A / m / x crystalline material, photovoltaic device, and preparation method therefor

Abstract

The present application provides an A / M / X crystalline material, a photovoltaic device, and a method for manufacturing the same, wherein the photovoltaic device comprises a photoactive crystalline material layer; the photoactive crystalline material layer comprises through-grains, wherein the through-grains are grains penetrating the photoactive crystalline material layer, and the ratio p≥80% of the number of through-grains to the total number of grains in the photoactive crystalline material layer; the photoactive crystalline material layer comprises a backlight side and backlight grains, wherein the backlight grains are grains exposed to the backlight side, and the backlight grains have backlight crystal planes exposed to the backlight side; and the average flatness factor Ravg≤75 in at least one region of the backlight side.

Description

Technology Field

[0001] This application is a divisional application, the filing date of the original application is December 23, 2021 and the application number is 202180095646.0, and the title of the invention is "A / M / X crystalline material, photovoltaic element and method for manufacturing the same".

[0002] The present application relates to the field of photovoltaic technology, and in particular to A / M / X crystalline materials, photovoltaic devices, and methods for manufacturing the same. Background Technology

[0003] A perovskite photovoltaic device is a photovoltaic device that performs photoelectric conversion using a photoactive perovskite structural material as a photoactive crystalline material layer.

[0004] Typical photoactive perovskite structural materials are organometal halides with the general formula AMX3, and generally have an octahedral or cubic structure. In a typical perovskite crystal, the A ion is located at the center of the cubic unit cell and is surrounded by 12 X ions to form a coordinated cubic octahedron, forming a three-dimensional periodic structure; the M ion is located at the vertex of the cubic unit cell and is coordinated with 6 X ions distributed around it in an octahedral symmetric structure.

[0005] Photoactive perovskite structural materials form two types of carriers, namely electrons and holes, under the radiation of light, and collect electrons and holes through two electrodes to obtain photocurrent. The characteristics of the perovskite structure are an important factor affecting the power conversion efficiency (PCE) of photovoltaic devices.

[0006] The purpose of the present application is to provide a photovoltaic device with higher energy conversion efficiency.

[0007] A first aspect of the present application provides a photovoltaic element, wherein the photovoltaic element comprises a photoactive crystalline material layer including a first region;

[0008] In the first region above, the photoactive crystalline material layer includes penetrating crystal grains, and the penetrating crystal grains are crystal grains that penetrate the photoactive crystalline material layer, and the ratio of the number of penetrating crystal grains to the total number of crystal grains of the photoactive crystalline material layer in the first region is p≥80%, and optionally, p≥90%;

[0009] In the first region above, the photoactive crystalline material layer comprises a backlight side and a backlight crystal grain, wherein the backlight crystal grain is a crystal grain having at least one surface exposed to the backlight side, and the surface of the backlight crystal grain exposed to the backlight side is a backlight crystal surface;

[0010] Here, the backlight side has an average flatness coefficient R avg With, R avg ≤75, and optionally 10≤R avg ≤70 and;

[0011] Here, the R on the backlight side mentioned above avg is calculated by the following formula, and

[0012] ;

[0013] Here, R i is the flatness coefficient of the i-th backlight grain in the first region above, and R i is calculated by the following formula, and

[0014] R i =d i / h i

[0015] Here, d i is the width of the backlight crystal plane of the i-th backlight crystal grain in the first region above;

[0016] h i is the height of the protrusion of the backlight crystal plane of the i-th backlight crystal grain in the first region above;

[0017] n is the number of total backlight crystal grains within the first region.

[0018] The solar element according to the above method has improved energy conversion efficiency.

[0019] In some embodiments, the photoactive crystalline material layer comprises an A / M / X crystalline material, and the A / M / X crystalline material has the following general formula,

[0020] [A] a [M] b [X] c

[0021] [M] comprises one or more first cations including metal ions, metalloid ions, or combinations thereof;

[0022] [A] comprises one or more secondary cations;

[0023] [X] contains one or more halogen anions;

[0024] a is 1 to 6, and optionally, a is 1, 2, 3, 4, 5 or 6;

[0025] b is 1 to 6, and optionally, b is 1, 2, 3, 4, 5 or 6;

[0026] c is 1 to 18, and optionally, c is 3, 6, 9 or 18.

[0027] The solar element according to the above method has improved energy conversion efficiency.

[0028] In some embodiments, the one or more first cations are 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+ , Bi3+, Sb3+, Pd 4+ , W 4+ , Re4+ , Os 4+ , Ir 4+ , Pt 4+ , Sn 4+ , Pb 4+ , Ge 4+ or Te 4+ Selected from.

[0029] Optionally, the one or more first cations are Cu 2+ , Pb 2+ , Ge 2+ or Sn 2+ Selected from;

[0030] (2) One or more of the above second cations are Cs + , (NR 1 R 2 R 3 R 4 ) + , (R 1 R 2 N=CR 3 R 4 ) + , (R 1 R 2 NC(R 5 )=NR 3 R 4 ) + or (R 1 R 2 NC(NR 5 R 6 )=R 3 R 4 ) + Selected from, where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently H, substituted or unsubstituted C 1-20 Selected from alkyl groups or substituted or unsubstituted aryl groups;

[0031] Optionally, one or more of the second cations are Cs + , (CH3NH3) + , (H2N-C(H)=NH2) + Selected from;

[0032] (3) The above halogen anion is Cl - , Br - or I - Selected from.

[0033] The solar element according to the above method has improved energy conversion efficiency.

[0034] In some embodiments, the A / M / X crystalline material is FAPbI3, FAPbBr3, FAPbCl3, FAPbF3, FAPbBr x I 3-x , FAPbBr x Cl 3-x , FAPbI x Br 3-x , FAPbI x Cl 3-x , FAPbCl x Br 3-x , FAPbI 3-x Cl x , CsPbI3, CsPbBr3, CsPbCl3, CsPbF3, CsPbBr x I 3-x , CsPbBr x Cl 3-x , CsPbI x Br 3-x , CsPbI x Cl 3-x , CsPbCl x Br 3-x , CsPbI 3-x Cl x , FA 1-y Cs y PbI3, FA 1-y Cs y PbBr3, FA 1-y Cs y PbCl3, FA 1-y Cs y PbF3, FA 1-y Cs y PbBr x I 3-x , FA 1-y Cs y PbBr x Cl 3-x , FA 1-y Csy PbI x Br 3-x , FA 1-y Cs y PbI x Cl 3-x , FA 1-y Cs y PbCl x Br 3-x , FA 1-y Cs y PbI 3-x Cl x or including a combination thereof;

[0035] Here, x=0-3 and y=0.01-0.25.

[0036] The solar element according to the above method has improved energy conversion efficiency.

[0037] In some embodiments, the A / M / X crystalline material is FAPbI3, CsPbI3, FA 1-y Cs y It includes PbI3 or a combination thereof, where y=0.01-0.25.

[0038] The solar element according to the above method has improved energy conversion efficiency.

[0039] In some embodiments, the thickness of the photoactive crystalline material layer is 100 nm or more, optionally 100 nm to 1000 nm, and optionally 300 nm to 700 nm.

[0040] The solar element according to the above method has improved energy conversion efficiency.

[0041] In some embodiments, the photovoltaic element further comprises a first charge transport layer and a second charge transport layer, said photoactive crystalline material layer, and is located between said first charge transport layer and second charge transport layer;

[0042] The first charge transport layer and the second charge transport layer are respectively an electron transport layer and a hole transport layer, or

[0043] The above first charge transport layer and second charge transport layer are a hole transport layer and an electron transport layer, respectively.

[0044] In some embodiments, the photovoltaic element further comprises the first electrode and the second electrode, and the electron transport layer, the hole transport layer and the photoactive crystalline material layer are located between the first electrode and the second electrode;

[0045] Optionally, the first electrode comprises a transparent conductive oxide;

[0046] Optionally, the second electrode comprises a metal.

[0047] The solar element according to the above method has improved energy conversion efficiency.

[0048] A second aspect of the present application provides a method for manufacturing an A / M / X crystalline material, wherein the A / M / X crystalline material has the following general formula, and

[0049] [A] a [M] b [X] c

[0050] [M] comprises one or more first cations including metal ions, metalloid ions, or combinations thereof;

[0051] [A] comprises one or more secondary cations;

[0052] [X] contains one or more halogen anions;

[0053] a is 1 to 6, for example, a=1 and;

[0054] b is 1 to 6, for example, b=1;

[0055] c is 1 to 18, for example, c=3;

[0056] The above method comprises the step of placing a precursor composition on a matrix; and the precursor composition is,

[0057] (a) at least one precursor compound;

[0058] (b) solvent;

[0059] (c) surfactant; and

[0060] (d) contains an amino compound as a component.

[0061] The A / M / X crystalline material manufactured based on the above method is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.

[0062] In some embodiments, the surfactant comprises an amphoteric surfactant. An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0063] In some embodiments, the amino compound comprises a nitrileamine compound, an amino acid compound (e.g., a sulfamic acid compound), a hydrazine compound, a urea compound (e.g., urea, urea, formaldehyde, biuret, triuret), a guanidine compound, or a salt or hydrate thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0064] In some embodiments, the surfactant comprises dodecylaminopropionate, dodecyl ethoxysulfobetaine, dodecyl dimethylhydroxypropylsulfobetaine, cationic polyacrylamide, octadecyl dihydroxyethylamine oxide, tetradecyl dihydroxyethylamine oxide, laurylamide propylamine oxide, dodecyl betaine, L-α-phosphatidylcholine, 3-(N,N-dimethyltetradecylammonium)propanesulfonate, dodecylbenzenesulfonate, or a combination thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0065] In some embodiments, the amino compound is urea formaldehyde (C3H8N2O3) and isobutylidene urea (C6H 14It includes N4O2), hydrazine (H4N2), guanidine (CH3N3O), nitrileamine (CH2N2), sulfamic acid (H3NO3S), or combinations thereof. The A / M / X crystalline material manufactured based on the above method is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.

[0066] In some embodiments, the precursor composition comprises a first solvent and a second solvent, wherein the boiling point of the first solvent is 40°C-165°C; and the boiling point of the second solvent is 170°C-250°C. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0067] In some embodiments, the first solvent is selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN). An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0068] In some embodiments, the second solvent is selected from one or more of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenyl sulfoxide (DPSO). An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0069] In some embodiments, the volume ratio of the first solvent to the second solvent is (4-10):1. An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0070] In some embodiments, the precursor composition is,

[0071] A first precursor compound containing a first cation; and

[0072] It includes a second precursor compound containing a second cation.

[0073] The A / M / X crystalline material manufactured based on the above method is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.

[0074] In some embodiments, the first precursor compound contains a halogen anion. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0075] In some embodiments, the second precursor compound contains a halogen anion. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0076] In some embodiments, the first precursor compound comprises lead iodide (PbI2), lead bromide (PbBr2), or a combination thereof;

[0077] In some embodiments, the second precursor compound comprises formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or a combination thereof.

[0078] The A / M / X crystalline material manufactured based on the above method is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.

[0079] In some embodiments, the method for manufacturing an A / M / X crystalline material further comprises the step of curing a precursor composition disposed on a matrix surface, and

[0080] Optionally, the curing treatment comprises vacuum treatment, air blading, infrared treatment, or a combination thereof. An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device exhibits improved energy conversion efficiency.

[0081] In some embodiments, the method for manufacturing an A / M / X crystalline material further comprises the step of annealing the hardened product, and

[0082] Optionally, the annealing temperature is 100℃-170℃;

[0083] Optionally, the annealing time is 5 min to 60 min.

[0084] The A / M / X crystalline material manufactured based on the above method is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.

[0085] A third aspect of the present application provides a method for manufacturing a photovoltaic device, wherein the photovoltaic device comprises a first electrode and a second electrode, a first charge transport layer and a second charge transport layer located between the first electrode and the second electrode, and an A / M / X crystalline material layer located between the first charge transport layer and the second charge transport layer;

[0086] The above method is,

[0087] A step of providing a first electrode having a first charge transport layer provided on its surface;

[0088] According to any one of the above methods for manufacturing an A / M / X crystalline material, a step of forming an A / M / X crystalline material layer on the surface of the first charge transport layer;

[0089] A step of forming a second charge transport layer on the above A / M / X crystalline material layer; and

[0090] The method includes the step of forming a second electrode in the second charge transport layer;

[0091] Here, the first charge transport layer and the second charge transport layer are respectively an electron transport layer and a hole transport layer, or

[0092] The above first charge transport layer and second charge transport layer are a hole transport layer and an electron transport layer, respectively.

[0093] Solar cells manufactured based on the above method have improved energy conversion efficiency.

[0094] [Beneficial Effects]

[0095] One or more technical solutions of the present application exhibit one or more of the following beneficial effects.

[0096] (1) The photovoltaic device exhibits a greatly improved power conversion efficiency (PCE);

[0097] (2) The photoactive crystalline material layer has a high penetration grain ratio p;

[0098] (3) The photoactive crystalline material layer has a low average flatness coefficient R avg Having;

[0099] (4) In the method for manufacturing a photoactive crystal layer, the surfactant and the nitrogen-containing compound exhibited an unexpected synergistic effect;

[0100] (5) The manufacturing method is inexpensive, highly efficient, and easy to scale up. Brief explanation of the drawing

[0101] FIG. 1 shows a schematic diagram of a photovoltaic element according to some embodiments of the present application. FIG. 2 shows a schematic diagram of a photoactive crystalline material layer according to some embodiments of the present application. Figures 3(a) and 3(b) respectively show schematic diagrams of a photoactive crystalline material layer according to some embodiment of the present application and a photoactive crystalline material layer according to a comparative embodiment. FIG. 4 shows a scanning electron microscope image of an intermediate product containing a photoactive crystalline material layer according to some embodiments of the present application. Specific details for implementing the invention

[0102] Hereinafter, embodiments of the A / M / X crystalline material, photovoltaic device, and method for manufacturing the same of the present application are disclosed in detail with appropriate reference to the drawings. However, unnecessary detailed descriptions may be omitted in some cases. For example, detailed descriptions of known matters and redundant descriptions of structures that are substantially identical may be omitted. This is intended to prevent the following description from becoming unnecessarily long and to aid the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter of the claims.

[0103] The “range” disclosed in this application is limited in the form of lower and upper limits, and a given range is limited by the selection of one lower limit and one upper limit, and the selected lower limit and upper limit define the boundaries of a specific range. A range limited in this way may or may not include endpoint values ​​and may be arbitrarily combined. That is, any lower limit and any upper limit may be combined to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a specific parameter, it should be understood that ranges of 60 to 110 and 80 to 120 are also expected. Additionally, if minimum range values ​​1 and 2 are listed and maximum range values ​​3, 4, and 5 are listed, 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 may all be expected. In this application, unless otherwise specified, the numeric range “a to b” represents an abbreviated expression of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numeric range “0 to 5” means that all real numbers between “0 to 5” are listed in this specification, and “0 to 5” is merely an abbreviated expression of a combination of these numeric values. Additionally, when a specific parameter is described as an integer ≥ 2, it is equivalent to disclosing that the parameter is an integer, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0104] Unless otherwise specified, all embodiments and optional embodiments of the present application may be combined with one another to form a new technical solution.

[0105] Unless otherwise specified, all technical features and optional technical features of this application may be combined with one another to form a new technical solution.

[0106] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, for example, sequentially. For example, the method may include steps (a) and (b), which indicates that the method may include steps (a) and (b) performed sequentially and steps (b) and (a) performed sequentially. For example, the said method may further include step (c), which indicates that step (c) may be added to the method in any order, for example, the method may include steps (a), (b), and (c), steps (a), (c), and (b), steps (c), (a), and (b), etc.

[0107] Unless otherwise specified, “comprehensive” and “include” as used in this application may mean open and closed forms. For example, “comprehensive” and “include” indicate that the term may further encompass or include other unlisted components, or may encompass or include only the listed components.

[0108] Unless otherwise specified, the term “or” in this application is inclusive. For example, the phrase “A or B” indicates “A, B, or both A and B.” More specifically, any of the following conditions satisfy the “A or B” condition: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or A and B are both true (or exist).

[0109] [Solar element]

[0110] A photovoltaic device (also called a solar cell) is a device designed to convert solar energy into electrical energy.

[0111] FIG. 1 shows a schematic diagram of a photovoltaic device according to some embodiments of the present application. FIG. 2 shows a schematic diagram of a photoactive crystalline material layer according to some embodiments of the present application.

[0112] Referring to FIG. 1-2, in some embodiments, the present application provides a photovoltaic element, said photovoltaic element comprising a photoactive crystalline material layer (103), said photoactive crystalline material layer (103) comprising a first region;

[0113] In the first region, the photoactive crystalline material layer (103) comprises penetrating crystals (313), and the penetrating crystals (313) are crystals that penetrate the photoactive crystalline material layer (103), and the ratio of the number of penetrating crystals (313) in the first region to the total number of crystals in the photoactive crystalline material layer (103) in the first region is p≥80%, optionally p≥90%, optionally p≥95%, optionally p≥99%, optionally p=100%;

[0114] In the first region above, the photoactive crystalline material layer (103) comprises a backlight side (113) and backlight crystals (31, 32, 33), wherein the backlight crystals (31, 32, 33) are crystals having at least one surface exposed to the backlight side (113), and the surface of the backlight crystals (31, 32, 33) exposed to the backlight side (113) is a backlight crystal face;

[0115] Here, the backlight side (113) has an average flatness coefficient R avg With the (Average Flatness Index), R avg ≤75, and optionally 10≤R avg ≤70, and optionally R avg The value of is 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, or 60-70;

[0116] Here, R of the backlight side (113) avg is calculated by the following formula, and

[0117] ;

[0118] Here, R i is the flatness coefficient of the i-th backlight crystal grain (31, 32, 33) in the first region, and R i is calculated by the following formula, and

[0119] R i =d i / h i

[0120] Here, d i is the width of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region;

[0121] h i is the height of the protrusion on the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region;

[0122] n is the number of total backlight crystal grains (31, 32, 33) within the first region.

[0123] In the above method, the inventor discovered that the energy conversion efficiency of a photovoltaic device can be significantly improved by optimizing the shape and arrangement of the crystal grains of the photoactive crystalline material layer. Specifically, the inventor has a ratio p≥80% of the number of penetrating crystal grains (313) in the photoactive crystalline material layer in the first region to the total number of crystal grains of the photoactive crystalline material layer (103) in the first region (based on the ratio of the number of penetrating crystal grains (313) in the cross-section of the photoactive crystalline material layer in the first region to the total number of crystal grains in the cross-section of the photoactive crystalline material layer in the first region), and at the same time, an average flatness coefficient R of the backlight crystal grains (31, 32, 33) of at least a portion of the backlight side of the photoactive crystalline material layer. avg It was discovered that when ≤75 (based on the average flatness factor of the backlight crystal grains (31, 32, 33) in the cross-section of the photoactive crystalline material layer corresponding to the first region), the photovoltaic element exhibits a significantly improved Power Conversion Efficiency (PCE).

[0124] Referring to FIG. 2, in some embodiments, the average flatness factor R avg The measurement and calculation method is explained in detail in FIG. 2. FIG. 2 shows a crystalline material layer (103), and the photoactive crystalline material layer (103) includes a backlight side (113) and backlight crystal grains (31, 32, 33), wherein the backlight crystal grains (31, 32, 33) are crystal grains exposed to the backlight side (113), and the backlight crystal grains (31, 32, 33) have a backlight crystal surface exposed to the backlight side;

[0125] Here, R of the backlight side (113) avg is calculated by the following formula, and

[0126] ;

[0127] Here, R iis the flatness coefficient of the i-th backlight crystal grain (31, 32, 33) in the first region, and R i is calculated by the following formula, and

[0128] R i =d i / h i

[0129] Here, d i is the width (d1, d2, d3) of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region;

[0130] h i is the height of the protrusion (h1, h2, h3) of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region;

[0131] n is the number of total backlight crystal grains (31, 32, 33) within the first region;

[0132] In the case of the first region of the photoactive crystal layer (103) shown in FIG. 2, since the total number of backlight crystal grains (31, 32, 33) in the first region is n=3, the value of i is 1 to 3.

[0133] In some embodiments, the value of n is 3 or more, e.g., 5 or more, e.g., 10 or more, e.g., 50 or more, e.g., 100 or more, e.g., 500 or more, e.g., 1000 or more.

[0134] Referring to FIG. 3, FIG. 3 (a) and (b) each show schematic diagrams of two photoactive crystalline material layers.

[0135] Referring to FIG. 3(a), a schematic diagram of a photoactive crystalline material layer in a first region is shown. As shown in the drawing, the ratio of the number of penetrating crystal grains (313) of the photoactive crystalline material layer in the first region to the total number of crystal grains of the photoactive crystalline material layer (103) in the first region is p=100%. Incident light (151) is incident from the light receiving surface (112) of the photoactive crystalline material layer in the first region, and since the crystal grains of the photoactive crystalline material layer in the first region are penetrating crystal grains (313), the incident light (151) can reach the backlight surface (113) with almost no blockage, so that the photoactive crystalline material layer in the first region can be sufficiently radiated by the incident light (151).

[0136] Referring to FIG. 3(b), a schematic diagram of a comparative photoactive crystalline material layer is shown. As shown in the drawing, all crystal grains of the comparative photoactive crystalline material layer are non-penetrating crystal grains (323), and the ratio of penetrating crystal grains to the total number of crystal grains of the photoactive crystalline material layer (103) in the area shown in the drawing is p=0%. Since all crystal grains of the comparative photoactive crystalline material layer (313) are non-penetrating crystal grains (323), incident light (151) is incident from the light-receiving surface (112) of the comparative photoactive crystalline material layer. Therefore, before the incident light (151) reaches the backlight surface (113), it is reflected or refracted by the crystal grain boundaries (315), so the comparative photoactive crystalline material layer cannot sufficiently absorb the radiant energy of the incident light (151).

[0137] The flatness factor is a coefficient that indicates the degree of flatness of the grain surface. A higher flatness factor indicates that the back-end crystal plane of the grain is closer to a flat plane, while a lower flatness factor indicates a higher degree of protrusion on the back-end crystal plane of the grain.

[0138] Referring to FIG. 3(a), the flatness factor of the backlight crystal grains (31, 32, 33) of the photoactive crystalline material layer in the first region is low (≤75), that is, the ratio (d / h) of the width and protrusion height of the backlight crystal grains (31, 32, 33) is low, and the backlight crystal grains (31, 32, 33) have a convex surface, so that the backlight side (113) of the photoactive crystalline material layer can concentrate most of the reflected light (152) within the layer of the photoactive crystalline material layer in the first region rather than outside the layer. This allows the photoactive crystalline material layer in the first region to fully utilize light energy.

[0139] Referring to FIG. 3(b), FIG. 3(b) shows a schematic diagram of a comparative photoactive crystalline material layer. As shown in the drawing, the flatness factor of the backlight crystal grains (31, 32, 33) of the photoactive crystalline material layer is high (>1000), that is, the backlight crystal grains (31, 32, 33) have a flat backlight crystal surface. The flat backlight surface reflects most of the reflected light (152) out of the layer, so that the comparative photoactive crystalline material layer (312) cannot fully utilize light energy.

[0140] In some embodiments, the first region refers to a part or the entire region of the photoactive crystal layer (103) in the direction of the layer surface.

[0141] In some embodiments, the size of the first region in at least one direction is 3 μm or more, for example 10 μm or more, for example 100 μm or more, for example 1 mm or more, for example 1 cm or more, for example 10 cm or more. Optionally, the size of the first region in at least two mutually perpendicular directions is 3 × 3 μm or more, for example 10 × 10 μm or more, for example 100 × 100 μm or more, for example 1 × 1 mm or more, for example 1 × 1 cm or more, for example 10 × 10 cm or more, for example 1 m × 1 m or more.

[0142] In some embodiments, the total number of crystal grains of the photoactive crystal layer in the first region is 9 (3 × 3) or more, for example 16 (4 × 4) or more, for example 25 (5 × 5) or more, for example 64 (8 × 8) or more, for example 100 (10 × 10) or more, for example 1000 or more.

[0143] In some embodiments, the area of ​​the first region corresponds to 10% or more of the area of ​​the backlight side or the light-receiving side of the photoactive crystal layer, for example, 50% or more, for example, 70% or more, for example, 90% or more, for example, 100%.

[0144] In some embodiments, the photoactive crystal layer (103) comprises a plurality of crystal grains. A crystal grain that penetrates the photoactive crystalline material layer (103) is a penetrating crystal grain (313). A crystal grain with at least one surface exposed to the backlight side (113) is a backlight crystal grain (31, 32, 33). It should be understood that a single crystal grain may belong to both the penetrating crystal grain (313) and the backlight crystal grain (31, 32, 33). Additionally, a single crystal grain may belong only to the backlight crystal grain (31, 32, 33) and not to the penetrating crystal grain (313).

[0145] In some embodiments, the term “crystal” refers to a crystalline compound having an extended 3D crystal structure. The crystalline compound generally exists in the form of crystals, or, in the case of a polycrystalline compound, in the form of microcrystals (i.e., multiple crystals with a particle size of 1 μm or less). When crystals are together, they form a layer. The crystals of the crystalline material may be of any size. If the crystals have a size within the range of 1 nm to 1000 nm in one or multiple dimensions, they may be referred to as nanocrystals.

[0146] In some embodiments, the term “layer” basically refers to any structure that is layered (e.g., basically extending in two vertical directions, but limited in extension in a third vertical direction). The layer may have a thickness that varies within the extension range of the layer. Generally, the thickness of the layer is nearly constant. As used herein, the “thickness” of the layer refers to the average thickness of the layer. The thickness of the layer can be easily measured using a microscopy method, such as electron microscopy of a thin film cross-section, or using a needle contour measuring instrument, such as surface contour measuring.

[0147] In some embodiments, the term “light-receiving surface” means a surface facing a light source when the photovoltaic element is in operation; and the term “backlight surface” means a surface facing away from a light source when the photovoltaic element is in operation.

[0148] In some embodiments, the term “grain” as used in this application means “single crystal grain.” For example, one grain means one single crystal grain; and the number of grains means the number of single crystal grains. The term “single crystal” may be defined as a single crystal body of crystalline material that contains no large-angle boundaries or twin boundaries, as described in ASTM F1241.

[0149] In some embodiments, the term "penetration" refers to a section from one side of the photoactive crystal layer to the other, for example, from the light-receiving side to the backlight side. "Penetrating crystal grain" refers to a crystal grain that penetrates in the thickness direction of the photoactive crystal layer, for example, a crystal grain that penetrates from the light-receiving side to the backlight side of the photoactive crystal layer.

[0150] In some embodiments, the height of the protrusions on the backlight crystal planes is obtained by observing and measuring a micrograph of a cross-sectional view of a photoactive crystalline material layer. In the micrograph of the cross-sectional view, the height of the contour of the backlight crystal planes convex with respect to the backlight crystal plane base surface is defined as the height of the protrusions on the backlight crystal planes (distance from the highest point of the backlight crystal plane protrusions to the backlight crystal plane base surface); and the width of the contour of the backlight crystal planes convex with respect to the backlight crystal plane base surface is the width of the backlight crystal planes. The backlight crystal plane base surface basically refers to a continuous and basically horizontal surface that penetrates the lowest point of each backlight crystal plane. For example, the backlight crystal plane base surface is a surface fitted to be nearly horizontal to encompass as many lowest points as possible after first finding the lowest point on each backlight crystal plane. The backlight crystal plane lowest point refers to the point where adjacent crystal grains first come into contact with each other when facing the light-receiving plane direction from the backlight crystal plane, and as shown in FIG. 2, the backlight crystal plane lowest point is the junction point of the arc planes corresponding to two adjacent crystal grains.

[0151] In some embodiments, the photoactive crystalline material comprises an A / M / X crystalline material, and the A / M / X crystalline material has the following general formula,

[0152] [A] a [M] b [X] c

[0153] [M] comprises one or more first cations including metal ions, metalloid ions, or combinations thereof;

[0154] [A] comprises one or more secondary cations;

[0155] [X] contains one or more halogen anions;

[0156] a is 1 to 6, and optionally, a is 1, 2, 3, 4, 5 or 6;

[0157] b is 1 to 6, and optionally, b is 1, 2, 3, 4, 5 or 6;

[0158] c is 1 to 18, and optionally, c is 3, 6, 9, or 18. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0159] In some embodiments, the one or more first cations are 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+ , Bi3+, Sb3+, Pd 4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4+ , Sn 4+ , Pb 4+ , Ge 4+ or Te 4+ It is selected from. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0160] In some embodiments, the one or more first cations are Cu 2+ , Pb 2+ , Ge 2+ or Sn 2+ It is selected from. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0161] In some embodiments, the one or more second cations are Cs + , (NR 1 R 2 R 3 R 4 ) + , (R 1 R2 N=CR 3 R 4 ) + , (R 1 R 2 NC(R 5 )=NR 3 R 4 ) + or (R 1 R 2 NC(NR 5 R 6 )=R 3 R 4 ) + Selected from, where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently H, substituted or unsubstituted C 1-20 It is selected from alkyl groups or substituted or unsubstituted aryl groups. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0162] In some embodiments, the one or more second cations are Cs + , (CH3NH3) + , (H2N-C(H)=NH2) + It is selected from. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0163] In some embodiments, the halogen anion is Cl - , Br - or I - It is selected from. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0164] In some embodiments, the A / M / X crystalline material is FAPbI3, FAPbBr3, FAPbCl3, FAPbF3, FAPbBr x I 3-x , FAPbBr x Cl 3-x , FAPbI x Br3-x , FAPbI x Cl 3-x , FAPbCl x Br 3-x , FAPbI 3-x Cl x , CsPbI3, CsPbBr3, CsPbCl3, CsPbF3, CsPbBr x I 3-x , CsPbBr x Cl 3-x , CsPbI x Br 3-x , CsPbI x Cl 3-x , CsPbCl x Br 3-x , CsPbI 3-x Cl x , FA 1-y Cs y PbI3, FA 1-y Cs y PbBr3, FA 1-y Cs y PbCl3, FA 1-y Cs y PbF3, FA 1-y Cs y PbBr x I 3-x , FA 1-y Cs y PbBr x Cl 3-x , FA 1-y Cs y PbI x Br 3-x , FA 1-y Cs y PbI x Cl 3-x , FA 1-y Cs y PbCl x Br 3-x , FA 1-y Cs y PbI 3-x Cl x or including a combination thereof;

[0165] Here, x=0-3 and y=0.01-0.25. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0166] In some embodiments, the A / M / X crystalline material is FAPbI3, CsPbI3, FA 1-y Cs y It includes PbI3 or a combination thereof, where y=0.01-0.25. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0167] In some embodiments, the A / M / X crystalline material is a perovskite material. Optionally, the A / M / X crystalline material is a metal halide perovskite. The term “metal halide perovskite” means a perovskite in which the formula includes at least one metal cation and at least one halogen anion. Optionally, the A / M / X crystalline material is a mixed halide perovskite. The term “mixed halide perovskite” means a perovskite or mixed perovskite containing at least two types of halogen anions. Optionally, the A / M / X crystalline material is a mixed cationic perovskite. The term “mixed cationic perovskite” means a perovskite of mixed perovskite containing at least two types of A cations. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0168] In some embodiments, the term “perovskite” refers to a material having a three-dimensional crystal structure related to the three-dimensional crystal structure of CaTiO3, or a layer material having a structure related to the structure of CaTiO3. A material related to the three-dimensional crystal structure of CaTiO3 may be referred to as a perovskite having a “3D perovskite structure” or simply as “3D perovskite.” The structure of CaTiO3 can be represented by the formula AMX3, where A and M are cations of various sizes and X is an anion. In a unit cell, cation A is located at (0, 0, 0), cation M is located at (1 / 2, 1 / 2, 1 / 2), and anion X is located at (1 / 2, 1 / 2, 0). Cation A is generally larger than cation M. Those skilled in the art will understand that when A, M, and X are changed, various ion sizes can transform the structure of the perovskite material from a structure applicable to CaTiO3 to a deformed structure of lower symmetry. Materials containing a perovskite material layer are known. For example, material structures using a K2NiF4 type structure contain a perovskite material layer. These are referred to in the art as “2D layered perovskites” and are structurally different from the 3D perovskites mentioned above. 2D layered perovskites can be represented by the formula [A]2[M][X]4, where [A] is at least one cation, [M] is at least one cation of a different size from the cation [A], and [X] is at least one anion.

[0169] In some embodiments, the thickness of the photoactive crystalline material layer is 100 nm or more, optionally 100-1000 nm, and optionally 300-700 nm. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0170] In some embodiments, the photovoltaic element further comprises a first charge transport layer (104) and a second charge transport layer (102), and the photoactive crystalline material layer (103) is located between the first charge transport layer (104) and the second charge transport layer (102);

[0171] The first charge transport layer (104) and the second charge transport layer (102) are each an electron transport layer and a hole transport layer, or

[0172] The first charge transport layer (104) and the second charge transport layer (102) are respectively a hole transport layer and an electron transport layer. Based on the above method, the photovoltaic device has improved energy conversion efficiency.

[0173] In some embodiments, the photovoltaic element further comprises a first electrode (105) and a second electrode (101), wherein the electron transport layer, the hole transport layer and the photoactive crystalline material layer are located between the first electrode (105) and the second electrode (101);

[0174] Optionally, the first electrode (105) comprises a transparent conductive oxide;

[0175] Optionally, the second electrode (101) comprises a metal. Based on the above method, the photovoltaic element has improved energy conversion efficiency.

[0176] In some embodiments, the present application provides a method for manufacturing an A / M / X crystalline material, wherein the A / M / X crystalline material has the following general formula, and

[0177] [A] a [M] b [X] c

[0178] [M] comprises one or more first cations including metal ions, metalloid ions, or combinations thereof;

[0179] [A] comprises one or more secondary cations;

[0180] [X] contains one or more halogen anions;

[0181] a is 1 to 6, for example, a=1 and;

[0182] b is 1 to 6, for example, b=1;

[0183] c is 1 to 18, for example, c=3.

[0184] The above method comprises the step of placing a precursor composition on a matrix; and the precursor composition is,

[0185] (a) at least one precursor compound;

[0186] (b) solvent;

[0187] (c) surfactant; and

[0188] (d) Amino compounds (Organic nitrogen-containing compounds); include.

[0189] In the above method, the inventors discovered that by combining a surfactant and an amino compound and using them in a precursor composition for manufacturing an A / M / X crystalline material, the manufactured A / M / X crystalline material possesses a high through-grain ratio and a low flatness modulus, and the A / M / X crystalline material is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0190] In some embodiments, the concentration of at least one precursor compound in the precursor composition is 0.5 mol / L to 2.5 mol / L, for example 0.5 mol / L to 1.5 mol / L, and 1.5 mol / L to 2.5 mol / L.

[0191] In some embodiments, the concentration of the surfactant in the precursor composition is 0.05 wt%-0.5 wt%, for example 0.1 wt%-0.2 wt%, 0.2 wt%-0.3 wt%, 0.3 wt%-0.4 wt%, or 0.4 wt%-0.5 wt%.

[0192] In some embodiments, the concentration of the amino compound in the precursor composition is 1 wt%-10 wt%, for example 2 wt%-4 wt%, 4 wt%-6 wt%, 6 wt%-8 wt%, or 8 wt%-10 wt%.

[0193] In some embodiments, the term “surfactant” refers to an amphiphilic compound (molecule or ion) comprising hydrophilic and lipophilic portions. Surfactants generally accumulate and act at the oil-water interface to reduce surface tension by orienting the hydrophilic portion toward the aqueous phase and the lipophilic portion toward the hydrophobic phase. Suitable surfactants include water-insoluble surfactants, water-dispersible surfactants, and water-soluble surfactants.

[0194] In some embodiments, the surfactant comprises an amphoteric surfactant.

[0195] The term “amphoteric surfactant” refers to a compound having cationic and anionic centers connected in the same molecule. In particular, the cationic portion is based on a primary amine, secondary amine, tertiary amine, or quaternary ammonium cation. The anionic portion includes, but is not limited to, carboxylates, sulfonates, and phosphates. In particular, the “amphoteric surfactant” is N₂ bonded to a C(O)O, SO₃H, or SO₃ functional group. + O functional group, quaternary N + It means a compound having a functional group, and a compound having a tertiary N functional group bonded to a C(O)OH, C(O)O, SO3H, or SO3 functional group.

[0196] For a general overview of amphoteric surfactants and their properties, see Amphoteric Surfactants, 2nd ed., edited by EGLomax, 1996, published by Marcel Dekker. Surfactants of this type include betaines such as fatty alkyl betaines, fatty alkylamide betaines, sulfo betaines, hydroxysulfo betaines, and betaines derived from imidazoline; amine oxides such as fatty alkylamine oxides and fatty alkylamide amine oxides; amphoteric glycinates and amphoteric propionates; and so-called “balanced” amphoteric polycarboxyglycinates and amphoteric polycarboxypropionates.

[0197] In some embodiments, the amino compound comprises an aminonitrile compound, an amino acid compound, a hydrazine compound, a urea compound (e.g., urea, urea, formaldehyde, biuret, triuret), a guanidine compound, or a salt or hydrate thereof.

[0198] In some embodiments, the term “amino compounds” means any compound comprising at least one primary amine, secondary amine or tertiary amine or quaternary ammonium group.

[0199] In some embodiments, the amino compound is a C1-C20 compound, for example, a C1-C15 compound, for example, a C1-C10 compound, for example, a C1-C5 compound, or a C15-C20 compound.

[0200] In some embodiments, the term “aminonitrile compound” means a compound containing at least one “amino group-methyl group-cyano group”. Optionally, the “aminonitrile compound” comprises aminonitrile (AAN), iminodiacetonitrile (IDAN), or ethylenediaminediacetonitrile (EDN).

[0201] In some embodiments, the term “amino acid” means a molecule having at least one amino group and at least one carboxyl group.

[0202] In some embodiments, the term “sulfamic acid compound” means a molecule comprising at least one amino group and at least one sulfonyl group.

[0203] In some embodiments, the term “hydrazine compound” includes hydrazine and substituted hydrazine.

[0204] In some embodiments, substitution means that the H atom of an unsubstituted compound is substituted by an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group.

[0205] In some embodiments, the term “urea compound” is -NR 1 R 2 -C(=S)-NR 3 R 4 It refers to a compound having a - group, and each R 1 , R 2 , R 3 and R 4 is independently selected from H, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups, and heterocyclic groups. Optionally, urea compounds include urea (urea), thiourea, urea formaldehyde, biuret, triuret, and their substituents.

[0206] In some embodiments, the surfactant comprises dodecylaminopropionate, dodecyl ethoxysulfobetaine, dodecyl dimethylhydroxypropylsulfobetaine, cationic polyacrylamide, octadecyl dihydroxyethylamine oxide, tetradecyl dihydroxyethylamine oxide, laurylamide propylamine oxide, dodecyl betaine, L-α-phosphatidylcholine, 3-(N,N-dimethyltetradecylammonium)propanesulfonate, dodecylbenzenesulfonate, or a combination thereof. Based on the above method, the photovoltaic device has improved energy conversion efficiency. An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0207] In some embodiments, the surfactant comprises dodecyl betaine, 3-(N,N-dimethyltetradecylammonium)propanesulfonate, laurylamide propylamine oxide, L-α-phosphatidylcholine, or a combination thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0208] In some embodiments, the amino compound is urea formaldehyde (C3H8N2O3) and isobutylidene urea (C6H 14 It includes N4O2), hydrazine (H4N2), guanidine (CH3N3O), nitrileamine (CH2N2), sulfamic acid (H3NO3S), or combinations thereof. Based on the above method, the photovoltaic device has improved energy conversion efficiency. The A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0209] In some embodiments, the amino compound comprises guanidine, sulfamic acid, urea, or a combination thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0210] In some embodiments, the precursor composition comprises a first solvent and a second solvent; the boiling point of the first solvent is 40°C-165°C (e.g., 40°C-60°C, 60°C-80°C, 80°C-100°C, 100°C-120°C, 120°C-140°C, or 140°C-160°C); and the boiling point of the second solvent is 170°C-250°C (e.g., 170°C-190°C, 190°C-210°C, 210°C-230°C, or 230°C-250°C). In the above method, by using a combination of a first solvent with a specific boiling point and a second solvent with a specific boiling point, the film coverage and crystal quality of the A / M / X crystalline material can be effectively improved.

[0211] In some embodiments, the first solvent is selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN). An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0212] In some embodiments, the second solvent is selected from one or more of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenyl sulfoxide (DPSO). An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0213] In some embodiments, the volume ratio of the first solvent and the second solvent is (4-10):1. By combining and using the first solvent of a specific boiling point and the second solvent of a specific boiling point in the above specific ratio, the film coverage and crystal quality of the A / M / X crystalline material can be effectively improved.

[0214] In some embodiments, the precursor composition is,

[0215] A first precursor compound containing a first cation; and

[0216] It includes a second precursor compound containing a second cation. The A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0217] In some embodiments, the first precursor compound contains a halogen anion. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0218] In some embodiments, the second precursor compound contains a halogen anion. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0219] In some embodiments, the first precursor compound comprises lead iodide (PbI2), lead bromide (PbBr2), or a combination thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0220] In some embodiments, the second precursor compound comprises formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or a combination thereof. An A / M / X crystalline material prepared based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0221] In some embodiments, the method for manufacturing an A / M / X crystalline material further comprises the step of curing a precursor composition disposed on a matrix surface, and

[0222] Optionally, the curing treatment includes vacuum treatment, air blading, infrared treatment, or a combination thereof. An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0223] In some embodiments, the method for manufacturing an A / M / X crystalline material further includes the step of annealing the cured product. The A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0224] In some embodiments, the annealing temperature is 100°C to 170°C (e.g., 100°C to 120°C, 120°C to 140°C, 140°C to 160°C, or 160°C to 170°C). An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0225] In some embodiments, the annealing time is 5 min to 60 min (e.g., 5 min to 15 min, 15 min to 25 min, 25 min to 35 min, 35 min to 45 min, or 45 min to 55 min). An A / M / X crystalline material manufactured based on the above method is used in a photovoltaic device, and the photovoltaic device has improved energy conversion efficiency.

[0226] In some embodiments, the present application further provides a method for manufacturing a photovoltaic device, wherein the photovoltaic device comprises a first electrode (105) and a second electrode (101), a first charge transport layer (104) and a second charge transport layer (102) located between the first electrode (105) and the second electrode (101), and an A / M / X crystalline material layer located between the first charge transport layer (104) and the second charge transport layer (102);

[0227] The above method is,

[0228] A step of providing a first electrode (105) having a first charge transport layer (104) provided on its surface;

[0229] According to any one of the above methods for manufacturing an A / M / X crystalline material, a step of forming an A / M / X crystalline material layer on the surface of the first charge transport layer (104);

[0230] A step of forming a second charge transport layer (102) on the above A / M / X crystalline material layer; and

[0231] The method includes the step of forming a second electrode (101) on the second charge transport layer (102).

[0232] Here, the first charge transport layer (104) and the second charge transport layer (102) are each an electron transport layer and a hole transport layer, or

[0233] The first charge transport layer (104) and the second charge transport layer (102) are respectively a hole transport layer and an electron transport layer. A photovoltaic device manufactured based on the above method has improved energy conversion efficiency.

[0234] In some embodiments, the photovoltaic elements are arranged in the following order:

[0235] · First electrode (e.g., including a transparent conductive oxide);

[0236] · First charge transport material layer (e.g., hole transport material layer);

[0237] · Photoactive crystalline material layer;

[0238] · A second charge transport material layer (e.g., an electron transport material layer); and

[0239] · May include a second electrode (e.g., including a single metal). A photovoltaic device manufactured based on the above method has improved energy conversion efficiency.

[0240] In some embodiments, the photovoltaic elements are arranged in the following order:

[0241] · First electrode (e.g., including a transparent conductive oxide);

[0242] · First charge transport material layer (e.g., electron transport material layer);

[0243] · Photoactive crystalline material layer;

[0244] · Second charge transport material layer (e.g., hole transport material layer);

[0245] · May include a second electrode (e.g., including a single metal). A photovoltaic device manufactured based on the above method has improved energy conversion efficiency.

[0246] [Photoactive crystalline material layer]

[0247] In some embodiments, “photoactive crystalline material” refers to a material capable of generating free carriers (e.g., electrons and holes) immediately after absorbing light.

[0248] In some embodiments, the photoactive crystalline material can generally absorb and / or emit photons in the visible region, such as photons in the blue light region of the spectrum. Accordingly, the photoactive crystalline material can be described as a photoemitting material (i.e., a material capable of emitting light) or a photoabsorbing material (i.e., a material capable of absorbing light). For example, the photoactive crystalline material can emit and / or absorb at least one photon having a wavelength of, for example, 450 to 700 nm, for example, 450 to 650 nm.

[0249] In some embodiments, the photoactive crystalline material may comprise 5 wt% or more of an A / M / X crystalline material. For example, the photoactive crystalline material comprises 80 wt% or more of an A / M / X crystalline material, for example, 95 wt% or more of an A / M / X crystalline material, for example, 99 wt% or more of an A / M / X crystalline material. The photoactive crystalline material may be composed of an A / M / X crystalline material or may be composed of an A / M / X crystalline material.

[0250] In some embodiments, for example, the photoactive crystalline material is a solid.

[0251] In some embodiments, the photoactive crystalline material layer comprises a thin film of an A / M / X crystalline material. Generally, since the A / M / X crystalline material is polycrystalline, the photoactive crystalline material comprises a correspondingly polycrystalline A / M / X crystalline material.

[0252] In some embodiments, the photoactive crystalline material layer may comprise a plurality of layers. Part or all of each layer may comprise an A / M / X crystalline material.

[0253] In some embodiments, the A / M / X crystalline material may be distributed uniformly or non-uniformly across the entire photoactive crystalline material layer. For example, the photoactive crystalline material may comprise a layer, which is basically a layer composed of the A / M / X crystalline material or a layer composed solely of the A / M / X crystalline material. Generally or additionally, the photoactive crystalline material may comprise the substrate (e.g., in powder form or thin film form) having the A / M / X crystalline material on the substrate.

[0254] [Electronic Transport Layer]

[0255] In some embodiments, the electron transport layer is a layer containing an electron transport material (also referred to as an n-type semiconductor material). The electron transport material may be a single electron transport compound or a single material, or a mixture of two or more electron transport compounds or single materials. The electron transport compound or single material may not be doped or may be doped with one or more doping elements.

[0256] Embodiments of electron transport materials are already known to those skilled in the art.

[0257] Electron transport materials may include fullerenes or fullerene derivatives such as C60, C70, PCBM, PC71BM, bis[C60]BM (i.e., bis-C60-methylbutyrate), and ICBA (CAS: 1207461-57-1).

[0258] The electron transport material may include organic electron transport materials such as perylene or its derivatives, P(NDI2ODT2) (CAS: 1100243-40-0) or vasocuproin (BCP).

[0259] The electron transport material may include inorganic electron transport materials such as metal oxides, metal sulfides, metal selenides, metal tellurides, perovskites, amorphous silicon, 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 IIV semiconductors, any one of which may be doped or not doped.

[0260] [Primary Transport Layer]

[0261] In some embodiments, the hole transport layer refers to a layer containing a hole transport material (also called a p-type semiconductor material).

[0262] Embodiments of hole transport materials are already known to those skilled in the art. The hole transport material may be a single hole transport compound or a single material, or a mixture of two or more hole transport compounds or single materials. The hole transport compound or single material may be undoped or doped with one or more doping elements.

[0263] For example, organic hole transport materials may include spiro-OMeTAD, P3HT, PCPDTBT, poly-TPD, spiro(TFSI)2, and PVK.

[0264] Inorganic hole transport materials may include 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, and these inorganic materials may be doped or not doped.

[0265] [electrode]

[0266] The term “electrode” means a region or layer composed of electrode material or basically composed of electrode material.

[0267] The photovoltaic element of the present application may further include a first electrode and a second electrode.

[0268] The first electrode may comprise 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), or indium-doped tin oxide (ITO)). Generally, the first electrode is a transparent electrode. Thus, the first electrode generally comprises a transparent conductive oxide such as FTO, ITO, or AZO. The thickness of the layer of the first electrode is, for example, 10 nm to 1000 nm, and also, for example, 40 nm to 400 nm.

[0269] The second electrode may be limited to the first electrode described above, and for example, the second electrode may comprise a metal (e.g., silver, gold, aluminum, or tungsten), an organic conductive material (e.g., PEDOT:PSS), or a transparent conductive oxide (e.g., fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), or indium-doped tin oxide (ITO)). Generally, the second electrode comprises a metal (e.g., a single metal) or is composed primarily of a metal (e.g., a single metal). The second electrode material may comprise a metal such as silver, gold, copper, aluminum, platinum, palladium, or tungsten, or be composed primarily of a metal. The second electrode may be formed by deposition by vacuum evaporation. The thickness of the second electrode material layer may be, for example, 10 nm to 1000 nm, and for example, 50 nm to 150 nm.

[0270] [Example]

[0271] The technical solution of the present application is described in detail below in conjunction with specific examples and comparative examples. Unless otherwise specified, the reagents, methods, and equipment used in the present application are food-grade reagents, methods, and equipment conventional in the art. Unless otherwise specified, the test conditions used in the examples of the present application are standard test conditions in the art. Unless otherwise specified, all reagents used in the examples of the present application are commercially available.

[0272] The CAS numbers of some raw materials and reagents are as follows.

[0273]

[0274] Example 1

[0275] Referring to FIG. 1, in the direction of light irradiation indicated by an arrow in the drawing, the photovoltaic element according to Example 1 includes a substrate (106), a first electrode (105), a first charge transport layer (104), a photoactive crystalline material layer (103), a second charge transport layer (102), and a second electrode (101) that are sequentially stacked.

[0276] The method for manufacturing a photovoltaic element according to Example 1 is as follows.

[0277] (1) 1362 mg of formamidine hydroiodide (FAI), 228.6 mg of cesium iodide (CsI), and 4056.9 mg of lead iodide (PbI2) were dissolved in 8 mL of solvent to prepare a perovskite precursor solution, wherein the molar concentration of FAI was 0.99 mol / L, the molar concentration of CsI was 0.11 mol / L, and the molar concentration of PbI2 was 1.1 mol / L. The solvent was a mixture of DMF (N,N-dimethylformamide) and NMP (N-methylpyrrolidone) in a volume ratio of 7:1. Then, a surfactant and a nitrogen-containing compound were added to the solvent, with weight percentages of 0.1 wt% and 5 wt%, respectively. In Example 1, the surfactant is dodecyl betaine, and the nitrogen-containing compound is urea.

[0278] (2) Provides a 2 cm × 2 cm FTO conductive glass (FTO conductive glass is glass coated with an FTO conductive layer on its surface, FTO stands for Fluorine doped tin oxide). The FTO conductive glass comprises a glass plate and an FTO conductive layer deposited on the glass plate. Using a laser engraving technique, a 0.66 cm wide FTO conductive layer is removed from the mutually facing edges of the FTO conductive glass, and a 2 cm × 1.34 cm FTO conductive layer is retained on the FTO conductive glass. Here, the glass plate is used as a substrate (106), and the FTO conductive layer is used as a first electrode (105).

[0279] (3) A first charge transport layer (104) (nickel oxide layer) is formed on a first electrode (105) (FTO conductive layer) using magnetron sputtering technology, and the thickness of the nickel oxide layer is about 20 nm. Here, the first charge transport layer (104) is used as a hole transport layer.

[0280] (4) The precursor solution is applied to the nickel oxide layer. Then, the sample is transferred to a vacuum chamber and left to stand for 120 seconds at a vacuum of 100 Pa to allow the precursor solution to cure and form a film. The cured sample is placed on a heat stage and subjected to annealing treatment; the annealing temperature is 150°C and the annealing time is 30 min; after annealing treatment, a good A / M / X crystalline material layer is formed on the nickel oxide layer. In this embodiment, the component of the A / M / X crystalline material is FA 0.9 Cs 0.1 It is PbI3. Here, the A / M / X crystalline material layer is used as a photoactive crystalline material layer (103).

[0281] (5) The sample obtained in the previous step is placed in the deposition system, and a second charge transport layer (102) is deposited on the photoactive crystalline material layer (103). Here, the second charge transport layer (102) is an electron transport layer. The second charge transport layer is formed by sequentially depositing a 30 nm thick C 60 It includes a (fullerene) layer and an 8 nm thick BCP (bathocuproine) layer.

[0282] (6) Still in the above deposition system, a second electrode (101) is formed on the second charge transport layer (102). The second electrode (101) is a metallic copper layer with a thickness of 100 nm, and a photovoltaic device according to Example 1 is obtained.

[0283] Examples 2-4

[0284] The difference between Examples 2-4 and Example 1 is that the type of surfactant and / or nitrogen-containing compound in the precursor solution is different.

[0285] Refer to Table 1 for detailed differences between surfactants and nitrogen-containing compounds.

[0286] Example 5 and Comparative Examples 1-3, 5-8

[0287] The difference between Comparative Example 1 and Example 1 is that the precursor solution does not contain surfactants or nitrogen-containing compounds.

[0288] The difference between Example 5 and Comparative Examples 2-3, 5-8 and Example 1 is that the precursor solution does not contain a surfactant and the type or content of the nitrogen-containing compound is different.

[0289] Refer to Table 1 for detailed differences between surfactants and nitrogen-containing compounds.

[0290] Analysis detection

[0291] 1. Shape Mark:

[0292] (1) Sample preparation: Steps (1) to (4) are performed according to the method of Example 4, and the product of step (4) is used as an observation sample. After making a straight scratch on one side of the glass plate of the observation sample with a glass cutter, the solar element is cut along the scratch to expose the cross-section.

[0293] (2) Sample observation: A cross-section was observed using a scanning electron microscope (SEM), and a photograph was taken at a magnification of 30,000 times. The photograph is as shown in FIG. 4. The observed sample includes a substrate (106), a first electrode (105) stacked on the substrate (106), a first charge transport layer (104) stacked on the first electrode (105), and a photoactive crystalline material layer (103) stacked on the first charge transport layer (104).

[0294] (3) Crystal shape of the photoactive crystalline material layer

[0295] As shown in FIG. 4, in the photo region, the cross-sectional length of the photoactive crystalline material layer (103) is 3.7 μm, and the total number of complete crystal grains in the region is 4.

[0296] First, the photoactive crystalline material layer (103) includes penetrating crystal grains (313), and the penetrating crystal grains (313) are crystal grains that penetrate the photoactive crystalline material layer (103), and the number of penetrating crystal grains (313) is 4, and the ratio p=100% of the total number of crystal grains of the photoactive crystalline material layer (103) in the area shown in the drawing.

[0297] Second, the photoactive crystalline material layer (103) includes a backlight side (113) and a backlight crystal grain, the backlight crystal grain is a crystal grain exposed to the backlight side (113), and the backlight crystal grain has a backlight crystal surface exposed to the backlight side (113);

[0298] In the photo area, the average flatness coefficient R on the backlight side avg =11.4 and;

[0299] Here, R of the photo area avg is calculated by the following formula, and

[0300] ;

[0301] Here, R i is the flatness coefficient of the i-th backlight grain in the photometric region, and R i is calculated by the following formula, and

[0302] R i =d i / h i

[0303] Here, d i is the width of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the photo region;

[0304] h i is the height of the protrusion on the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the photo region;

[0305] n is the total number of backlight crystal grains in the region, and n=4.

[0306] The products of step (6) obtained according to the methods of Examples 1-5 and Comparative Examples 1-3 and 5-8 were each observed using a scanning electron microscope, and a cross-section of a photoactive crystalline material layer with a length of 3.7 μm was collected, and

[0307] (1) The ratio of penetrating grains (313) to the total number of grains in the photoactive crystalline material layer in the photo region p; and

[0308] (2) Average flatness coefficient R of the backlight side avg ; produced

[0309] The specific results are shown in Table 1.

[0310] 2. Indicators of Energy Conversion Efficiency

[0311] For the photovoltaic elements obtained according to the methods of Examples 1-5 and Comparative Examples 1-3 and 5-8, standard simulated sunlight (AM 1.5G, 100 mW / cm²) 2 The energy conversion efficiency (PCE) of the photovoltaic device is tested under the investigation of ). For specific test methods, refer to the literature Stabilizing perovskite-substrate interfaces for high-performance perovskite modules, Science 373, 902 (2021), and the test results are shown in Table 1.

[0312] Table 1

[0313]

[0314] Analysis Results:

[0315] (1) Regarding solar cells

[0316] The energy conversion efficiency of the photovoltaic element according to Example 1-5 is 18.9%-21.1%, which is significantly higher than that of Comparative Examples 1-3 and 5-8, which is only 16%-17.9%.

[0317] The energy conversion efficiency of the photovoltaic device according to Examples 1-4 is significantly improved because the photoactive crystal layer of the photovoltaic device simultaneously satisfies the following features a) and b), and

[0318] a) The ratio of penetrating grains (313) to the total number of grains in the photoactive crystalline material layer in the photo region is p≥80, and for example, reaches p=100;

[0319] b) Average flatness coefficient R on the backlight side avg ≤75, for example, R avgReaches 11.4-59.

[0320] The energy conversion efficiency of the photovoltaic device according to Example 5 is significantly improved because the photoactive crystal layer of the photovoltaic device satisfies the ideal characteristic a.

[0321] (2) Regarding the synergistic effect of surfactants and nitrogen-containing compounds

[0322] Compared to Example 5 and Comparative Examples 1-3 and 5-8, the precursor solution of Example 1-4 contains a surfactant and a nitrogen-containing compound in addition to the precursor compound.

[0323] In the present application, the proportion of penetrating crystal grains (313) p≥80 and the average flatness coefficient R avg It was found that it is difficult to obtain a photoactive crystalline material layer with ≤75. As shown in Example 5 and Comparative Examples 1-3, 5-8, when a surfactant and a nitrogen-containing compound are not added to the precursor solution, or when a surfactant is added alone or a nitrogen-containing compound is added alone, the ratio of penetrating crystal grains (313) p≥80 and the average flatness coefficient R avg A photoactive crystalline material layer with ≤75 cannot be obtained, and a photoactive crystalline material layer with improved light absorption cannot be obtained.

[0324] In the present application, when a surfactant and a nitrogen-containing compound are simultaneously added to a precursor solution, the proportion of penetrating crystal grains (313) p≥80 and the average flatness coefficient R avg It was discovered that a photoactive crystalline material layer with a value of ≤75 can be successfully obtained.

[0325] It should be emphasized that the surfactant and the nitrogen-containing compound created a synergistic effect, significantly improving the photoelectric conversion performance of the photoactive crystalline material layer. The last column of Table 1 calculated the increase rate of the photoelectric conversion efficiency of other comparative examples and Examples 1-4 compared to Comparative Example 1, using the photoelectric conversion efficiency of Comparative Example 1 as the blank reference.

[0326] The PCE growth rate of Example 1 (26%) is significantly higher than the simple sum of the growth rates of Example 5 and Comparative Example 6 (18%+3%=21%);

[0327] The PCE growth rate of Example 2 (28%) is significantly higher than the simple sum of the growth rates of Comparative Examples 2 and 5 (3%+2%=5%);

[0328] The PCE growth rate of Example 3 (31%) is significantly higher than the simple sum of the growth rates of Comparative Examples 3 and 7 (7%+8%=15%);

[0329] It can be found that the PCE increase rate of Example 4 (32%) is significantly higher than the simple sum of the increase rates of Example 5 and Comparative Example 8 (18+12%=30%);

[0330] The surfactant and the nitrogen-containing compound produced an unexpected synergistic effect, significantly improving the light absorption of the photoactive crystalline material layer. Specifically, the ratio of penetrating crystal grains (313) in the active crystalline material layer is p≥80, and at the same time, the average flatness coefficient is R avg A photovoltaic device with significantly improved energy conversion efficiency was obtained, with a value of ≤75.

[0331] It should be noted that the present application is not limited to the above embodiments. The above embodiments are merely examples, and any embodiments having the same configuration as the technical concept and exhibiting the same operation and effect within the scope of the technical solution of the present application are included within the technical scope of the present application. Furthermore, various modifications that a person skilled in the art may conceive of regarding the embodiments may be made without departing from the gist of the present application, and other forms configured by combining some of the components of the embodiments are also included within the scope of the present application. Explanation of the symbols

[0332] 106: Substrate, 105: First electrode, 104: First charge transport layer, 103: Photoactive crystalline material layer, 102: Second charge transport layer, 101: Second electrode, 313: Through grain, 31, 32, 33: Backlight grain, di : Width of backlight grain, h i : Height of backlight grain protrusion, 113: Backlight surface, 151: Incident light, 152: Reflected light, 112: Receiving plane, 325: Grain boundary.

Claims

Claim 1 A photovoltaic element, wherein the photovoltaic element comprises a photoactive crystalline material layer (103) including a first region; wherein in the first region, the photoactive crystalline material layer (103) comprises penetrating crystal grains (313), and the penetrating crystal grains (313) are crystal grains that penetrate the thickness of the photoactive crystalline material layer (103), and the ratio p≥80% of the number of penetrating crystal grains (313) in the first region to the total number of crystal grains of the photoactive crystalline material layer (103) in the first region; and wherein the area of ​​the first region is 10% or more of the backlight side or light receiving side area of ​​the photoactive crystalline material layer (103). Claim 2 A photovoltaic device according to claim 1, wherein the ratio of the number of penetrating crystal grains (313) in the first region to the total number of crystal grains of the photoactive crystalline material layer (103) in the first region is p≥90%, and optionally, p≥95%, p≥99%, or p =100%. Claim 3 In claim 1 or 2, in the first region, the photoactive crystalline material layer (103) comprises a backlight side (113) and backlight crystal grains (31, 32, 33), wherein the backlight crystal grains (31, 32, 33) are crystal grains having at least one surface exposed to the backlight side (113), and the surface of the backlight crystal grains (31, 32, 33) exposed to the backlight side (113) is a backlight crystal surface; and the backlight side (113) has an average flatness coefficient R avg With, R avg ≤75, and optionally 10≤R avg ≤70 and; R of the backlight side (113) avg is calculated by the following formula, and ;R i is the flatness coefficient of the i-th backlight crystal grain (31, 32, 33) in the first region, and R i is calculated by the following formula, and R i =d i / h i d i is the width of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region; h i is the height of the protrusion on the backlight crystal surface of the i-th backlight crystal grain (31, 32, 33) in the first region; and n is the number of total backlight crystal grains (31, 32, 33) in the first region, a photovoltaic element. Claim 4 In claim 1 or 2, in the first region, the photoactive crystalline material layer (103) comprises a backlight side (113) and backlight crystal grains (31, 32, 33), wherein the backlight crystal grains (31, 32, 33) are crystal grains having at least one surface exposed to the backlight side (113), and the surface of the backlight crystal grains (31, 32, 33) exposed to the backlight side (113) is a backlight crystal surface; and the backlight side (113) has an average flatness coefficient R avg With, 10≤R avg ≤59, and optionally 10≤R avg ≤20, 11.4≤R avg ≤59, 11.4≤R avg ≤40, 40≤R avg ≤59, 26≤R avg ≤59, 26≤R avg ≤40, 11.4≤R avg ≤26 or 11.4≤R avg ≤20 and; R of the backlight side (113) avg is calculated by the following formula, and ;R i is the flatness coefficient of the i-th backlight crystal grain (31, 32, 33) in the first region, and R i is calculated by the following formula, and R i =d i / h i d i is the width of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region; h i is the height of the protrusion on the backlight crystal surface of the i-th backlight crystal grain (31, 32, 33) in the first region; and n is the number of total backlight crystal grains (31, 32, 33) in the first region, a photovoltaic element. Claim 5 In claim 1 or 2, in the first region, the photoactive crystalline material layer (103) comprises a backlight side (113) and backlight crystal grains (31, 32, 33), wherein the backlight crystal grains (31, 32, 33) are crystal grains having at least one surface exposed to the backlight side (113), and the surface of the backlight crystal grains (31, 32, 33) exposed to the backlight side (113) is a backlight crystal surface; and the backlight side (113) has an average flatness coefficient R avg With, 1≤R avg ≤10, 20≤R avg ≤30, 30≤R avg ≤40, 40≤R avg ≤50, 50≤R avg ≤60, 60≤R avg ≤70, 11.4≤R avg ≤70, 11.4≤R avg ≤75; and R of the backlight side (113) avg is calculated by the following formula, and ;R i is the flatness coefficient of the i-th backlight crystal grain (31, 32, 33) in the first region, and R i is calculated by the following formula, and R i =d i / h i d i is the width of the backlight crystal plane of the i-th backlight crystal grain (31, 32, 33) in the first region; h i is the height of the protrusion on the backlight crystal surface of the i-th backlight crystal grain (31, 32, 33) in the first region; and n is the number of total backlight crystal grains (31, 32, 33) in the first region, a photovoltaic element. Claim 6 A photovoltaic device according to claim 1, wherein the area of ​​the first region is 50% or more of the area of ​​the backlight side or the light receiving side of the photoactive crystal layer. Claim 7 In claim 1, the photoactive crystalline material layer is a photovoltaic device capable of emitting and / or absorbing at least one photon having a wavelength of 450 to 700 nm, optionally a wavelength of 450 to 650 nm. Claim 8 In claim 1, the photoactive crystalline material layer comprises an A / M / X crystalline material, and the A / M / X crystalline material has the following general formula, [A] a [M] b [X] c [M] comprises one or more first cations comprising a metal ion, a metalloid ion, or a combination thereof; [A] comprises one or more second cations; [X] comprises one or more halogen anions; a is 1 to 6, optionally, a is 1, 2, 3, 4, 5, or 6; b is 1 to 6, optionally, b is 1, 2, 3, 4, 5, or 6; c is 1 to 18, optionally, c is 3, 6, 9, or 18; a photovoltaic device. Claim 9 In paragraph 8, (1) the above one or more first cations are 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+ A feature selected from; optionally, one or more first cations are Cu 2+ , Pb 2+ , Ge 2+ or Sn 2+ (2) one or more second cations are selected from Cs + , (NR 1 R 2 R 3 R 4 ) + , (R 1 R 2 N=CR 3 R 4 ) + , (R 1 R 2 NC(R 5 )=NR 3 R 4 ) + or (R 1 R 2 NC(NR 5 R 6 )=R 3 R 4 ) + Selected from, where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently H, substituted or unsubstituted C 1-20 A feature selected from alkyl groups or substituted or unsubstituted aryl groups; optionally, one or more second cations are Cs + , (CH3NH3) + , (H2N-C(H)=NH2) + (3) selected from the halogen anion Cl - , Br - or I - A photovoltaic element having one or more features selected from. Claim 10 In claim 8, the above A / M / X crystalline material is FAPbF3, FAPbBr x I 3-x , FAPbBr x Cl 3-x , FAPbI x Cl 3-x , CsPbF3, CsPbBr x I 3-x , CsPbBr x Cl 3-x , CsPbI x Cl 3-x , FA 1-y Cs y PbF3, FA 1-y Cs y PbBr x I 3-x , FA 1-y Cs y PbBr x Cl 3-x , FA 1-y Cs y PbI x Cl 3-x A photovoltaic element comprising , or a combination thereof, wherein x=0-3, y=0.01-0.

25. Claim 11 In claim 8, the above A / M / X crystalline material is FAPbI3, FAPbBr3, FAPbCl3, FAPbF3, CsPbI3, CsPbBr3, CsPbCl3, CsPbF3, FA 1-y Cs y PbI3, FA 1-y Cs y PbBr3, FA 1-y Cs y PbCl3, FA 1-y Cs y A photovoltaic device comprising PbF3, or a combination thereof, with y=0.01-0.

25. Claim 12 In claim 8, the above A / M / X crystalline material is FAPbI3, CsPbI3, FA 1-y Cs y A photovoltaic device comprising PbI3 or a combination thereof, with y=0.01-0.

25. Claim 13 In claim 8, the photoactive crystalline material comprises a photovoltaic device comprising 5 wt% or more of an A / M / X crystalline material, optionally 80 wt% or more of an A / M / X crystalline material, more optionally 95 wt% or more of an A / M / X crystalline material, and more optionally 99 wt% or more of an A / M / X crystalline material. Claim 14 A photovoltaic device according to claim 1, wherein the thickness of the photoactive crystalline material layer is 100 nm or more, optionally 100 nm to 1000 nm, and optionally 300 nm to 700 nm. Claim 15 A photovoltaic device according to claim 1, further comprising a first charge transport layer (104) and a second charge transport layer (102), wherein the photoactive crystalline material layer (103) is located between the first charge transport layer (104) and the second charge transport layer (102); wherein the first charge transport layer (104) and the second charge transport layer (102) are each an electron transport layer and a hole transport layer, or wherein the first charge transport layer (104) and the second charge transport layer (102) are each a hole transport layer and an electron transport layer. Claim 16 In claim 15, the photovoltaic device further comprises a first electrode (105) and a second electrode (101), wherein the electron transport layer, the hole transport layer, and the photoactive crystalline material layer are located between the first electrode (105) and the second electrode (101); optionally, the first electrode (105) comprises a transparent conductive oxide; and optionally, the second electrode (101) comprises a metal. Claim 17 In a method for manufacturing an A / M / X crystalline material, the A / M / X crystalline material has the following general formula,[A] a [M] b [X] c [M] comprises one or more first cations comprising metal ions, metalloid ions, or a combination thereof; [A] comprises one or more second cations; [X] comprises one or more halogen anions; a is 1 to 6, optionally a=1; b is 1 to 6, optionally b=1; c is 1 to 18, optionally c=3; the method comprises the step of placing a precursor composition on a matrix; wherein the precursor composition comprises as components (a) at least one precursor compound; (b) a solvent; and (d) an amino compound. Claim 18 A method according to claim 17, wherein the concentration of at least one precursor compound in the precursor composition is 0.5 mol / L to 2.5 mol / L, optionally 0.5 mol / L to 1.5 mol / L or 1.5 mol / L to 2.5 mol / L. Claim 19 A method according to claim 17, wherein the concentration of the amino compound in the precursor composition is 1 wt%-10 wt%, optionally 2 wt%-4 wt%, 4 wt%-6 wt%, 6 wt%-8 wt%, or 8 wt%-10 wt%. Claim 20 In claim 17, the above precursor composition further comprises (c) a surfactant. Claim 21 A method according to claim 20, wherein the concentration of the surfactant in the precursor composition is 0.05 wt%-0.5 wt%, optionally 0.1 wt%-0.2 wt%, 0.2 wt%-0.3 wt%, 0.3 wt%-0.4 wt%, or 0.4 wt%-0.5 wt%. Claim 22 A method according to claim 20, wherein (1) the surfactant comprises an amphoteric surfactant; and (2) the amino compound comprises one or more of a nitrileamine compound, an amino acid compound, a hydrazine compound, a urea compound, a guanidine compound, or a salt or hydrate thereof. Claim 23 A method according to claim 22, wherein the amphoteric surfactant contains a cation and an anion, the cation comprises a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium, and the anion comprises a carboxylate ion, a sulfonate ion, or a phosphate ion. Claim 24 In claim 20, the surfactant comprises dodecylaminopropionate, dodecyl ethoxysulfobetaine, dodecyl dimethylhydroxypropylsulfobetaine, cationic polyacrylamide, octadecyl dihydroxyethylamine oxide, tetradecyl dihydroxyethylamine oxide, laurylamide propylamine oxide, dodecyl betaine, L-α-phosphatidylcholine, 3-(N,N-dimethyltetradecylammonium)propanesulfonate, dodecylbenzenesulfonate, or a combination thereof. Claim 25 In claim 17, the method wherein the amino compound comprises a sulfamic acid compound, aminonitrile, iminodiacetonitrile, ethylenediaminediacetonitrile, unsubstituted hydrazine, substituted hydrazine, urea compound, or a salt or hydrate thereof. Claim 26 In paragraph 25, the above urea compound is -NR 1 R 2 -C(=S)-NR 3 R 4 Includes compounds of the - group, and R 1 , R 2 , R 3 and R 4 A method independently selected from H, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups, and heterocyclic groups. Claim 27 In paragraph 25, the method comprises the urea compound comprising urea, thiourea, urea formaldehyde, biuret, triuret or a substitute thereof, or a combination thereof. Claim 28 In paragraph 17, the amino compounds are urea formaldehyde (C3H8N2O3) and isobutylidene diurea (C6H 14 A method comprising N4O2), hydrazine (H4N2), guanidine (CH3N3O), nitrileamine (CH2N2), sulfamic acid (H3NO3S), or a combination thereof. Claim 29 In claim 20, the surfactant comprises dodecyl betaine, 3-(N,N-dimethyltetradecylammonium)propanesulfonate, laurylamide propylamine oxide, L-α-phosphatidylcholine, or a combination thereof. Claim 30 In claim 17, the method wherein the amino compound comprises urea, guanidine, sulfamic acid, or a combination thereof. Claim 31 A method according to claim 20, wherein the surfactant comprises dodecyl betaine and the amino compound comprises urea; or, the surfactant comprises 3-(N,N-dimethyltetradecylammonium)propanesulfonate and the amino compound comprises guanidine; or, the surfactant comprises laurylamide propylamine oxide and the amino compound comprises sulfamic acid; or, the surfactant comprises L-α-phosphatidylcholine and the amino compound comprises urea. Claim 32 A method according to claim 17, wherein the precursor composition comprises a first solvent and a second solvent, the boiling point of the first solvent is 40°C-165°C; and the boiling point of the second solvent is 170°C-250°C. Claim 33 A method according to claim 32 comprising: (1) the first solvent being selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN); (2) the second solvent being selected from one or more of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenyl sulfoxide (DPSO); and (3) the volume ratio of the first solvent to the second solvent being (4-10):

1. Claim 34 A method according to any one of claims 17 to 33, wherein the precursor composition comprises: a first precursor compound containing a first cation; and a second precursor compound containing a second cation. Claim 35 A method according to claim 34 comprising one or more of: (1) the first precursor compound containing a halogen anion; and (2) the second precursor compound containing a halogen anion. Claim 36 A method according to claim 34, comprising: (1) that the first precursor compound comprises lead iodide (PbI2), lead bromide (PbBr2), or a combination thereof; and (2) that the second precursor compound comprises one or more of formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or a combination thereof. Claim 37 A method according to claim 17, further comprising the step of curing a precursor composition disposed on a matrix surface, wherein, optionally, the curing treatment comprises vacuum treatment, air blading, infrared treatment, or a combination thereof. Claim 38 A method according to claim 37, further comprising the step of annealing the cured product, optionally wherein the annealing temperature is 100℃-170℃; and optionally wherein the annealing time is 5 min-60 min. Claim 39 A method for manufacturing a photovoltaic element comprises, wherein the photovoltaic element comprises a first electrode (105) and a second electrode (101), a first charge transport layer (104) and a second charge transport layer (102) located between the first electrode (105) and the second electrode (101), and an A / M / X crystalline material layer located between the first charge transport layer (104) and the second charge transport layer (102); the method comprises the steps of: providing a first electrode (105) having a first charge transport layer (104) provided on its surface; forming the A / M / X crystalline material layer on the surface of the first charge transport layer (104) according to any one of claims 17 to 38; and forming the second charge transport layer (102) on the A / M / X crystalline material layer. The method comprises the step of forming a second electrode (101) on the second charge transport layer (102), wherein the first charge transport layer (104) and the second charge transport layer (102) are each an electron transport layer and a hole transport layer, or the first charge transport layer (104) and the second charge transport layer (102) are each a hole transport layer and an electron transport layer.

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