optical delay stage. A spintronic emitter (2 nm tungsten, 1.8 nm Co on a quartz substrate) was used. 40 Fe 40 B 20 THz radiation was generated using a 2 nm platinum laser. Transmitted THz radiation was measured in a 1 mm thick ZnTe(110) crystal using a gated beam with a wavelength of 800 nm originating from the same laser system described above. The polarization of the gated beam was measured using a quarter-wave plate, a Wollaston prism, and a balanced photodiode detector.

[0264] The relative change in THz transmission through excited and unexcited thin films was measured by selectively blocking half of the pump pulse and half of the THz pulse using two optical choppers, and recording four different transmission signals (THz-on-pump-off, THz-off-pump-off, THz-on-pump-on, THz-off-pump-on) using a custom FPGA-based data acquisition board. T The photoinduced conductivity σ of the thin film can be expressed as:

[0265] in d It is the thickness of the thin film. n sub It is the refractive index of the quartz substrate ( n sub =2.1 2 ), T It is the difference between the THz radiation transmitted through the light-excited sample and the sample in darkness, and T is the electric field intensity of the THz radiation transmitted through the sample in darkness. 0 and c These are the dielectric constant of free space and the speed of light, respectively.

[0266] Total mobility of charge carriersµ Starting from the initial value of THz conductivity at t=0, the photoinduced conductivity and photoexcited charge carrier pair density are used. n Calculate based on the relationship between them.

[0267] in e It is electronic charge. Photoexcites charge carriers. n The number density at (t=0) is estimated from the absorption spectrum, assuming that all absorbed photons are converted into electron-hole pairs. This assumption is reasonable for lead halide perovskites at room temperature, given their low exciton binding energy.

[0268] Photoluminescence imaging Photoluminescence (PL) images taken for this work were produced in collaboration with Dasgupta, A. et al. Visualizing Macroscopic Inhomogeneities in Perovskite Solar Cells The same setup was used. The sample was optically excited using a 440nm LED and electronically contacted via a source meter (Keithley 2636). The excitation intensity was controlled by adjusting the LED's current consumption. The LED intensity corresponding to an equivalent solar irradiance was determined by measuring the current under short-circuit conditions and varying the intensity until it matched the current measured on a solar simulator. Spatially resolved photoluminescence maps were obtained using a scientific CMOS camera sensor (Andor Zyla 4.2, Oxford Instruments). A long-pass filter was used to block the excitation light from entering the camera, ensuring only photoluminescence (PL) was incident on the sensor.

[0269] X-ray diffraction X-ray diffraction (XRD) patterns were measured at room temperature using a PANalytical X'Pert PRO diffractometer equipped with a Cu line-focusing X-ray tube operated at 4 kV with a tube current of 40 mA (Cu Kα radiation, λ = 1.506 Å). In the Bragg-Brentano geometry, a 1D detector collected data from each sample, with a typical collection time of 60 minutes per sample. Alignment was calibrated using ITO to avoid any peak shifts due to sample tilt. Lattice parameters were calculated using TOPAS software.

[0270] Grazing incidence wide-angle X-ray scattering Grazing-incidence wide-angle X-ray scattering (GIWAXS) data were recorded using a Rigaku SmartLab diffractometer equipped with a HyPix-3000 hybrid pixel array 2D detector and a rotating 3kW Cu Kα source (operating at 40kV, 45mA). X-ray photons with an energy of 8.048keV and CBO-f optics were incident on an aligned sample surface, held at grazing incidence angles of 0.5° and 1.5°. The sample was mounted on a 2D-XRD accessory stage with a beam stop for direct beams, located 65mm from the detector. The detector image was integrated and resampled into Q-space and combined using a script based on the PyFAI and pygix libraries. These libraries were also used for 1D curves of azimuth integration (Ashiotis, G. et al.). The fast azimuthal integration Python library: pyFAI For variable-angle GIWAXS measurements (αi = 0.5°–1.5°), samples were measured using different 2D-XRD aperture slit configurations prior to processing as described herein, which included parallel-beam optics, a 0.5° in-plane parallel slit collimator, a 0.1 mm incident slit, and a 10 mm long confinement slit at a single detector position.

[0271] Scanning electron microscope Scanning electron microscopy (SEM) samples were prepared following the perovskite solar cell fabrication process down to the perovskite layer, and subsequently treated with different aminosilane molecules. Top-down SEM images were captured on a FEI Quanta 600 FEG at an accelerating voltage of 3 kV. The SEM chamber was evacuated to 2 × 10⁻⁶. -4 mbar high vacuum.

[0272] Time-of-flight secondary ion mass spectrometry The perovskite samples used for time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements were prepared according to the same procedure used for solar cells. Measurements were performed using a TOF.SIMS 5 instrument (IONTOF GmbH), equipped with a bismuth primary ion source and O2. + A sputtering source was used to detect positive atoms and / or fragment ions. A 30keV Bi320B sputtering source was employed. + 3D ToF SIMS data were acquired using a primary ion beam within a 100 × 100 µm region. This was followed by a sputtering process, with each cycle lasting 1.5 seconds. During each sputtering cycle, 1 keV O2 was used in an alternating mode. + An ion beam bombards a 350 × 350 µm region of the sample. The sample holder containing the sample is sealed in an argon-filled container and transferred to the instrument immediately before testing.

[0273] Electronic structure calculation and modeling The Vienna Ab-initio Simulation Package (VASP) was calculated ab initio in Vienna (see Kresse, G. et al.). Ab initio molecular dynamics for liquid metals Kresse, G, et al. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse G. et al. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set First-principles simulations were performed within the framework of density functional theory (DFT) based on projected fused wave (PAW) fundamentals. All volumetric and surface structures were simulated using the generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE) modified for solids (PBEsol) with exchange correlation functions (see Perdew, JP et al.). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces All atomic species use the VASP-recommended PAW pseudopotential for (C:2s). 2 2p 2 N:2s 2 2p 3 H:1s 1 Pb:5d 10 6s 2 6p 2 、I:5s 2 5p 5 O:2s 2 2p 4 and Si:3s 2 3p 2 Because of the presence of organic molecules, Grimme's DFT-D3 dispersion correction was considered (Grimme, S. et al.). A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu All calculations were performed with a 500 eV plane-wave energy cutoff and Brillouin zone (BZ) sampling using a Γ-centered k-grid. More refined properties, such as density of states (DOS), charge density difference, surface energy, and binding energy, were computed using a 4×4×4 k-point grid (4×4×1 for the surface plate). All structural optimizations were performed with a Gaussian smear of 0.1, and a 0.01 Gaussian smear was used for more refined properties. The conjugate gradient algorithm was used to fully relax the cell volume, shape, and atomic positions of the bulk structure, as well as the atomic positions only of the surface plate, until the force on each atom converged to 0.01 eV Å. -1 The following. Equivalently, for electronic degrees of freedom, use 10. -6 The energy convergence criterion is eV.

[0274] 2. Passivation using silane components This paper demonstrates that a vapor-based aminosilane passivation strategy reduces photovoltage defects in perovskite solar cells, including mixed cations and mixed anions, to 100–120 mV. It shows that primary aminosilane passivation disrupts perovskite crystallinity and destroys long-range ordering and charge transport, while aminosilane molecules containing secondary or tertiary amines can both provide passivation and maintain long-range conductivity in the perovskite absorber. De novo molecular dynamics simulations reveal atomic-scale details of the strong passivating agent binding of aminosilane molecules on defective perovskite surfaces. Due to severe undercoordination of surface Pb ions adjacent to iodide vacancies, aminosilane adsorption via N-Pb and O-Pb bonds functions by increasing Pb coordination and eliminating surface vacancy defects, thereby promoting enhanced surface passivation. Importantly, it is shown that passivated and encapsulated perovskite solar cells can retain 95% of their initial efficiency for over 1500 hours under open-circuit conditions and simulated full-spectrum sunlight at 85°C in ambient air. It is believed that both silane and amine units can interact with and interact with each other on the perovskite surface, thereby affecting the electronic passivation of the surface.

[0275] This paper investigates the effects of APTMS vapor-phase passivation on mixed cation-lead mixed anion perovskite films and positive intrinsic anion perovskite solar cells (e.g., Figure 1 (b is shown schematically) (see Jariwala, S. et al.) Reducing Surface Recombination Velocity of Methylammonium-Free Mixed-Cation Mixed-Halide Perovskites via Surface Passivation, And Pothoof, J. et al. Surface Passivation Suppresses Local Ion Motion in Halide Perovskites For perovskite absorbents, Cs components with "methylammonium ion-free" composition are used. 0.13 FA 0.87 Pb(I 0.9 Br 0.1 )3 (FA = formamidinium ion). With Jariwala, S. et al., Reducing Surface Recombination Velocity of Methylammonium-Free Mixed- Cation Mixed-Halide Perovskites via Surface Passivation Consistent with previous work, a significant increase in PLQY was measured for perovskite films before and after APTMS passivation, ranging from approximately 6% to 24%. A diagram illustrating the vapor-phase passivation treatment is shown below. Figure 1 As shown in c.

[0276] To integrate into pin PV devices, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz) and [6,6]-phenyl-C61-butyrate methyl ester (PC) were used, respectively. 61 BM serves as both the hole and electron transport layer. Current density-voltage (JV) characteristics and other relevant PV performance parameters were obtained from optimized APTMS-treated PV cells and reference PV cells. Figure 29As shown, the PV performance of the APTMS-treated battery is relatively poor and significantly inferior to the untreated reference battery, with a noticeable hysteresis in the JV characteristics. Without being bound by theory, it is assumed that an excessively thick layer of APTMS forms, which inhibits electron extraction.

[0277] To understand whether the structure of silane molecules affects passivation or function in PV cells, perovskite films were prepared and treated with APTMS and other aminosilane molecules that deviate from APTMS. Figure 1 a), the other aminosilane molecules include trimethoxy(propyl)silane (PTMS), trimethoxy[3-(methylamino)propyl]silane (MAPTMS), (N,N-dimethylaminopropyl)trimethoxysilane (DMAPTMS), [3-(2-aminoethylamino)propyl]trimethylsilane (AEAPTMS), and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane[(AE)2APTMS] ( Figure 1 d).

[0278] The composition of Cs was examined 0.13 FA 0.87 Pb(I 0.9 Br 0.1 )3 and Cs 0.15 FA 0.85 Pb(I 0.6 Br 0.4 )3 (hereinafter referred to as I) 90 Br 10 and I 60 Br 40 ) perovskite membrane.

[0279] Aminosilane (AS) molecules are deposited in the gas phase using the following methods: i) Selected from... Figure 1 a) Load AS molecules into a petri dish; ii) Heat the petri dish containing the passivation molecules at 100°C for a short time (i.e., a few minutes) until all molecules vaporize; iii) Place the grown perovskite film sample in the petri dish for tens of seconds to a few minutes.

[0280] For I 90 Br 10 Compared to the reference, all aminosilane molecules (except PTMS, which has no amino functional group) showed increased PLQY (e.g. Figure 1 (as shown in e), while for I 60 Br 40 Besides PTMS and DMAPTMS, PLQY enhancement was observed after treatment. Figure 2 In particular, for wider bandwidth I... 60 Br 40Perovskite (~1.77 eV) showed an increase in PLQY from ~1.5% to 3% after APTMS treatment. However, for AEAPTMS and (AE)2APTMS treatments, this value increased to over 7% and over 20%, respectively.

[0281] A series of PLQY measurements were performed on various perovskite films and "semi-stacks" using AEAPTMS, consisting of indium oxide-tin oxide (ITO) glass substrate / hole transport layer (HTL, containing Me-4PACz and aluminum oxide nanoparticles) / perovskite, or glass substrate / aluminum oxide nanoparticles / perovskite / electron transport layer (ETL, containing PC61BM and copper bath, BCP). Significant enhancements were observed for aminosilane molecules containing primary and secondary amine groups [i.e., AEAPTMS and (AE)2APTMS]. For example, I... 90 Br 10 I 60 Br 40 and Cs 0.17 FA 0.83 Pb(I 0.77 Br 0.23 )3 (hereinafter referred to as I) 77 Br 23 This shows a significant increase in PLQY. Figure 3 ), for glass / I 60 Br 40 The PLQY of the / ETL stack increased from 0.07% in the control to 4.11% in the AEAPTM-treated membrane. Figure 4 a). At the same time, in Figure 4 Figure b shows the corresponding calculated quasi-Fermi level split (QFLS) values ​​for further comparison. This indicates that passivation specifically suppresses nonradiative recombination at the perovskite / ETL interface.

[0282] To further investigate the effect of passivation treatment, on I 90 Br 10 The samples underwent UV-Vis absorption spectroscopy and non-contact transient terahertz photoconductivity measurements because we observed the greatest PLQY enhancement in this perovskite composition when using APTMS. Figure 6 The UV-Vis absorption spectra of perovskite films with and without surface passivation are shown in the figure. Surprisingly, a significant decrease in optical density was observed in the perovskite film passivated with APTMS, less than half over the entire absorption range, indicating a bulk change in the perovskite film after passivation. Compared to the reference film, all other passivated films showed a small decrease in optical absorption.

[0283] Optically pumped terahertz (THz) probe spectroscopy revealed changes in the conductivity of the sample after photoexcitation and was used to determine the “short-range” charge carrier mobility. This technique revealed surprising differences in the sample. Figure 1 f and Figure 7 and Figure 8 For the reference membrane, the total mobility is approximately 60 cm⁻¹. 2 / Vs, this is a very high value for lead halide perovskites. For all passivation treatments, except PTMS, the mobility ( Figure 1 f) all decreased. For I processed by APTMS 90 Br 10 For the sample, this decrease in mobility is drastic, with the total mobility value dropping to 1.5 cm. 2 V -1 s -1 This indicates that the crystal order is significantly disrupted across the entire APTMS-treated perovskite film at a sufficiently short length scale, thereby suppressing charge carrier mobility originating from the THz. In contrast, the reduction in charge carrier mobility is much milder for other passivation molecules studied; for example, we determined the total mobility of the APTMS-treated film to be 46 cm⁻¹. 2 / Vs.

[0284] Given the severe disruption of the crystallization sequence in the APTMS-treated film, inferred from the decrease in THz mobility and light absorption intensity, changes in film crystallinity, as determined by electron microscopy or X-ray diffraction (XRD), are expected to be discernible. Firstly, the crystallinity is determined by scanning electron microscopy (SEM). Figure 9 The surface morphology of the samples was examined, and the influence of different aminosilane molecules on the film quality was investigated. Characteristic polycrystalline morphology was observed in all perovskite films, with SEM grain diameters ranging from approximately 150 to 200 nm. However, for I... treated with APTMS and MAPTMS... 90 Br 10 The perovskite film appears unclear and "cloudy" over a significant portion. This could be due to a complete morphological alteration in these areas or the presence of a thick overlay of amorphous material. For films treated with AEAPTMS and (AE)2APTMS, the polycrystalline structure is discernible across the entire surface area, but there is more "blurring" in the images, suggesting a surface coating with an insulating material.

[0285] Figure 31A series of XRD 2θ plots of the treated films are shown, revealing significant differences once again. The XRD traces of the PTMS, DMAPTMS, and AEAPTMS-treated samples showed no significant difference from the untreated samples, and all samples exhibited the characteristic XRD pattern of polycrystalline perovskite films without any additional diffraction peaks or significant changes in scattering intensity. For the (AE)2APTMS-treated samples, a slight decrease in peak intensity was observed, and the full width at half maximum (FWHM) of the first perovskite peak broadened, while the AEAPTMS-treated samples showed a narrower FWHM value for this perovskite characteristic peak compared to the untreated films (see Table 1). However, for the APTMS-treated I... 90 Br 10 In the samples, the intensities of all perovskite scattering peaks decreased by more than an order of magnitude. Furthermore, an additional peak at ~12 degrees was observed in the MAPTMS-treated samples, which can be attributed to PbI₂.

[0286]

[0287] Table 1. Full width at half maximum of perovskite characteristic peaks.

[0288] A clear picture has emerged from THz mobility measurements, SEM images, XRD patterns, and UV-Vis absorption traces. APTMS treatment has a strong effect on the crystallinity of the entire perovskite film, introducing short-range scattering defects or disrupting crystal domains to the extent that charge carriers are subject to short-range scattering and severely limit their mobility. Notably, even for perovskite nanocrystals with a crystal diameter of 7 nm, the charge carrier mobility is only reduced by a factor of three compared to the "bulk mobility" in polycrystalline films. Here, a 40-fold reduction in mobility indicates that the disruption of crystal order or the introduction of charge scattering sites occurs on a length scale much shorter than 7 nm, and therefore within the grains, not just at the polycrystalline grain boundaries. In contrast, the application of AEAPTMS and (AE)₂APTMS molecules appears to leave the crystal order and carrier mobility largely unaffected.

[0289] To explore in more detail how APTMS, MAPTMS, and AEAPTMS affect perovskite, grazing incidence wide-angle X-ray scattering (GIWAXS) was used to investigate their effects on treated I2O2. 90 Br 10The influence of orientation and crystallinity of perovskite films. A low incident angle (0.5°) GIWAXS was used, which is relatively close to the critical angle. This method provides information about the surface region extending tens of nanometers deep into the sample. The brighter ring color observed in the AEAPTMS-treated perovskite sample indicates higher crystallinity near the surface compared to the reference sample. Furthermore, after treatment, in the low Q space (i.e., 0.5 Å)... - A pair of broad rings appeared in (¹ below). This observation suggests that the organic passivation molecules are located in the upper part of the perovskite layer and may not extend deeper than the top 70 nm. At higher incident angles (1.5°), information about deeper regions within the perovskite samples was obtained. This was observed in all samples at Q xy =1.0, 1.4, 1.7, 2.0 Å -1 The continuous Debye-Scherrer diffraction rings at the location correspond to the (100), (110), (111), and (200) diffraction peaks in the 1D XRD pattern, respectively. This observation indicates that the isotropic orientation of the bulk perovskite is maintained with or without passivation treatment.

[0290] On the other hand, for APTMS-treated perovskite samples, no obvious Debye-Scherrer scattering rings were observed in the GIWAXS pattern at lower incident angles, consistent with the "disintegration" of the perovskite structure caused by APTMS molecules. As seen in the 1D in-plane and out-of-plane integrals of the 2D GIWAXS, all perovskite-specific rings disappeared, and in Q... xy =0.4Å -1 Wide isotropic rings appeared nearby. Based on the knowledge that primary amines can strongly interact with and “solvate” metal halide perovskites, these observations indicate that the perovskite film underwent a solvation process during APTMS treatment, reforming into a material with much lower crystallinity and a much shorter domain range, which is almost indistinguishable by X-ray diffraction. This APTMS-triggered solvation process caused visual changes in the film during treatment. Characterized by the retention of at least half of the absorption intensity in the UV-Vis view, and the maintenance of photoluminescence at the expected energy for 3D perovskites, and its extreme strength. This suggests that the 3D perovskite still exists, but in the form of well-passivated nanoscale domains.

[0291] For the MAPTMS sample, in addition to the perovskite ring, a highly oriented 2D phase appeared by fitting a Ruddlesden-Popper (RP) phase. Figure 10 From in-plane and out-of-plane 1D line cuts, it is clear that most 2D phase perovskites are oriented out-of-plane. The scattering vector Q along the z-axis... xy=0.43, 0.72 and 0.87 Å -1 Sharp diffraction peaks appeared at [a point], which we indexed to the (002), (102), and (004) planes of the RP-phase perovskite, with an interlayer spacing of approximately 14.2 Å. Figure 10 ).

[0292] Finally, to confirm this assertion regarding the penetration depth of treatments with APTMS, MAPTMS, and AEAPTMS, the films were further examined using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to examine the elemental depth distribution. While APTMS and MAPTMS exhibited varying degrees of silicon signal penetration throughout the film, the silicon signal in the film treated with AEAPTMS molecules remained on the surface of the perovskite layer. This observation held true even when the treatment duration was tripled.

[0293] To gain a deeper understanding of the structure and interactions of aminosilane molecules on perovskite surfaces, density functional theory (DFT) and ab initio molecular dynamics (AIMD) methods were used to investigate four types of silane molecules covering different possible amine positions: primary (APTMS), secondary (MAPTMS), primary and secondary (AEAPTMS), and the case without amine (PTMS). Their interactions on pristine perovskite surfaces and surfaces with iodide vacancy defects were examined. Iodide vacancy defects are known to play a key detrimental role in affecting the operating efficiency and stability of perovskite solar cells, including promoting ion migration to the surface and recombination of non-radiative photocarriers. To investigate the key adsorption and structural trends of a range of aminosilanes on FA-based MA-free perovskite triiodides, the pristine FAPbI3 surface capped with (001)PbI2 was investigated, as it is one of the most stable and well-studied halide perovskite surfaces.

[0294] Figure 11 The optimized structure and calculated binding energy of aminosilane molecules on pristine surfaces and on iodide vacancy-defect surfaces are shown. Three important features emerge. First, the favorable binding energy indicates a strong binding affinity between the molecule and the surface, with the highest and lowest binding energies for AEAPTMS and PTMS, respectively; interestingly, only for AEAPTMS, the surface binding energy increases significantly from the pristine surface to the iodide vacancy-defect surface. Second, the strongest adsorption on AEAPTMS indicates the role of larger aminosilane molecules with primary and secondary amine groups in providing effective surface defect passivation. Due to the severe undercoordination of surface Pb ions adjacent to iodide vacancies (having tetracoordination while being octahedral in bulk), the strong passivating agent adsorption on AEAPTMS works by increasing the coordination around these Pb ions and eliminating surface vacancy defects.

[0295] Third, due to the long-standing speculation regarding the precise atomic interactions of aminosilane molecules on the perovskite surface, simulations revealed that the terminal amine in AEAPTMS binds to surface Pb atoms with an N-Pb bond length of 2.51 Å, significantly shorter than the 3.15 Å Pb-I bond length. (Illustrative) Figure 11 The diagram shows that the AEAPTMS molecule bridges two Pb ions adjacent to the iodide vacancy via N-Pb bonds. O-Pb bonds with an average bond length of 2.8 Å are also shown. The charge density distribution around all species varies ( Figure 11 (b) shows the surface charge transfer of silane around the surface Pb cations, again demonstrating the O-Pb and N-Pb chemical bonds. This multidentate interaction increases the bonding or anchoring strength on the surface, thereby enhancing effective passivation. Overall, the ab initio simulation results are in excellent agreement with experimental results and provide new structural and mechanistic insights at the atomic level.

[0296] 3. Solar cells A series of solar cells were fabricated and measured to screen a range of aminosilane molecules (Figure 12). For I-based 90 Br 10 The perovskite AEAPTMS molecule most significantly improves PV performance parameters. Cells treated with (AE)₂APTMS also exhibit enhanced PV performance, but in some cases, (AE)₂APTMS-treated cells were found to show lower J. SC And FF, therefore, the PCE is lower compared to cells treated with AEAPTMS, while requiring a very narrow process window (<10 seconds for vapor processing).

[0297] Figures 13a, 13b, and 13c show the use of I, respectively. 90 Br 10 I 77 Br 23 and I 60 Br 40 The reference and representative JV characteristics of AEAPTMS-treated cells. These pore sizes are 0.25 cm. 2 The battery exhibits the following corresponding PV parameters for the scan directions from forward bias to short circuit (FB-SC) conditions: V OC =1.22, 1.26 and 1.35V, J SC =22.3, 19.5 and 17.2 mAcm -2 FF=83.4, 84.0 and 80.9%, and PCE=22.6, 20.6 and 18.7%. Figure 14 , Figure 15 and Figure 16The corresponding external quantum efficiency (EQE) and 120-second maximum power point tracking (MPPT) are shown respectively. The MPP efficiency is compared with that of I... 90 Br 10 I 77 Br 23 and I 60 Br 40 The percentages of the batteries were 22.4%, 20.7%, and 18.6%, respectively. EQE analysis revealed that, compared to J measured from the corresponding batteries under simulated sunlight... SC In comparison, integral J SC It exhibits negligible changes (<1%), as shown in Figures 13a-3c. The PV bandgap derived by EQE for I 90 Br 10 I 77 Br 23 and I 60 Br 40 The values ​​are 1.60, 1.67, and 1.77 eV, respectively. OC J SC The statistical results for FF and PCE are respectively in Figure 17 , Figure 18 , Figure 19 and Figure 20 As shown.

[0298] It is particularly important to note that for 1.67 and 1.77 eV perovskites (i.e., I... 77 Br 23 and I 60 Br 40 The VOCs can reach as high as 1.28 and 1.38 V, respectively. This high photovoltage of mixed-cation and mixed-anion perovskite cells is crucial for the development of next-generation perovskite-based tandem solar cells. Multi-junction perovskite and all-perovskite cells on silicon typically employ thermally evaporated C... 60 As an ETL. To demonstrate the compatibility of the passivation treatment disclosed herein with this ETL, C with evaporation was fabricated. 60 and BCP's I 77 Br 23 This makes V OC The increase from 1.21 (control) to 1.26 V (passivated) confirms that the method discussed in this paper is applicable to tandem cells.

[0299] They also manufactured 1-cm 2 The battery, and the corresponding JV characteristics, MPPT, and EQE are shown in Figure 13d, ... Figure 13e and supplements Figure 21 The results show the PV parameter enhancements obtained (Table 2) and the minimum performance defect of 0.25 cm² when the battery area is increased. 2 Similarities were observed in small-area batteries. 1-cm2 The battery results demonstrate that the vapor passivation method can produce a highly uniform passivation effect. Detailed equilibrium V values ​​were estimated for different bandgap absorbers. OC The limit value was determined and compared with the value obtained in the device described herein. AEAPTMS can generally express V... OC The photovoltage was increased to over 90% of the theoretically achievable voltage. These results indicate that the photovoltage obtained from perovskite PV cells treated with AEAPTMS is close to that achievable from PV cells made from single-crystal epitaxially grown III-V semiconductors.

[0300]

[0301] Table 2. For using I 90 Br 10 (i.e., 1.60 eV), I 77 Br 23 (i.e., 1.67 eV) and I 60 Br 40 (i.e., 1.77 eV) as a light absorber, as shown in Figure 13d, 1-cm 2 The corresponding PV performance parameters obtained from solar cells treated with AEAPTMS.

[0302] Next, we investigated how AEAPTMS affects the long-term operational stability of solar cells. This was achieved by comparing the encapsulated reference and the AEAPTMS-treated I... 90 Br 10 The cells were aged in a laboratory environment with a relative humidity of 50-60%, under open-circuit conditions, and exposed to full-spectrum simulated sunlight at 85°C. These aging conditions were similar to those of the ISOS-L-3 protocol (ISOS: International Summit on Organic Photovoltaic Stability). The devices were then removed from the aging chamber, cooled to room temperature, and characterized at different time intervals under 1-solar simulated sunlight. The average maximum power point (MPP) tracking efficiency and JV-derived PCE and their standard deviations are plotted on... Figure 22a In the middle, the corresponding PV performance parameters are: V OC J SC The evolution of FF and FF respectively in Figure 23 , Figure 24 and Figure 25 The evolution of MPP efficiency and PCE data for each individual cell is shown in Figure 22b. Cells treated with AEAPTMS maintained high operating levels during aging, and the champion cell took approximately 1600 and 1440 hours, respectively, to decrease to its initial MPP (…). Figure 22a And Figure 22b, Figure 36 ) and PCE ( Figure 3595% (T) 95，冠军 This indicates that the mixed-cation mixed-halogen perovskite PV cell exhibits excellent stability. In comparison, this represents better stability than the best previously reported under the same aging conditions (Champion "T"). 80 "Lifetime (the time to reach 80% of peak performance) is an order of magnitude improved to 430 hours."

[0303] It was observed that even when encapsulating with a coverslip and epoxy edge seal for optimal stability, a "capping layer" was required to coat the entire device, for which CYTOP™ (an amorphous fluorinated polymer) was used. Without the capping layer on the cell, the cell area discolors. Since the cell was encapsulated in a nitrogen-filled glove box, this is thought to be due to the loss of iodine during photoinduced degradation, which leaves voids in the film and reacts with the metal electrodes. When comparing the external quantum efficiency (EQE) spectra measured from the aged cell (… Figure 26 No significant change in the initial EQE energy was observed, indicating minimal compositional changes during aging. However, compared to the AEAPTMS-treated cell, the reference cell suffered more severe full-color degradation on EQE, which is consistent with J SC The more severe decline is consistent. Notably, the dips in the EQE spectrum appear to be due to sporadic internal shunting of the aging device during the measurement process, which tends to self-correct.

[0304] Given the changes in battery performance observed during aging ( Figure 22a (See Figure 22b) for PL imaging of the battery to elucidate how AEAPTMS enhances long-term stability. Representative full-area 0.25-cm² data are used at different aging stages. 2 QFLS images of the battery and reference battery derived from AEAPTMS are shown in Figures 22c, 22d, and 22d. Figure 27 As shown. Interestingly, even the reference cell maintained a relatively high and stable QFLS plot comparable to its initial state over a period of 300 hours. The relative decay of the median QFLS was only 2.8% (from 1.160 eV to 1.128 eV, Figure 22g), demonstrating this stability. However, after 600 hours of aging, distinct regions of lower and higher QFLS appeared in the plot (Figures 22d, 22g, and...). Figure 27 This indicates that the battery underwent heterogeneous degradation over a length scale of 100 µm to mm. The QFLS of a complete device should be consistent with V. OC Closely related. However, as Figure 23 As shown, with the aging of the reference battery, QFLS and V OCThe difference gradually increases, reaching ~380 mV by the end of the aging process. This indicates that either (i) a significant energy shift (i.e., vacuum level) occurred at one or both charge-selective contacts, or (ii) the charge selectivity of one of the contacts has decreased. For the reference cell, in addition to V OC In addition to the loss of PV, other PV performance parameters also suffered significant losses. Figures 23-25 Therefore, PL imaging showed that the perovskite absorber could remain relatively intact under the stringent 85°C light immersion aging conditions, while other parts of the cell may have deteriorated significantly. The significant decay observed in the FF indicates increased resistance to charge extraction. Cells treated with AEAPTMS showed less degradation on QFLS and remained uniform throughout the aging process. Specifically, although the median in QFLS was initially 1.227 eV at 0 hours, this value only decreased from 1.187 eV at 300 hours to 1.167 eV at 1200 hours (Figs. 22c, 22g, and 22g). Figure 27 ).

[0305] While the QFLS plot provides valuable insights, it does not appear to be directly related to the order of battery degradation. Therefore, the charge collection quality derived from luminescence (QFLS plot) is not directly correlated with the order of battery degradation. col An evaluation was conducted. (Q) col It should be qualitatively related to J SC Proportional. Figures 22c and 22d show the Q values ​​of fresh and 600-hour aged devices. col The diagram, and in Figure 28 The image shows Q throughout the aging process. col The complete dataset. Consistent with macroscopic device JV measurements, the reference cell exhibits Q after aging. col A significant decrease (see Figure 22f). After 600 hours of aging, the median decreased from 0.963 at the initial state to 0.420 (see Figure 22h), indicating a degradation of over 56%. Notably, Q... col The lower Q values ​​correlate with the same region where QFLS is lower. Interestingly, even for the reference cell, there is still a considerably high Q value after aging. col This indicates that the degradation originates in specific defect areas, rather than being uniform across the entire device. In contrast, AEAPTMS-treated cells exhibit even higher initial median Q values. col (0.985), which only decreased to 0.914 after 1200 hours of aging and remained relatively uniform. Although the most stable device showed near-linear degradation in our stress tests, some cells were observed to have undergone positive light immersion (i.e., performance enhancement) or aging (i.e., early degradation) during the aging process for the reference and AEAPTMS treated devices (Fig. 22b).

[0306] This embodiment demonstrates that aminosilane molecules with different primary, secondary, and tertiary amine functional groups significantly affect the PLQY, crystal order, and charge carrier mobility of halide perovskites. AEAPTMS exhibits excellent surface passivation properties, establishing a strong bonding affinity with the perovskite surface. Notably, AEAPTMS treatment significantly improves the PLQY of perovskites with band gaps ranging from 1.6 to 1.8 eV, bringing their radiative efficiency closer to the theoretical limit. Furthermore, AEAPTMS-treated perovskite solar cells demonstrate state-of-the-art long-term stability under severe high-temperature light immersion aging conditions, highlighting the potential of this invention to advance durable and efficient perovskite solar energy technology.

[0307] Embodiments of the present invention are described in the following numbered paragraphs.

[0308] 1. A photovoltaic device comprising passivated A / M / X material, The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0309] 2. The photovoltaic device according to embodiment 1, wherein the organic compound comprises a silane portion and an amine portion, wherein the amine portion is a secondary amine, a tertiary amine, or a quaternary amine.

[0310] 3. The photovoltaic device according to Embodiment 1 or Embodiment 2, wherein the organic compound comprises a silane moiety and a plurality of amine moieties, wherein at least one of the amine moieties is a secondary amine, a tertiary amine, or a quaternary amine.

[0311] 4. The photovoltaic device according to Embodiment 1 or Embodiment 2, wherein the organic compound comprises a silane moiety and two to five amine moieties, wherein at least one of the amine moieties is a secondary amine, a tertiary amine, or a quaternary amine.

[0312] 5. The photovoltaic device according to embodiment 3 or embodiment 4, wherein at least one of the amine portions is a primary amine.

[0313] 6. The photovoltaic device according to embodiment 3 or embodiment 4, wherein one of the amine portions is a primary amine, and each of the other amine portions is independently selected from secondary amines, tertiary amines, and quaternary amines, preferably, one of the amine portions is a primary amine, and each of the other amine portions is a secondary amine.

[0314] 7. The photovoltaic device according to any one of embodiments 2 to 6, wherein the organic compound comprises an organic group bonded to a silicon atom of a silane moiety, wherein each of the amine moieties is present in the organic group.

[0315] 8. The photovoltaic device according to embodiment 7, wherein the organic group is C. 1-20 Alkyl groups, wherein each amine moiety, which is a secondary, tertiary, or quaternary amine, can interrupt C. 1-20 The carbon chain of an alkyl group, or present as a substituent at C10. 1-20 On an alkyl group, and wherein any amine moiety of a primary amine exists as a substituent at C. 1-20 On an alkyl group, and wherein C 1-20 Alkyl groups are either unsubstituted or substituted.

[0316] 9. The photovoltaic device according to Embodiment 7 or Embodiment 8, wherein the organic group is selected from thiols, C 1-10 One or more groups of alkylthio, arylthio, carboxyl, pyridyl, and bipyridyl are substituted.

[0317] 10. The photovoltaic device according to any one of embodiments 7 to 9, wherein the organic compound has formula (I). (I) in: R is the organic group; and E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted C 1-10 Alkyl, unsubstituted or substituted aryl, unsubstituted or substituted acyl, unsubstituted or substituted ester, unsubstituted or substituted acyloxy, hydroxyl and halogen.

[0318] 11. The photovoltaic device according to embodiment 10, wherein R is C as defined in embodiment 8. 1-20 Alkyl, and E 1 E 2 and E 3 Is it unsubstituted or substituted C? 1-10 Alkoxy, preferably unsubstituted C 1-10 Alkyl group, more preferably methoxy group.

[0319] 12. The photovoltaic device according to any one of the foregoing embodiments, wherein the organic compound has formula (II). (II) in: E 1 E 2 and E 3 As defined in Embodiment 10, and preferably independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted C 1-10 Alkyl groups, unsubstituted or substituted aryl groups, and unsubstituted or substituted aryl groups; q is 0 or an integer from 1 to 5; Each m is an independent integer from 1 to 5; Each n is independently 0 or 1; p is 0 or an integer from 1 to 5; G is NR 1 2 or CR 1 3; Each R 1 H or C independently 1-6 alkyl; Where each n is 0 and G is NR 1 2, or when q is 0 and G is NR 1 2, then at least one R 1 The group is C 1-6 Alkyl, and Preferably, when G is NR 1 2. If q is not 0, then p is not 0. 13. The photovoltaic device according to embodiment 12, wherein E 1 E 2 and E 3 Is it unsubstituted or substituted C? 1-10 Alkoxy, preferably unsubstituted C 1-10 Alkyl group.

[0320] 14. The photovoltaic device according to Example 12 or Example 13, wherein E 1 E 2 and E3 At least one of them is a methoxy group, preferably, wherein E 1 E 2 and E 3 At least two of them are methoxyl groups, more preferably, wherein E 1 E 2 and E 3 They are all methoxyl groups.

[0321] 15. The photovoltaic device according to any one of embodiments 12 to 14, wherein G is NR 1 2.

[0322] 16. The photovoltaic device according to any one of embodiments 12 to 15, wherein each R 1 Independently H or methyl, more preferably, wherein each R 1 For H.

[0323] 17. The photovoltaic device according to any one of embodiments 12 to 16, wherein q is 0, 1 or 2, preferably wherein q is 1 or 2.

[0324] 18. The photovoltaic device according to any one of embodiments 12 to 17, wherein q is 0.

[0325] 19. The photovoltaic device according to any one of embodiments 12 to 17, wherein q is an integer from 1 to 5, each m is independently 1, 2 or 3, and each n is 1, preferably, wherein q is 1 or 2, each m is 2, and each n is 1.

[0326] 20. The photovoltaic device according to any one of embodiments 12 to 19, wherein p is an integer from 1 to 5, preferably, wherein p is 1, 2 or 3.

[0327] 21. The photovoltaic device according to any one of embodiments 1 to 14, wherein the organic compound is selected from: (i) PTMS ; (ii) MAPTMS ; (iii) DMAPTMS ; (iv) AEAPTMS ;as well as (v)(AE)2APTMS , Optionally, the organic compound is selected from (ii) MAPTMS, (iii) DMAPTMS, (iv) AEAPTMS and (v) (AE)2APTMS.

[0328] 22. The photovoltaic device according to any one of embodiments 1 to 14 and 21, wherein the organic compound is AEAPTMS.

[0329] 23. The photovoltaic device according to any one of embodiments 1 to 14 and 21, wherein the organic compound is (AE)2APTMS.

[0330] 24. The photovoltaic device according to any one of the foregoing embodiments, wherein the dimer of the organic compound comprises (i) a first monomer unit, wherein the first monomer unit is an organic compound as defined in any of the foregoing embodiments, provided that the silicon atom of the silane portion of the first monomer unit is replaced by a linking atom or a group; and (ii) a second monomer unit, wherein the second monomer unit is an organic compound as defined in any of the foregoing embodiments, provided that the silicon atom of the silane portion of the second monomer unit is replaced by a linking atom or a group, wherein the linking atom or group is covalently bonded to the silicon atom of the silane portion of the first monomer unit and covalently bonded to the silicon atom of the silane portion of the second monomer unit to link the first monomer unit to the second monomer unit.

[0331] 25. The photovoltaic device according to embodiment 24, wherein the first monomer unit is an organic compound as defined in any one of embodiments 10 to 20, provided that the E of the first monomer unit is... 1 E 2 and E 3 One of them is the connecting atom or group, and the second monomer unit is an organic compound as defined in any one of embodiments 10 to 20, provided that the E of the second monomer unit is... 1 E 2 and E 3 One of them is the connecting atom or group.

[0332] 26. The photovoltaic device according to embodiment 24 or embodiment 25, wherein the dimer has formula (Ia) or formula (IIa): (Ia) Where L is the connecting atom or group, and each R, E 1 and E 2 Independently as defined in embodiment 10 or embodiment 11;

[0333] (IIa) Where L is the connecting atom or group, and each G, p, n, m, q, E 1 and E 2 Independently as defined in any of embodiments 12 to 20.

[0334] 27. The photovoltaic device according to any one of embodiments 24 to 26, wherein the connecting atom or group is a connecting atom, wherein the connecting atom is an oxygen atom.

[0335] 28. A photovoltaic device according to any one of embodiments 1 to 23, wherein the polymer of the organic compound comprises a monomer unit, the monomer unit being an organic compound as defined in any one of embodiments 1 to 23, provided that the silicon atom of the silane portion is replaced by at least one linking atom or group, wherein the linking atom or group, or each linking atom or group, is covalently bonded to the silicon atom and also covalently bonded to the silicon atom of the silane portion of another monomer unit in the polymer.

[0336] 29. The photovoltaic device according to embodiment 28, wherein the monomer unit is an organic compound as defined in any one of embodiments 10 to 20, provided that E 1 E 2 and E 3 At least one of them is the connecting atom or group, typically wherein E 1 E 2 and E 3 The two in the text are the connecting atoms or groups.

[0337] 30. The photovoltaic device according to embodiment 28 or embodiment 29, wherein each connecting atom or group is a connecting atom, wherein the connecting atom is an oxygen atom.

[0338] 31. The photovoltaic device according to any one of embodiments 28 to 30, wherein the polymer of the organic compound comprises a monomer unit of formula (Ib) or formula (IIb): (Ib) Where L is the connecting atom or group, and R and E 1 As defined in embodiment 10 or embodiment 11; (IIb) Where L is the connecting atom or group, and G, p, n, m, q and E 1 As defined in any of embodiments 12 to 20, Preferably, the polymer comprises at least three monomer units of formula (Ib) or formula (IIb).

[0339] 32. The photovoltaic device according to any one of embodiments 28 to 31, wherein the polymer comprises a structure of formula (Ic) or formula (IIc): (Ic) Where each L is the connecting atom or group, and each R and E 1 Independently as defined in embodiment 10 or embodiment 11, and z is an integer of at least 3; (IIc) Where each L is the connecting atom or group, and each G, p, n, m, q, and E 1 Independently as defined in any of embodiments 12 to 20, and z is an integer of at least 3.

[0340] 33. The photovoltaic device according to any one of the foregoing embodiments, wherein the passivating agent is disposed on the surface of the crystalline A / M / X material.

[0341] 34. The photovoltaic device according to any one of the foregoing embodiments, comprising a layer containing passivated A / M / X material.

[0342] 35. The photovoltaic device according to embodiment 34, wherein the layer comprising passivated A / M / X material comprises (i) a crystalline A / M / X material layer and (ii) a passivating agent layer disposed on the surface of the crystalline A / M / X material layer.

[0343] 36. The photovoltaic device according to embodiment 34 or embodiment 35, wherein the layer containing the passivated A / M / X material is composed of passivated A / M / X material.

[0344] 37. The photovoltaic device according to embodiment 34, wherein the layer comprising passivated A / M / X material comprises particles of passivated A / M / X material, optionally wherein the particles are nanoparticles, and optionally wherein each particle comprises particles of crystalline A / M / X material and the passivating agent disposed on the surface of the crystalline A / M / X material, and optionally wherein the layer further comprises a matrix material, and the particles are dispersed in the matrix material.

[0345] 38. The photovoltaic device according to any one of embodiments 34 to 37, comprising a photoactive region, wherein the photoactive region comprises an n-type region including at least one n-type layer, a p-type region including at least one p-type layer, and a layer disposed between the n-type region and the p-type region comprising a passivated A / M / X material. Optionally, the photoactive region is disposed between the first electrode and the second electrode.

[0346] 39. The photovoltaic device according to any one of embodiments 34 to 38, wherein the thickness of the layer comprising the passivated A / M / X material is from about 10 nm to about 100 μm, optionally from about 10 nm to about 10 μm, and preferably from about 100 nm to about 1000 nm.

[0347] 40. The photovoltaic device according to any one of embodiments 1 to 33, wherein the passivated A / M / X material comprises particles of the passivated A / M / X material, optionally wherein the particles are nanoparticles, optionally wherein each particle comprises particles of crystalline A / M / X material and the passivating agent disposed on the surface of the crystalline A / M / X material, and optionally, the particles are dispersed in a matrix material.

[0348] 41. The photovoltaic device according to any one of the foregoing embodiments, wherein formula [A] a [M] b [X] c The compound is a compound of formula [A][M][X]3, wherein [A], [M] and [X] are as defined in Embodiment 1.

[0349] 42. The photovoltaic device according to any one of the foregoing embodiments, wherein the one or more X anions are one or more halide anions, and preferably, wherein the one or more A cations are monovalent cations and the one or more M cations are divalent cations.

[0350] 43. The photovoltaic device according to any one of the foregoing embodiments, wherein the one or more A cations include at least one organic cation.

[0351] 44. The photovoltaic device according to any one of the foregoing embodiments, wherein [A] comprises two or more different A cations.

[0352] 45. The photovoltaic device according to any one of the foregoing embodiments, wherein each A cation is selected from: Alkali metal cations; Equation [R1R2R3R4N] + The cations, wherein R1, R2, R3, and R4 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl group, and at least one of R1, R2, R3 and R4 is not hydrogen; Equation [R5R6N=CH-NR7R8] + The cations, wherein R5, R6, R7, and R8 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C6-12 Aryl; and C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 cycloalkylimine ion, C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 The cycloalkylimine ions are each unsubstituted or selected from amino, C 1-6 Alkylamino, imino, C 1-6 Alkylimino, C 1-6 Alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6-12 One or more substituents of the aryl group are substituted; Preferably, each A cation is selected from Cs. + 、Rb + Formamidinium ion, guanidine ion, methylammonium ion and ethylammonium ion.

[0353] 46. ​​The photovoltaic device according to any one of the foregoing embodiments, wherein [X] comprises two or more different X anions, preferably, wherein the two or more different X anions are two or more different halide anions, and optionally, wherein [X] comprises Br and I.

[0354] 47. The photovoltaic device according to any one of the foregoing embodiments, wherein [A] comprises formamidinium ions, and optionally, wherein [A] further comprises Cs. + .

[0355] 48. The photovoltaic device according to any one of the foregoing embodiments, wherein [A] does not contain methylammonium ions, or [A] is composed of methylammonium ions and at least one A cation other than methylammonium ions, provided that the molar fraction of methylammonium ions in [A] is less than 15% of [A].

[0356] 49. The photovoltaic device according to any one of the foregoing embodiments, wherein [M] comprises components selected from Ca 2+ 、Sr 2+ Cd 2 + Cu 2+ Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ and Eu 2+ The M cation may optionally be selected from Sn. 2+ Pb 2 + Cu 2+ 、Ge 2 and Ni 2+ Preferably selected from Sn 2+ and Pb 2+ Preferably, [M] contains Pb 2+ .

[0357] 50. The photovoltaic device according to any one of the foregoing embodiments, wherein formula [A] a [M] b [X] c The compound is of formula [Cs] x (H2N–C(H)=NH2) 1-x ]Pb[I y Br 1-y Compounds of type 3, wherein x is greater than 0 and less than 1, and y is greater than 0 and less than 1.

[0358] 51. The photovoltaic device according to any one of the foregoing embodiments, wherein the photovoltaic device is a solar cell.

[0359] 52. The photovoltaic device according to any one of the foregoing embodiments, wherein the photovoltaic device is a multi-junction or stacked-junction photovoltaic device.

[0360] 53. The use of passivated A / M / X materials as sensitizers in photovoltaic devices. The passivated A / M / X material includes crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds.

[0361] 54. A method for producing passivated A / M / X materials, The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: Production of photovoltaic devices including passivated A / M / X materials.

[0362] 55. A method for producing passivated A / M / X materials, The passivated A / M / X material comprises a crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X]c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, passivating agents may include dimers or polymers of organic compounds. The method includes: (i) Treat the crystalline A / M / X material with the passivating agent; or (ii) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: Passivated A / M / X materials are used as sensitizers in photovoltaic devices.

[0363] 56. The method according to Example 54 or Example 55, wherein the passivated A / M / X material is in the form of a layer, and the method includes (i) Treating a layer containing the crystalline A / M / X material with the passivating agent, wherein the layer containing the crystalline A / M / X material is disposed on a substrate; or (ii) In the presence of the passivating agent, a layer comprising the crystalline A / M / X material is produced on a substrate, the production comprising exposing the substrate to the one or more A cations, the one or more M cations, the one or more X anions and the passivating agent, optionally wherein the one or more A cations, the one or more M cations, the one or more X anions and the passivating agent are present in one or more different phases selected from the gas phase and the solution phase.

[0364] 57. The method according to embodiment 56, wherein the substrate includes a first charge transport region and an optional first electrode, the first charge transport region comprising at least one layer of a first charge transport material. Optionally, the method further includes arranging a second charge transport region and an optional second electrode on a layer comprising the crystalline A / M / X material, the second charge transport region comprising at least one layer of a second charge transport material. Preferably, the first charge transport region is a hole transport region and the first charge transport material is a hole transport material, the second charge transport region is an electron transport region and the second charge transport material is an electron transport material; or the first charge transport region is an electron transport region and the first electron transport material is an electron transport material, the second charge transport region is a hole transport region and the second charge transport material is a hole transport material. 58. The method according to any one of embodiments 54 to 57, wherein (i) treating the crystalline A / M / X material with the passivating agent comprises vaporizing the passivating agent to produce a passivating agent in the gas phase, and treating the crystalline A / M / X material with the passivating agent in the gas phase.

[0365] 59. The method according to any one of embodiments 54 to 57, wherein (i) treating the crystalline A / M / X material with the passivating agent comprises preparing a solution of the passivating agent and treating the crystalline A / M / X material with a solution of the passivating agent.

Claims

1. A photovoltaic device comprising passivated A / M / X material, in, The passivated A / M / X material includes crystalline A / M / X material and a passivating agent. The crystalline A / M / X material includes compounds of the following formula. [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, the passivating agent may comprise a dimer or polymer of the organic compound.

2. The photovoltaic device according to claim 1, wherein, The organic compound comprises a silane moiety and an amine moiety, wherein the amine moiety is a secondary amine, a tertiary amine, or a quaternary amine.

3. The photovoltaic device according to claim 1 or 2, wherein, The organic compound comprises a silane moiety and a plurality of amine moieties, wherein at least one of the amine moieties is a secondary amine, a tertiary amine, or a quaternary amine, and optionally, wherein at least one of the amine moieties is a primary amine.

4. The photovoltaic device according to claim 2 or 3, wherein, The organic compound comprises an organic group bonded to a silicon atom of the silane moiety, wherein each of the amine moieties is present in the organic group.

5. The photovoltaic device according to claim 4, wherein, The organic group is C. 1-20 Alkyl groups, wherein each amine moiety, which is a secondary, tertiary, or quaternary amine, can interrupt C. 1-20 The carbon chain of the alkyl group, or present as a substituent in the C group. 1-20 On an alkyl group, and wherein any amine moiety of a primary amine exists as a substituent in the C group. 1-20 On the alkyl group, and wherein the C 1-20 Alkyl groups are either unsubstituted or substituted.

6. The photovoltaic device according to claim 4 or 5, wherein, The organic compound has formula (I). （I） in: R is the organic group; and E 1 E 2 and E 3 Independently selected from H, unsubstituted or substituted C 1-10 Alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted C 1-10 Alkyl, unsubstituted or substituted aryl, unsubstituted or substituted acyl, unsubstituted or substituted ester, unsubstituted or substituted acyloxy, hydroxyl and halogen.

7. The photovoltaic device according to claim 6, wherein, R is C as defined in claim 5. 1-20 Alkyl, and E 1 E 2 and E 3 Is it unsubstituted or substituted C? 1-10 Alkoxy, preferably unsubstituted C 1-10 Alkyl group, more preferably methoxy group.

8. The photovoltaic device according to any one of the preceding claims, wherein, The organic compound has formula (II). (II) in: E 1 E 2 and E 3 As defined in claim 6, and preferably independently selected from H, unsubstituted or substituted C. 1-10 Alkoxy, unsubstituted or substituted C 1-10 Alkyl groups, unsubstituted or substituted aryl groups, and unsubstituted or substituted aryl groups; q is 0 or an integer from 1 to 5; Each m is an independent integer from 1 to 5; Each n is independently 0 or 1; p is 0 or an integer from 1 to 5; G is NR 1 2 or CR 1 3; Each R 1 H or C independently 1-6 alkyl; Where each n is 0 and G is NR 1 2, or when q is 0 and G is NR 1 2, then at least one R 1 The group is C 1-6 Alkyl, and Preferably, when G is NR 1 2. If q is not 0, then p is not 0.

9. The photovoltaic device according to any one of the preceding claims, wherein, The organic compounds are selected from: (i) PTMS ； (ii) MAPTMS ； (iii) DMAPTMS ； (iv) AEAPTMS ;as well as (v)(AE)2APTMS ， Optionally, the organic compound is selected from (ii) MAPTMS, (iii) DMAPTMS, (iv) AEAPTMS and (v) (AE)2APTMS.

10. The photovoltaic device according to any one of the preceding claims, wherein, The dimer of the organic compound comprises (i) a first monomer unit, wherein the first monomer unit is an organic compound as defined in any of the preceding claims, provided that the silicon atom of the silane portion of the first monomer unit is replaced by a linking atom or group; and (ii) a second monomer unit, wherein the second monomer unit is an organic compound as defined in any of the preceding claims, provided that the silicon atom of the silane portion of the second monomer unit is replaced by the linking atom or group, wherein the linking atom or group is covalently bonded to the silicon atom of the silane portion of the first monomer unit and covalently bonded to the silicon atom of the silane portion of the second monomer unit to link the first monomer unit to the second monomer unit.

11. The photovoltaic device according to claim 10, wherein, The dimer has formula (Ia) or formula (IIa): (It) Where L is the connecting atom or group, and each R, E 1 and E 2 Independently as defined in claim 6 or claim 7; (IIa) Where L is the connecting atom or group, and each G, p, n, m, q, E 1 and E 2 Independently as defined in claim 8.

12. The photovoltaic device according to any one of claims 1 to 9, wherein, The polymer of the organic compound comprises a monomer unit, the monomer unit being an organic compound as defined in any one of claims 1 to 9, provided that the silicon atom of the silane moiety is replaced by at least one linking atom or group, wherein the linking atom or group, or each linking atom or group, is covalently bonded to the silicon atom and also covalently bonded to the silicon atom of the silane moiety of another monomer unit in the polymer.

13. The photovoltaic device according to claim 12, wherein, The polymer of the organic compound comprises monomer units of formula (Ib) or formula (IIb): (One) Where L is the connecting atom or group, and R and E 1 As defined in claim 6 or claim 7; (IIb) Where L is the connecting atom or group, and G, p, n, m, q and E 1 As defined in claim 8, Preferably, the polymer comprises at least three monomer units of formula (Ib) or formula (IIb).

14. The photovoltaic device according to claim 12 or 13, wherein, The polymer comprises a structure of formula (Ic) or formula (IIc): (Ic) Where each L is the connecting atom or group, and each R and E 1 Independently as defined in claim 6 or claim 7, and z is an integer of at least 3; (IIc) Where each L is the connecting atom or group, and each G, p, n, m, q, and E 1 Independently as defined in claim 8, and z is an integer of at least 3.

15. The photovoltaic device according to any one of the preceding claims, wherein, Each type of A cation is selected from: Alkali metal cations; Equation [R1R2R3R4N] + The cations, wherein R1, R2, R3, and R4 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl group, and at least one of R1, R2, R3 and R4 is not hydrogen; Equation [R5R6N=CH-NR7R8] + The cations, wherein R5, R6, R7, and R8 are each independently selected from hydrogen, unsubstituted or substituted C4. 1-20 Alkyl and unsubstituted or substituted C 6-12 Aryl; and C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 cycloalkylimine ion, C 1-10 Alkyl ammonium ion, C 2-10 alkenyl ammonium ion, C 1-10 Alkylimine ions, C 3-10 cycloalkylammonium ions and C 3-10 The cycloalkylimine ions are each unsubstituted or selected from amino, C 1-6 Alkylamino, imino, C 1-6 Alkylimino, C 1-6 Alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6-12 One or more substituents of the aryl group are substituted; Preferably, each A cation is selected from Cs. + 、Rb + Formamidinium ion, guanidine ion, methylammonium ion and ethylammonium ion.

16. The photovoltaic device according to any one of the preceding claims, wherein, [X] contains two or more different X anions, preferably, wherein the two or more different X anions are two or more different halide anions, and optionally, wherein [X] contains Br and I.

17. The photovoltaic device according to any one of the preceding claims, wherein, [A] contains formamidinium ions, and optionally, [A] also contains Cs. + .

18. The photovoltaic device according to any one of the preceding claims, wherein, [M] contains selections from Ca 2+ 、Sr 2+ Cd 2+ Cu 2 + Ni 2+ Mn 2+ Fe 2+ Co 2+ Pd 2+ 、Ge 2+ Sn 2+ Pb 2+ Yb 2+ and Eu 2+ The M cation may optionally be selected from Sn. 2+ Pb 2+ Cu 2 + 、Ge 2 and Ni 2+ Preferably selected from Sn 2+ and Pb 2+ Preferably, [M] contains Pb 2+ .

19. The photovoltaic device according to any one of the preceding claims, wherein, Formula [A] a [M] b [X] c The compound is of formula [Cs] x (H2N–C(H)=NH2) 1-x ]Pb[I y Br 1-y Compounds of type 3, wherein x is greater than 0 and less than 1, and y is greater than 0 and less than 1.

20. The photovoltaic device according to any one of the preceding claims, wherein, The photovoltaic device is a solar cell.

21. The photovoltaic device according to any one of the preceding claims, wherein, The photovoltaic device is a tandem or multi-junction photovoltaic device.

22. The use of passivated A / M / X materials as sensitizers in photovoltaic devices. in, The passivated A / M / X material includes crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, the passivating agent may comprise a dimer or polymer of the organic compound.

23. A method for producing passivated A / M / X materials, in, The passivated A / M / X material includes crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, the passivating agent may comprise a dimer or polymer of the organic compound. The method includes: (iii) Treat the crystalline A / M / X material with the passivating agent; or (iv) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; Thus, the passivated A / M / X material is produced. And the method described therein also includes: Producing photovoltaic devices that include the passivated A / M / X materials.

24. A method for producing passivated A / M / X materials, in, The passivated A / M / X material includes crystalline A / M / X material and a passivating agent. The crystalline A / M / X material described herein comprises compounds of the following formula: [A] a [M] b [X] c in: [A] contains one or more A cations; [M] contains one or more M cations, wherein the M cations are metal or quasi-metal cations; [X] contains one or more X anions; 'a' is a number from 1 to 6; b is a number from 1 to 6; and c is a number from 1 to 18, and The passivating agent comprises an organic compound, wherein the organic compound comprises a silane moiety and (a) does not contain an amine moiety, or (b) contains an amine moiety, wherein the amine moiety is a secondary, tertiary, or quaternary amine. Alternatively, the passivating agent may comprise a dimer or polymer of the organic compound. The method includes: (iii) Treat the crystalline A / M / X material with the passivating agent; or (iv) The crystalline A / M / X material is produced from the one or more A cations, the one or more M cations, and the one or more X anions in the presence of the passivating agent; This allows for the production of passivated A / M / X materials. And the method described therein also includes: The passivated A / M / X material is used as a sensitizer in photovoltaic devices.

25. The method according to claim 23 or 24, wherein, The passivated A / M / X material is in the form of a layer, and the method includes... (i) Treating the layer containing the crystalline A / M / X material with the passivating agent, wherein the layer containing the crystalline A / M / X material is disposed on a substrate; or (ii) In the presence of the passivating agent, a layer comprising the crystalline A / M / X material is produced on a substrate, the production comprising exposing the substrate to the one or more A cations, the one or more M cations, the one or more X anions and the passivating agent, optionally wherein the one or more A cations, the one or more M cations, the one or more X anions and the passivating agent are present in one or more different phases selected from the gas phase and the solution phase.

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