WO2023115449A1 - A/m/x晶体材料、光伏器件及其制备方法 - Google Patents
A/m/x晶体材料、光伏器件及其制备方法 Download PDFInfo
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- WO2023115449A1 WO2023115449A1 PCT/CN2021/140788 CN2021140788W WO2023115449A1 WO 2023115449 A1 WO2023115449 A1 WO 2023115449A1 CN 2021140788 W CN2021140788 W CN 2021140788W WO 2023115449 A1 WO2023115449 A1 WO 2023115449A1
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- C—CHEMISTRY; METALLURGY
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- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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Definitions
- the present application relates to the field of photovoltaic technology, in particular to an A/M/X crystal material, a photovoltaic device and a preparation method thereof.
- a perovskite photovoltaic device is a photovoltaic device that uses a photoactive perovskite structure material as a photoactive crystal material layer to perform photoelectric conversion.
- a typical photoactive perovskite structure material is an organometallic halide, which has a general formula AMX 3 , and generally has an octahedral or cubic structure.
- the A ion is in the center of the cubic unit cell, and is marked by 12 X ions to obtain a coordination cubic octahedron, forming a three-dimensional periodic structure; the M ion is located at the corner of the cubic unit cell. , around which 6 X ions are coordinated to form an octahedral symmetric structure.
- the photoactive perovskite structure material forms two kinds of carriers, namely electrons and holes, and collects electrons and holes through two electrodes respectively, that is, obtains photogenerated current.
- the nature of the perovskite structure is a key factor affecting the power conversion efficiency (PCE) of photovoltaic devices.
- the purpose of this application is to provide a photovoltaic device with higher energy conversion efficiency.
- the first aspect of the present application provides a photovoltaic device, including a layer of photoactive crystal material, and the layer of photoactive crystal material includes a first region;
- the photoactive crystal material layer includes penetrating crystal grains, the penetrating grains are crystal grains penetrating the photoactive crystal material layer, and the number of the penetrating crystal grains accounts for 10% of the photoactive crystal material layer.
- the percentage of the total number of grains of the material layer in said first region p ⁇ 80%, optionally p ⁇ 90%;
- the photoactive crystal material layer includes a backlight side and backlight crystal grains, the backlight crystal grains are crystal grains with at least one surface exposed to the backlight side, and the backlight crystal grains are exposed to the backlight crystal grains.
- the surface on the backlight side is the backlight crystal surface;
- the backlight side has an average flatness coefficient R avg , R avg ⁇ 75, optionally 10 ⁇ R avg ⁇ 70;
- R avg of the backlight side is calculated by the following formula:
- R i is the flatness coefficient of the i-th backlight grain in the first region, and R i is calculated by the following formula:
- d i is the width of the backlight crystal plane of the i-th backlight grain in the first region
- h i is the protrusion height of the backlight crystal plane of the ith backlight crystal grain in the first region
- n is the number of all backlight grains in the first region.
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the photoactive crystalline material comprises an A/M/X crystalline material having the following general formula:
- [M] comprising one or more first cations comprising metal ions, metalloid ions, or combinations thereof;
- [A] includes one or more second cations
- [X] comprises one or more halide 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.
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the one or more first cations are selected from Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ , Eu 2+ , Bi3 + , Sb3+, Pd 4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4 + , Sn 4+ , Pb 4+ , Ge 4+ or Te 4+ .
- the one or more first cations are selected from Cu 2+ , Pb 2+ , Ge 2+ or Sn 2+ ;
- the halogen anion is selected from Cl - , Br - or I - .
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the A/M/X crystalline material comprises FAPbI 3 , FAPbBr 3 , FAPbCl 3 , FAPbF 3 , 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 , CsPbI 3 , CsPbBr 3 , CsPbCl 3 , CsPbF 3 , 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 PbI 3 , FA 1-y Cs y PbBr 3 , FA 1-y Cs y
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the thickness of the photoactive crystal material layer is more than 100nm, optionally 100nm-1000nm, optionally 300nm-700nm.
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the photovoltaic device further comprises a first charge transport layer and a second charge transport layer, the layer of photoactive crystalline material being located between the first charge transport layer and the second charge transport layer;
- the first charge transport layer and the second charge transport layer are respectively an electron transport layer and the hole transport layer, or
- the first charge transport layer and the second charge transport layer are respectively a hole transport layer and an electron transport layer.
- the photovoltaic device further includes a first electrode and a second electrode, the electron transport layer, the hole transport layer, and the layer of photoactive crystalline material positioned between the first electrode and the second electrode;
- the first electrode comprises a transparent conductive oxide
- the second electrode comprises metal.
- Photovoltaic devices based on the above schemes have improved energy conversion efficiency.
- the second aspect of the present application provides a method for preparing an A/M/X crystal material, and the A/M/X crystal material has the following general formula:
- [M] comprising one or more first cations comprising metal ions, metalloid ions, or combinations thereof;
- [A] includes one or more second cations
- [X] comprises one or more halide anions
- the method includes disposing a precursor composition on the substrate, the precursor composition comprising the following components:
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the surfactant comprises an amphoteric surfactant.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the amino compounds include: nitrile amine compounds, amino acid compounds (such as sulfamic acid compounds), hydrazine compounds, urea compounds (such as urea, urea-formaldehyde, biuret, triuret) , a guanidine compound, or a salt or hydrate thereof.
- amino acid compounds such as sulfamic acid compounds
- hydrazine compounds such as urea, urea-formaldehyde, biuret, triuret
- urea compounds such as urea, urea-formaldehyde, biuret, triuret
- a guanidine compound such as urea, urea-formaldehyde, biuret, triuret
- the surfactant comprises laurylaminopropionate, dodecylethoxysulfobetaine, dodecyldimethylhydroxypropylsulfobetaine, zwitterion Polyacrylamide, Octadecyldihydroxyethylamine Oxide, Tetradecyldihydroxyethylamine Oxide, Laurylamidopropylamine Oxide, Lauryl Betaine, L- ⁇ -Phosphotidylcholine, 3 -(N,N-Dimethyltetradecylammonium)propanesulfonate, dodecylbenzenesulfonate, or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the amino compound includes: urea-formaldehyde (C 3 H 8 N 2 O 3 ), isobutylidene diurea (C 6 H 14 N 4 O 2 ), hydrazine (H 4 N 2 ), guanidine ( CH 3 N 3 O), nitrile amine (CH 2 N 2 ), sulfamic acid (H 3 NO 3 S), or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the precursor composition includes a first solvent and a second solvent, the boiling point of the first solvent is 40°C-165°C; the boiling point of the second solvent is 170°C-250°C.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the first solvent is selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN).
- DMF N,N-dimethylformamide
- ACN acetonitrile
- the second solvent is selected from one or more of dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenylsulfoxide (DPSO).
- DMSO dimethylsulfoxide
- NMP N-methylpyrrolidone
- DPSO diphenylsulfoxide
- the volume ratio of the first solvent to the second solvent is (4-10):1.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the precursor composition includes:
- a second precursor compound containing a second cation A second precursor compound containing a second cation.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the first precursor compound contains a halide anion.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the second precursor compound contains a halide anion.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the first compound comprises lead iodide (PbI 2 ), lead bromide (PbBr 2 ), or a combination thereof;
- the second compound comprises formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or combinations thereof.
- FI formamidine hydroiodide
- FABr formamidine hydrobromide
- CsI cesium iodide
- CsBr cesium bromide
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the method for preparing A/M/X crystal material also includes the step of curing the precursor composition disposed on the surface of the substrate;
- the curing treatment includes: vacuum treatment, air blade treatment (air blading), infrared light treatment or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the method for preparing the A/M/X crystal material further includes annealing the cured product
- the temperature of the annealing treatment is 100°C-170°C;
- the time for the annealing treatment is 5 min-60 min.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices exhibit improved energy conversion efficiency.
- the third aspect of the present application provides a method for preparing a photovoltaic device, the photovoltaic device comprising 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 layer, and a layer of A/M/X crystal material positioned between said first and second charge transport layers;
- the methods include:
- first charge transport layer and the second charge transport layer are respectively the electron transport layer and the hole transport layer, or
- the first charge transport layer and the second charge transport layer are respectively a hole transport layer and an electron transport layer.
- the photovoltaic device prepared based on the above scheme has improved energy conversion efficiency.
- Photovoltaic devices exhibit significantly enhanced power conversion efficiency (Power Conversion Efficiency, PCE);
- the photoactive crystalline material layer has a relatively high proportion p of through grains
- the photoactive crystal material layer has a lower average flatness coefficient R avg ;
- the preparation method has low cost, high efficiency and easy scale-up.
- Fig. 1 shows the schematic diagram of the photovoltaic device of some embodiments of the present application
- Figure 2 shows a schematic diagram of a photoactive crystal material layer in some embodiments of the present application
- FIG. 3 show schematic diagrams of photoactive crystal material layers of some embodiments of the present application and comparative embodiments, respectively;
- Figure 4 shows a scanning electron micrograph of an intermediate product containing a layer of photoactive crystalline material according to some embodiments of the present application.
- Incident light 151 reflected light 152 , light receiving surface 112 , and grain boundary 325 .
- ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
- the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
- a certain parameter is an integer ⁇ 2
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
- steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
- the “comprising” and “comprising” mentioned in this application mean open or closed.
- the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
- the term "or” is inclusive unless otherwise stated.
- the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: 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 both A and B are true (or exist).
- Photovoltaic devices also known as photovoltaic cells or solar cells
- solar cells are devices used to convert solar energy into electrical energy.
- 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 crystal material layer according to some embodiments of the present application.
- the present application provides a photovoltaic device, which includes a photoactive crystalline material layer 103, and the photoactive crystalline material layer 103 includes a first region;
- the photoactive crystal material layer 103 includes a backlight side 113 (backlight side) and backlight crystal grains (31, 32, 33) (backlight crystal), and the backlight crystal grains (31, 32, 33 ) is a crystal grain with at least one surface exposed to the backlight side 113, and the surface of the backlight crystal grain (31, 32, 33) exposed to the backlight side 113 is a backlight crystal face (backlight crystal face);
- the backlight side 113 has an average flatness coefficient R avg (Average Flatness Index), R avg ⁇ 75, optionally 10 ⁇ R avg ⁇ 70, and optionally the value of R avg is 1-10, 10-20, 20-30, 30-40, 40-50, 50-60 or 60-70;
- R avg of the backlight side 113 is calculated by the following formula:
- R i is the flatness coefficient of the i-th backlight grain (31, 32, 33) in the first region, and R i is calculated by the following formula:
- d i is the width of the backlight crystal plane of the i-th backlight grain (31, 32, 33) in the first region;
- h i is the protrusion height of the backlight crystal plane of the ith backlight grain (31, 32, 33) in the first region;
- n is the number of all backlight crystal grains (31, 32, 33) in the first region.
- the inventors unexpectedly found that by optimizing the grain shape and arrangement of the photoactive crystal material layer, the energy conversion efficiency of the photovoltaic device can be significantly improved. Specifically, the inventors found that when the number of penetrating crystal grains 313 in the photoactive crystal material layer accounts for the percentage p ⁇ 80% of the total crystal grain number of the photoactive crystal material layer 103 in the first region, at the same time, the light When the average flatness coefficient R avg of the backlight crystal grains (31, 32, 33) in at least part of the area on the backlight side of the active crystal material layer is ⁇ 75, the photovoltaic device exhibits significantly enhanced power conversion efficiency (Power Conversion Efficiency, PCE).
- PCE Power Conversion Efficiency
- FIG. 2 shows a layer 103 of photoactive crystalline material comprising a backlight side 113 and backlight grains (31, 32, 33) that are exposed to the backlight a die on side 113, said backlight die (31, 32, 33) having a backlight facet exposed to said backlight side;
- R avg of the backlight side 113 is calculated by the following formula:
- R i is the flatness coefficient of the i-th backlight grain (31, 32, 33) in the first region, and R i is calculated by the following formula:
- d i is the width (d 1 , d 2 , d 3 ) of the backlight crystal plane of the ith backlight grain (31, 32, 33) in the first region;
- h i is the protrusion height (h 1 , h 2 , h 3 ) of the backlight crystal plane of the ith backlight crystal grain (31, 32, 33) in the first region;
- n is the number of all backlight grains (31, 32, 33) in the first region
- the number n 3 of all backlight crystal grains ( 31 , 32 , 33 ), therefore, the value of i ranges from 1 to 3.
- the value of n is above 3, such as above 5, such as above 10, such as above 50, such as above 100, such as above 500, such as above 1000.
- FIG. 3 (a) and (b) of FIG. 3 respectively show schematic diagrams of two kinds of photoactive crystal material layers.
- FIG. 3 a schematic diagram of the first photoactive crystal material layer is shown.
- the incident light 151 enters from the light-receiving surface 112 of the first photoactive crystal material layer. Since the crystal grains of the first photoactive crystal material layer penetrate the crystal grains 313, the incident light 151 can reach the backlight surface 113 almost unobstructed. This enables the first photoactive crystal material layer to be sufficiently irradiated by the incident light 151 .
- the incident light 151 is incident from the light-receiving surface 112 of the comparative photoactive crystal material layer, since the crystal grains of the comparative photoactive crystal material layer 313 are non-penetrating crystal grains 323 . Therefore, the incident light 151 will be reflected or refracted by the grain boundary 325 before reaching the backlight surface 113 , which results in that the contrast photoactive crystal material layer cannot sufficiently absorb the radiant energy of the incident light 151 .
- the flatness coefficient is the coefficient of the degree of flatness of the grain from the surface. The higher the flatness coefficient, the backlight crystal surface of the grain is close to the plane, and the lower the flatness coefficient is, the higher the convexity of the backlight crystal plane of the grain is.
- the backlight grains ( 31 , 32 , 33 ) of the first photoactive crystal material layer have relatively low flatness coefficients ( ⁇ 75), that is, the broadband of the backlight grains ( 31 , 32 , 33 ) is the same as
- the ratio of raised heights (d/h) is low and the backlight grains (31, 32, 33) have a raised surface, which enables the backlight side 113 of the layer of contrasting light-active crystal material to absorb the reflected light 152 for the most part. Concentrates into the layer of the first layer of photoactive crystalline material rather than reflecting out of the layer. This enables the first photoactive crystal material layer to fully utilize light energy.
- FIG. 3 shows a schematic diagram of a contrasting photoactive crystal material layer, as shown in the figure, the backlight grains (31, 32, 33) of the contrasting photoactive crystal material layer
- the flatness factor of is relatively high (>1000), that is, the backlight crystal grains (31, 32, 33) have flat backlight crystal planes.
- the flat backlit surface will largely reflect the reflected light 152 out of the layer, which prevents the contrast light active crystal material layer 312 from fully utilizing the light energy.
- the first region refers to a part or all of the region of the photoactive crystal layer 103 along the surface of the layer.
- the size of the first region in at least one direction is greater than 3 ⁇ m, such as greater than 10 ⁇ m, such as greater than 100 ⁇ m, such as greater than 1 mm, such as greater than 1 cm, such as greater than 10 cm.
- the size of the first region in at least two mutually perpendicular directions is 3 ⁇ 3 ⁇ m or larger, for example 10 ⁇ 10 ⁇ m or larger, for example 100 ⁇ 100 ⁇ m or larger, for example 1 ⁇ 1 mm or larger, for example 1 ⁇ 1 cm or larger, for example 10 ⁇ More than 10cm, for example, more than 1m ⁇ 1m.
- the total number of grains in the first region of the photoactive crystal layer is more than 9 (3 ⁇ 3), for example more than 16 (4 ⁇ 4), 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.
- the area of the first region corresponds to more than 10%, such as more than 50%, such as more than 70%, such as more than 90%, such as 100%, of the area of one side of the photoactive crystal layer.
- the layer of photoactive crystals 103 includes a plurality of crystal grains.
- the grains penetrating through the photoactive crystal material layer 103 are penetrating grains 313 .
- the dies with at least one surface exposed to the backlight side 113 are backlight dies (31, 32, 33). It should be understood that a die can belong to both the through die 313 and the backlight die ( 31 , 32 , 33 ). In addition, a die may only belong to the backlight die ( 31 , 32 , 33 ) and not belong to the through die 313 .
- the term "crystalline" refers to a crystalline compound, which is a compound having an extended 3D crystal structure.
- Crystalline compounds generally exist in the form of crystals or, in the case of polycrystalline compounds, as microcrystals (ie a plurality of crystals having a particle size of less than or equal to 1 ⁇ m). Crystals together tend to form layers.
- the crystals of crystalline material may be of any size. When crystals have sizes in the range of 1 nm to 1000 nm in one or more dimensions, they may be referred to as nanocrystals.
- the term "layer” refers to any structure that is substantially laminar (eg, extending substantially in two perpendicular directions, but having limited extension in a third perpendicular direction).
- a layer may have a thickness that varies over the extent of the layer. Typically, a layer has an approximately constant thickness.
- thickness of a layer refers to the average thickness of the layer. The thickness of a layer can be easily measured, for example, by using microscopy, such as electron microscopy of film cross-sections, or by surface profilometry, such as using a stylus profilometer.
- the term “light receiving surface” refers to the surface of the photovoltaic device facing the light source during operation; the term “backlight surface” refers to the surface of the photovoltaic device facing away from the light source during operation.
- the term "grain” as used herein refers to a "single crystal grain.”
- one grain refers to one single crystal grain; the number of grains refers to the number of single crystal grains.
- single crystal can be defined as "a single crystal body of crystalline material that contains no large-angle boundaries or twin boundaries", such as As described in ASTM F1241.
- the term "through" means from one side of the photoactive crystal layer to the other side, eg, from the light receiving side to the backlight side.
- the protrusion height of the backlight crystal plane is measured by micrograph observation of the cross-section of the photoactive crystal material layer.
- the profile of the crystal plane to be lighted is defined as the raised height of the crystal plane being lighted relative to the height of the basal plane being lighted;
- the width of the protrusion on the base surface is the width of the crystal surface to be lighted.
- illuminated base surface is meant a continuous, substantially flat surface that extends substantially through the lowest point of each illuminated crystal surface.
- the photoactive crystalline material comprises an A/M/X crystalline material having the following general formula:
- [M] comprising one or more first cations comprising metal ions, metalloid ions, or combinations thereof;
- [A] includes one or more second cations
- [X] comprises one or more halide 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. Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the one or more first cations are selected from Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ , Eu 2+ , Bi3 + , Sb3+, Pd 4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4 + , Sn 4+ , Pb 4+ , Ge 4+ or Te 4+ . Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the one or more first cations are selected from Cu 2+ , Pb 2+ , Ge 2+ , or Sn 2+ . Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the halide anion is selected from Cl ⁇ , Br ⁇ or I ⁇ . Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the A/M/X crystalline material comprises FAPbI 3 , FAPbBr 3 , FAPbCl 3 , FAPbF 3 , 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 , CsPbI 3 , CsPbBr 3 , CsPbCl 3 , CsPbF 3 , 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 PbI 3 , FA 1-y Cs y PbBr 3 , FA 1-y Cs y
- the A/M/X crystalline material is a perovskite material.
- the A/M/X crystal material is a metal halide perovskite.
- metal halide perovskite refers to a perovskite having a formula comprising at least one metal cation and at least one halide anion.
- the A/M/X crystal material is a mixed halide perovskite.
- mixed halide perovskite refers to a perovskite or mixed perovskite comprising at least two types of halide anions.
- the A/M/X crystal material is a mixed cation perovskite.
- mixed cation perovskite refers to a perovskite comprising a mixed perovskite of at least two types of A cations. Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the term "perovskite” refers to a material having a three-dimensional crystal structure related to the three-dimensional crystal structure of CaTiO3 , or including layer materials having a structure related to the structure of CaTiO3 .
- Materials with a three-dimensional crystal structure related to CaTiO3 can be referred to as perovskites with a "3D perovskite structure", or as "3D perovskites”.
- the structure of CaTiO 3 can be represented by the formula AMX 3 , where A and M are cations of different sizes, and X is an anion.
- cation A is at (0,0,0)
- cation M is at (1/2,1/2,1/2)
- anion X is at (1/2,1/2,0) place.
- Cation A is generally larger than cation M.
- Materials comprising layers of perovskite materials are well known.
- a material structure employing a K2NiF4-type structure includes a layer of perovskite material.
- a 2D layered perovskite can be represented by the formula [A] 2 [M][X] 4 , where [A] is at least one cation, [M] is at least one cation different in size from cation [A], and [X] is at least one anion.
- the thickness of the photoactive crystal material layer is more than 100 nm, optionally 100-1000 nm, and optionally 300-700 nm. Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the photovoltaic device further comprises a first charge transport layer 104 and a second charge transport layer 102, the photoactive crystalline material layer 103 is located between the first charge transport layer 104 and the second charge transport layer 102 ;
- the first charge transport layer 104 and the second charge transport layer 102 are respectively an electron transport layer and the hole transport layer, or
- 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 solutions, photovoltaic devices have improved energy conversion efficiency.
- the photovoltaic device further includes a first electrode 105 and a second electrode 101, and the electron transport layer, the hole transport layer and the photoactive crystal material layer are located between the first electrode 105 and the second electrode 101;
- the first electrode 105 includes a transparent conductive oxide
- the second electrode 101 includes metal. Based on the above solutions, photovoltaic devices have improved energy conversion efficiency.
- the present application also provides a method for preparing A/M/X crystalline material, the A/M/X crystalline material has the following general formula:
- [M] comprising one or more first cations comprising metal ions, metalloid ions, or combinations thereof;
- [A] includes one or more second cations
- [X] comprises one or more halide anions
- the method includes disposing a precursor composition on the substrate, the precursor composition comprising the following components:
- the inventors unexpectedly found that by applying the surfactant and the amino compound in combination to the precursor composition for preparing the A/M/X crystal material, the A/M/X crystal material prepared has relatively high With a high through-grain ratio and a low flatness coefficient, the A/M/X crystal material is used in photovoltaic devices with improved energy conversion efficiency.
- the concentration of at least one precursor compound in the precursor composition is 0.5 mol/L-2.5 mol/L, such as 0.5 mol/L-1.5 mol/L, 1.5 mol/L-2.5 mol/L L.
- the concentration of surfactant in the precursor composition is 0.05wt%-0.5wt%, such as 0.1wt%-0.2wt%, 0.2wt%-0.3wt%, 0.3wt%-0.4wt% Or 0.4wt%-0.5wt%.
- the concentration of the amino compound in the precursor composition is 1wt%-10wt%, such as 2wt%-4wt%, 4wt%-6wt%, 6wt%-8wt%, or 8wt%-10wt%.
- surfactant refers to any amphiphilic compound (molecule or ion) that includes hydrophilic and lipophilic moieties.
- Surfactants generally work by accumulating at the oil-water interface, orienting the hydrophilic portion towards the water phase and the lipophilic portion towards the hydrophobic phase, thereby reducing surface tension.
- Suitable surfactants include water insoluble surfactants, water dispersible surfactants and water soluble surfactants.
- the surfactant comprises an amphoteric surfactant.
- amphoteric surfactant refers to a compound having cationic and anionic centers attached to the same molecule.
- the cationic moieties are based on primary, secondary or tertiary amines or quaternary ammonium cations.
- Anionic moieties include, but are not limited to, carboxylates, sulfonates and phosphates.
- amphoteric surfactant refers to a compound having an N + -O- functional group combined with a C(O)O-, SO 3 H or SO 3 - functional group, a quaternary N + functional group, and a compound with a C( Compounds with tertiary N functional groups in combination with O)OH, C(O)O-, SO 3 H or SO 3 -functional groups.
- amphoteric surfactants For a review of amphoteric surfactants and their properties, reference may be made to Amphoteric Surfactants, 2nd Edition, edited by E.G. Lomax, 1996, Marcel Decker Press (Amphoteric Surfactants, 2nd ed., E.G. Lomax, Ed. , 1996, Marcel Dekker).
- Such surfactants include betaines, such as fatty alkyl betaines, fatty alkylamide betaines, sultaines, hydroxysultaines, and betaines derived from imidazolines; amine oxides, such as fatty alkyl betaines; amine oxides and fatty alkyl amidoamine oxides; amphoglycinates and amphopropionates; and so-called "balanced" amphopolycarboxyglycinates and amphopolycarboxypropionates.
- betaines such as fatty alkyl betaines, fatty alkylamide betaines, sultaines, hydroxysultaines, and betaines derived from imidazolines
- amine oxides such as fatty alkyl betaines
- amine oxides and fatty alkyl amidoamine oxides amphoglycinates and amphopropionates
- the amino compound includes: amino nitrile compounds, amino acid compounds, hydrazine compounds, urea compounds (such as urea, urea-formaldehyde, biuret, triuret), guanidine compounds, or salts thereof or hydrate.
- amino compounds refers to any compound containing at least one primary, secondary or tertiary amine or quaternary ammonium group.
- the amino compound is a C1-C20 compound, such as a C1-C15 compound, such as a C1-C10 compound, such as a C1-C5 compound, or a C15-C20 compound.
- aminonitrile compound refers to a compound containing at least one "amino-methyl-cyano” group.
- Alternative “aminonitriles” include aminonitriles (AAN), iminodiacetonitrile (IDAN) or ethylenediaminediacetonitrile (EDN).
- amino acid refers to a molecule having at least one amino group and at least one carboxyl group.
- sulfamate refers to a molecule containing at least one amino group and at least one sulfo group.
- hydrazine compound includes hydrazine and substituted hydrazines.
- substitution means that the H atom of the substituted compound is replaced by one or more of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl and heterocyclyl
- Alternative urea compounds include urea (urea), thiourea, urea-formaldehyde, biuret, triuret, and substitutions thereof.
- the surfactant comprises laurylaminopropionate, dodecylethoxysulfobetaine, dodecyldimethylhydroxypropylsulfobetaine, zwitterion Polyacrylamide, Octadecyldihydroxyethylamine Oxide, Tetradecyldihydroxyethylamine Oxide, Laurylamidopropylamine Oxide, Lauryl Betaine, L- ⁇ -Phosphotidylcholine, 3 -(N,N-Dimethyltetradecylammonium)propanesulfonate, dodecylbenzenesulfonate, or a combination thereof.
- photovoltaic devices have improved energy conversion efficiency.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the surfactants include lauryl betaine, 3-(N,N-dimethyltetradecylammonium) propanesulfonate, lauryl amidopropylamine oxide, L-alpha - Phosphatidylcholine, or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the amino compounds include: urea-formaldehyde (C 3 H 8 N 2 O 3 ), isobutylidene diurea (C 6 H 14 N 4 O 2 ), hydrazine (H 4 N 2 ), guanidine (CH 3 N 3 O), nitrile amine (CH 2 N 2 ), sulfamic acid (H 3 NO 3 S), or a combination thereof.
- photovoltaic devices have improved energy conversion efficiency.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the amino compound includes: guanidine, sulfamic acid, urea, or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the precursor composition includes a first solvent and a second solvent; the boiling point of the first solvent is 40°C-165°C (eg, 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); the boiling point of the second solvent is 170°C-250°C (such as 170°C-190°C, 190°C-210°C, 210°C-230°C or 230°C-250°C).
- the combined use of the first solvent with a specific boiling point and the second solvent with a specific boiling point can effectively improve the film coverage and crystallization quality of the A/M/X crystal material.
- the first solvent is selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN).
- DMF N,N-dimethylformamide
- ACN acetonitrile
- the second solvent is selected from one or more of dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenylsulfoxide (DPSO).
- DMSO dimethylsulfoxide
- NMP N-methylpyrrolidone
- DPSO diphenylsulfoxide
- the volume ratio of the first solvent to the second solvent is (4-10):1.
- the combined use of the first solvent with a specific boiling point and the second solvent with a specific boiling point in the above specific ratio can effectively improve the film coverage and crystallization quality of the A/M/X crystal material.
- the precursor composition includes
- a second precursor compound containing a second cation is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the first precursor compound contains a halide anion.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the second precursor compound contains a halide anion.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the first compound includes lead iodide (PbI 2 ), lead bromide (PbBr 2 ), or a combination thereof.
- PbI 2 lead iodide
- PbBr 2 lead bromide
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the second compound comprises formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or combinations thereof.
- FI formamidine hydroiodide
- FABr formamidine hydrobromide
- CsI cesium iodide
- CsBr cesium bromide
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the method for preparing the A/M/X crystal material further includes the step of curing the precursor composition disposed on the surface of the substrate;
- the curing treatment includes: vacuum treatment, air blade treatment (air blading), infrared light treatment or a combination thereof.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the method for preparing the A/M/X crystalline material further includes annealing the cured product.
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the temperature of the annealing treatment is 100°C-170°C (eg, 100°C-120°C, 120°C-140°C, 140°C-160°C, or 160°C-170°C).
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the time of the annealing treatment is 5min-60min (for example, 5min-15min, 15min-25min, 25min-35min, 35min-45min or 45min-55min).
- the A/M/X crystal material prepared based on the above scheme is used in photovoltaic devices, and the photovoltaic devices have improved energy conversion efficiency.
- the present application also provides a method for preparing a photovoltaic device, the photovoltaic device includes a first electrode 105 and a second electrode 101, and the first electrode 105 and the second electrode 101 are located between the first electrode 105 and the second electrode 101.
- the methods include:
- the A/M/X crystal material layer is formed on the surface of the first charge transport layer 104;
- first charge transport layer 104 and the second charge transport layer 102 are respectively an electron transport layer and the hole transport layer, or
- the first charge transport layer 104 and the second charge transport layer 102 are respectively a hole transport layer and an electron transport layer. Photovoltaic devices prepared based on the above scheme have improved energy conversion efficiency.
- a photovoltaic device may include the following layers in the following order:
- a first electrode eg comprising a transparent conductive oxide
- a first layer of charge transport material eg a layer of hole transport material
- a second layer of charge transport material eg, a layer of electron transport material
- a second electrode for example comprising an elemental metal.
- Photovoltaic devices prepared based on the above scheme have improved energy conversion efficiency.
- a photovoltaic device may include the following layers in the following order:
- a first electrode eg comprising a transparent conductive oxide
- a first charge transport material layer eg electron transport material layer
- a second layer of charge transport material eg a layer of hole transport material
- a second electrode for example comprising an elemental metal.
- Photovoltaic devices prepared based on the above scheme have improved energy conversion efficiency.
- photoactive crystalline material refers to a material capable of absorbing light and subsequently generating free charge carriers (eg, electrons and holes).
- the photoactive crystalline material is generally capable of absorbing and/or emitting photons in the visible region of the spectrum, eg, in the blue region of the visible spectrum.
- photoactive crystalline materials may be described as light-emitting materials (ie, materials capable of emitting light) or light-absorbing materials (ie, materials capable of absorbing light).
- a photoactive crystalline material is eg capable of emitting and/or absorbing at least one photon at a wavelength of 450 to 700 nm, such as 450 to 650 nm.
- the photoactive crystalline material can include greater than or equal to 5 wt% A/M/X crystalline material.
- the photoactive crystalline material comprises greater than or equal to 80 wt% A/M/X crystalline material, such as greater than or equal to 95 wt% A/M/X crystalline material, such as greater than or equal to 99 wt% A/M/X crystalline material .
- the photoactive crystalline material may consist of or consist essentially of A/M/X crystalline material.
- the photoactive crystalline material is, for example, a solid.
- the layer of photoactive crystalline material comprises a thin film of A/M/X crystalline material.
- A/M/X crystalline materials are polycrystalline, thus photoactive crystalline materials accordingly include polycrystalline A/M/X crystalline materials.
- the layer of photoactive crystalline material can include multiple layers. Some or all of the various layers may include A/M/X crystal material.
- the A/M/X crystalline material can be distributed uniformly or non-uniformly throughout the layer of photoactive crystalline material.
- the photoactive crystalline material may comprise a layer consisting essentially or exclusively of A/M/X crystalline material.
- the photoactive crystalline material may comprise the substrate with the A/M/X crystalline material on the substrate (eg in powder form or thin film form).
- an electron transport layer is a layer comprising 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 material, or a mixture of two or more electron transport compounds or material.
- the electron transport compound or elemental material can be undoped or doped with one or more doping elements.
- Electron transport materials may include fullerenes or fullerene derivatives such as C60, C70, PCBM, PC71BM, bis[C60]BM (i.e., bis-C60-methylbutyrate), ICBA (CAS: 1207461-57- 1)
- Electron transport materials may include organic electron transport materials such as perylene or its derivatives, P(NDI2OD-T2) (CAS: 1100243-40-0) or bathocuproine (BCP).
- organic electron transport materials such as perylene or its derivatives, P(NDI2OD-T2) (CAS: 1100243-40-0) or bathocuproine (BCP).
- Electron transport materials can 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 III-V semiconductors, n Type II-VI semiconductors, n-type I-VII semiconductors, n-type IV-VI semiconductors, n-type V-VI semiconductors, and n-type II-V semiconductors, any of which may be doped or unadulterated.
- inorganic electron transport materials such as metal oxides, metal sulfides, metal selenides, metal tellurides, perovskites, amorphous silicon, n-type Group IV semiconductors, n-type III-V semiconductors, n Type II-VI semiconductors, n-type I-VII semiconductors, n-type IV-VI semiconductors, n-type V-VI semiconductors, and n-type II-V semiconductors, any of which may be doped or unadulterated.
- a hole transport layer refers to a layer comprising a hole transport (also known as p-type semiconductor material) material.
- the hole transport material may be a single hole transport compound or material, or a mixture of two or more hole transport compounds or material.
- the hole transport compound or elemental material can be undoped or doped with one or more doping elements.
- Organic hole transport materials can include, for example, spiro-OMeTAD, P3HT, PCPDTBT, poly-TPD, spiro(TFSI) 2 , and PVK.
- Inorganic hole transport materials may include oxides of nickel (such as NiO), vanadium, copper, or molybdenum; CuI, CuBr, CuSCN, Cu2O , CuO, or CIS; perovskites; amorphous silicon; p-type III-V semiconductors, p-type II-VI semiconductors, p-type I-VII semiconductors, p-type IV-VI semiconductors, p-type V-VI semiconductors and p-type II-V semiconductors, these inorganic Materials can be doped or undoped.
- nickel such as NiO
- perovskites amorphous silicon
- p-type III-V semiconductors p-type II-VI semiconductors, p-type I-VII semiconductors, p-type IV-VI semiconductors, p-type V-VI semiconductors and p-type II-V semiconductors, these inorganic Materials can be doped or und
- electrode means a region or layer consisting or consisting essentially of an electrode material.
- the photovoltaic device of the present application may further include a first electrode and a second electrode.
- the first electrode may comprise a metal such as silver, gold, aluminum, or tungsten, an organic conducting material such as PEDOT:PSS, or a transparent conducting oxide such as fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO) or indium-doped tin oxide (ITO).
- FTO fluorine-doped tin oxide
- AZO aluminum-doped zinc oxide
- ITO indium-doped tin oxide
- the first electrode is a transparent electrode. Therefore, the first electrode usually includes a transparent conductive oxide, such as FTO, ITO or AZO.
- the thickness of the layer of the first electrode is eg It is 10nm to 1000nm, another example is 40nm to 400nm.
- the second electrode may be as defined above for the first electrode, for example, the second electrode may comprise a metal (such as silver, gold, aluminum or tungsten), an organic conductive material (such as PEDOT:PSS) or a transparent conductive oxide (such as Fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO) or indium-doped tin oxide (ITO).
- the second electrode comprises a metal (such as a simple metal) or consists essentially of a metal (such as elemental metal).
- the second electrode material may include an example of a metal or consist essentially of a metal, such as silver, gold, copper, aluminum, platinum, palladium, or tungsten.
- the second electrode may be deposited by vacuum evaporation.
- the second electrode The thickness of the material layer is, for example, 10 to 1000 nm, such as 50 nm to 150 nm.
- the technical solution of the present application will be described in detail below in conjunction with specific examples and comparative examples.
- the reagents, methods and equipment used in this application are conventional food-grade reagents, methods and equipment in the art.
- the test conditions used in the examples of the present application are conventional test conditions in the art.
- all reagents used in the examples of this application are commercially available.
- the photovoltaic device of embodiment 1 comprises substrate 106, first electrode 105, first charge transport layer 104, photoactive crystal material layer 103, second charge transport layer stacked in sequence 102 and the second electrode 101.
- the preparation method of the photovoltaic device of embodiment 1 is as follows:
- Example 1 a surfactant and a nitrogen-containing compound were added to the above solvent, and the weight percentages of the two were 0.1wt% and 5wt%, respectively.
- the surfactant is lauryl betaine
- the nitrogen-containing compound is urea.
- FTO conductive glass is glass with FTO conductive layer on the surface
- FTO is the abbreviation of Fluorine doped tin oxide
- FTO conductive glass includes a glass plate and an FTO conductive layer deposited on the glass plate.
- the FTO conductive layer with a width of 0.66 cm on two opposite edges of the FTO conductive glass was removed by laser engraving technique, and the FTO conductive layer with a size of 2 cm ⁇ 1.34 cm remained on the FTO conductive glass.
- the glass plate serves as the substrate 106 and the FTO conductive layer serves as the first electrode 105 .
- a first charge transport layer 104 (nickel oxide layer) is formed on the first electrode 105 (FTO conductive layer), and the thickness of the nickel oxide layer is about 20 nm.
- the first charge transport layer 104 serves here as a hole transport layer.
- the sample was transferred to a vacuum chamber, and stood for 120 seconds under a vacuum of 100 Pa, so that the precursor solution was solidified to form a film.
- the cured sample was placed on a hot stage for annealing treatment, the temperature of the annealing treatment was 150°C, and the annealing treatment time was 30 minutes; after the annealing treatment, a good A/M/X crystal material layer was formed on the nickel oxide layer.
- the composition of the A/M/X crystal material is FA 0.9 Cs 0.1 PbI 3 .
- the A/M/X crystalline material layer serves as the photoactive crystalline material layer 103 here.
- the second charge transport layer 102 is an electron transport layer.
- the second charge transport layer includes a C 60 (fullerene) layer with a thickness of 30 nm and a BCP (bathocuproine) layer with a thickness of 8 nm formed by sequential evaporation.
- the second electrode 101 is formed on the second charge transport layer 102 .
- the second electrode 101 is a metal copper layer with a thickness of 100 nm, and the photovoltaic device of Example 1 is obtained.
- Example 1 lies in the types of surfactants and/or nitrogen-containing compounds in the precursor solution.
- Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the precursor solution does not contain surfactants and nitrogen-containing compounds.
- Comparative Examples 2-8 and Example 1 The difference between Comparative Examples 2-8 and Example 1 is that the precursor solution does not contain surfactant and the type or content of nitrogen-containing compound is different.
- Sample preparation according to the scheme of Example 4, implement steps (1) to (4), and use the product of step (6) as an observation sample. Use a glass knife to draw a straight line scratch on the side of the glass plate where the sample is observed, and then break the photovoltaic device along the scratch to expose the cross section.
- the observation sample includes a substrate 106, a first electrode 105 laminated on the substrate 106, a first charge transport layer 104 laminated on the first electrode 105, and a photoactive crystal material layer 103 laminated on the first charge transport layer 104 .
- the cross-sectional length of the photoactive crystal material layer 103 is 3.7 ⁇ m, and the total number of complete crystal grains in this area is four.
- the photoactive crystal material layer 103 includes a backlight side 113 and a backlight grain, the backlight grain is a grain exposed to the backlight side 113, and the backlight grain has a backlight crystal plane exposed to the backlight side 113;
- the R avg of the photo area is calculated by the following formula:
- R i is the flatness coefficient of the i-th backlight grain in the photo area, and R i is calculated by the following formula:
- d i is the width of the backlight crystal plane of the ith backlight grain (31,32,33) in the photo area;
- hi is the raised height of the backlight crystal plane of the ith backlight grain (31, 32, 33) in the photo area;
- step (6) obtained by the schemes of Examples 1-4 and Comparative Examples 1-8 were respectively subjected to scanning electron microscope observation, and the section of the photoactive crystal material layer with a length of 3.7 ⁇ m was collected, and calculated:
- the backlight side has an average flatness coefficient R avg .
- the energy conversion efficiency of the photovoltaic devices of Examples 1-4 is 20.1%-21.1%, significantly higher than that of Comparative Examples 1-8, which is only 16%-18.9%.
- the significantly improved energy conversion efficiency of the photovoltaic devices of Examples 1-4 is attributed to the fact that the photoactive crystal layer of the photovoltaic device simultaneously satisfies the following characteristics a) and b)
- the precursor solutions of Examples 1-4 contain surfactants and nitrogen-containing compounds in addition to the precursor compounds.
- the present application finds that it is difficult to obtain a photoactive crystal material layer with a ratio of p ⁇ 80 through the crystal grains 313 and an average flatness coefficient R avg ⁇ 75.
- Comparative Examples 1-8 without adding surfactants and nitrogen-containing compounds to the precursor solution, adding surfactants alone, or adding nitrogen-containing compounds alone, it is not possible to obtain a proportion of 313 through the grains p ⁇ 80 while being flat on average
- the photoactive crystal material layer with coefficient R avg ⁇ 75 cannot obtain the photoactive crystal material layer with improved light absorption properties.
- the present applicant unexpectedly found that a photoactive crystal material layer with a penetrating crystal grain 313 proportion p ⁇ 80 and an average flatness coefficient R avg ⁇ 75 can be successfully obtained by simultaneously adding a surfactant and a nitrogen-containing compound in the precursor solution.
- the light absorption properties of the photoactive crystal material layer are significantly improved, specifically shown in the proportion of the penetrating grains 313 of the active crystal material layer p ⁇ 80, and at the same time
- the average flatness coefficient R avg is less than or equal to 75, thereby obtaining a photovoltaic device with significantly improved energy conversion efficiency.
- the present application is not limited to the above-mentioned embodiments.
- the above-mentioned embodiments are merely examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same function and effect are included in the technical scope of the present application.
- various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .
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Abstract
Description
CAS | |
3-(N,N-二甲基十四烷基铵)丙烷磺酸盐 | 14933-09-6 |
十二烷基甜菜碱 | 683-10-3 |
月桂酰胺丙基氧化胺 | 61792-31-2 |
L-α-磷脂酰胆碱 | 8002-43-5 |
Claims (20)
- 一种光伏器件,其中,包括光活性晶体材料层(103),所述光活性晶体材料层(103)包括第一区域;在所述第一区域,所述光活性晶体材料层(103)包括贯穿晶粒(313),所述贯穿晶粒(313)为贯穿所述光活性晶体材料层(103)的晶粒,所述贯穿晶粒(313)的数量占所述光活性晶体材料层(103)在所述第一区域的总晶粒数量的百分比p≥80%,可选地,p≥90%;且在所述第一区域,所述光活性晶体材料层(103)包括背光侧(113)和背光晶粒(31,32,33),所述背光晶粒(31,32,33)为至少一个面暴露于所述背光侧(113)的晶粒,所述背光晶粒(31,32,33)的暴露于所述背光侧(113)的面为背光晶面;其中,所述背光侧(113)具有平均平坦系数R avg,R avg≤75,可选地10≤R avg≤70;其中,所述背光侧(113)的R avg通过下式计算:其中,R i为所述第一区域内第i个背光晶粒(31,32,33)的平坦系数,R i通过下式计算:R i=d i/h i其中,d i为所述第一区域内第i个背光晶粒(31,32,33)的背光晶面的宽度;其中,h i为所述第一区域内第i个背光晶粒(31,32,33)的背光晶面的凸起高度;其中,n为所述第一区域内全部背光晶粒(31,32,33)的数量。
- 根据权利要求1所述的光伏器件,其中,所述光活性晶体材料包括A/M/X晶体材料,所述A/M/X晶体材料具有以下通式:[A] a[M] b[X] c[M]包括一种或多种第一阳离子,所述第一阳离子包括金属离子、准金属离子、或其组合;[A]包括一种或多种第二阳离子;[X]包括一种或多种卤素阴离子;a为1至6,可选地,a为1、2、3、4、5或6;b为1至6,可选地,b为1、2、3、4、5或6;c为1至18,可选地,c为3、6、9、或18。
- 根据权利要求2所述的光伏器件,其具有以下一项或多项特征:(1)所述一种或多种第一阳离子选自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+或Te 4+;可选地,所述一种或多种第一阳离子选自Cu 2+、Pb 2+、Ge 2+或Sn 2+;(2)所述一种或多种第二阳离子选自Cs +、(NR 1R 2R 3R 4) +、(R 1R 2N=CR 3R 4) +、(R 1R 2N-C(R 5)=NR 3R 4) +或(R 1R 2N-C(NR 5R 6)=R 3R 4) +,其中,R 1,R 2,R 3,R 4,R 5和R 6各自独立地选自H、取代或非取代的C 1-20烷基或取代或非取代的芳基;可选地,所述一种或多种第二阳离子选自Cs +、(CH 3NH 3) +、(H 2N-C(H)=NH 2) +(3)所述卤素阴离子选自Cl -、Br -或I -。
- 根据权利要求2-3任一项所述的光伏器件,其中,所述A/M/X晶体材料包括FAPbI 3、FAPbBr 3、FAPbCl 3、FAPbF 3、FAPbBr xI 3-x、FAPbBr xCl 3-x、FAPbI xBr 3-x、FAPbI xCl 3-x、FAPbCl xBr 3-x、FAPbI 3-xCl x、CsPbI 3、CsPbBr 3、CsPbCl 3、CsPbF 3、CsPbBr xI 3-x、CsPbBr xCl 3-x、CsPbI xBr 3-x、CsPbI xCl 3-x、CsPbCl xBr 3-x、CsPbI 3-xCl x、FA 1-yCs yPbI 3、FA 1-yCs yPbBr 3、FA 1-yCs yPbCl 3、FA 1-yCs yPbF 3、FA 1-yCs yPbBr xI 3-x、FA 1-yCs yPbBr xCl 3-x、FA 1-yCs yPbI xBr 3-x、FA 1-yCs yPbI xCl 3-x、FA 1-yCs yPbCl xBr 3-x、FA 1-yCs yPbI 3-xCl x、或其组合;其中,x=0-3,y=0.01-0.25。
- 根据权利要求2-4任一项所述的光伏器件,其中,所述A/M/X晶体材料包括FAPbI 3、CsPbI 3、FA 1-yCs yPbI 3、或其组合,其中,y=0.01-0.25。
- 根据权利要求2-5任一项所述的光伏器件,其中,所述光活性晶体材料层的厚度为100nm以上,可选为100-1000nm,可选为300-700nm。
- 根据权利要求1-6任一项所述的光伏器件,其中,还包括第一电荷传输层(104)和第二电荷传输层(102),所述光活性晶体材料层(103)位于所述第一电荷传输层(104)和第二电荷传输层(102)之间;所述第一电荷传输层(104)和第二电荷传输层(102)分别为电子传输层和所述空穴传输层,或者所述第一电荷传输层(104)和第二电荷传输层(102)分别为空穴传输层和电子传输层。
- 根据权利要求1所述的光伏器件,其中,还包括第一电极(105)和第二电极(101),所述电子传输层、空穴传输层和光活性晶体材料层位于所述第一电极(105)和第二电极(101)之间;可选地,所述第一电极(105)包括透明导电氧化物;可选地,所述第二电极(101)包括金属。
- 一种制备A/M/X晶体材料的方法,所述A/M/X晶体材料具有以下通式:[A] a[M] b[X] c[M]包括一种或多种第一阳离子,所述第一阳离子包括金属离子、准金属离子、或其组合;[A]包括一种或多种第二阳离子;[X]包括一种或多种卤素阴离子;a为1至6,例如a=1;b为1至6,例如b=1;c为1至18,例如c=3;所述方法包括在基体上设置前体组合物,所述前体组合物包含以下组分:(a)至少一种前体化合物;(b)溶剂;(c)表面活性剂;以及(d)氨基类化合物。
- 根据权利要求9所述的方法,其包括以下一项或多项:(1)所述表面活性剂包括两性表面活性剂;(2)所述氨基化合物包括:腈胺类化合物、氨基酸类化合物(例如氨基磺酸类化合物)、肼类化合物、脲类化合物(例如尿素、脲醛、缩二脲、缩三脲)、胍类化合物、或其盐或水合物。
- 根据权利要求9-10任一项所述的方法,其中,所述表面活性剂包括十二烷基氨基丙酸盐、十二烷基乙氧基磺基甜菜碱、十二烷基二甲基羟丙基磺基甜菜碱、两性离子聚丙烯酰胺、十八烷基二羟乙基氧化胺、十四烷基二羟乙基氧化胺、月桂酰胺丙基氧化胺、十二烷基甜菜碱、L-α-磷酸脂胆碱、3-(N,N-二甲基十四烷基铵)丙烷磺酸盐、十二烷基苯磺酸盐、或其组合。
- 根据权利要求9-11任一项所述的方法,其中,所述氨基化合物包括:脲醛(C 3H 8N 2O 3)、异丁叉二脲(C 6H 14N 4O 2)、肼(H 4N 2)、胍(CH 3N 3O)、腈胺(CH 2N 2)、氨基磺酸(H 3NO 3S)、或其组合。
- 根据权利要求9-12任一项所述的方法,所述前体组合物包括第一溶剂和第二溶剂,所述第一溶剂的沸点为40-165℃;所述第二溶剂的沸点为170-250℃。
- 根据权利要求13所述的方法,其包括以下一项或多项:(1)所述第一溶剂选自N,N-二甲基甲酰胺(DMF)、2-甲氧基乙醇、乙腈(ACN)中的一种或多种;(2)所述第二溶剂选自二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、二苯亚砜(DPSO)中的一种或多种。(3)所述第一溶剂与第二溶剂的体积比为(4-10):1。
- 根据权利要求9-14任一项所述的方法,所述前体组合物包括第一前体化合物,所述第一前体化合物含有第一阳离子;以及第二前体化合物,所述第二前体化合物含有第二阳离子。
- 根据权利要求15所述的方法,其包括以下一项或多项;(1)所述第一前体化合物含有卤素阴离子;(2)所述第二前体化合物含有卤素阴离子。
- 根据权利要求9-16任一项所述的方法,其包括以下一项或多项;(1)所述第一化合物包括碘化铅(PbI 2)、溴化铅(PbBr 2)、或其组合;(2)所述第二化合物包括甲脒氢碘酸盐(FAI)、甲脒氢溴酸盐(FABr)、碘化铯(CsI)、溴化铯(CsBr)、或其组合。
- 根据权利要求9-17任一项所述的方法,还包括对设置在基体表面的前体组合物实施固化处理的步骤;可选地,所述固化处理包括:真空处理、风刀处理、红外光处理或其组合。
- 根据权利要求18所述的方法,还包括对固化处理的产物进行退火处理;可选地,所述退火处理的温度为100℃-170℃;可选地,所述退火处理的时间为5min-60min。
- 一种制备光伏器件的方法,所述光伏器件包括第一电极(105)和第二电极(101),位于所述第一电极(105)和第二电极(101)之间的第一电荷传输层(104)和第二电荷传输层(102),以及位于所述第一电荷传输层(104)和第二电荷传输层(102)之间的A/M/X晶体材料层;所述方法包括:提供表面设置有第一电荷传输层(104)的第一电极(105);按照权利要求9-19任一项所述的制备A/M/X晶体材料的方法,在所述第一电荷传输层(104)的表面形成所述A/M/X晶体材料层;在所述A/M/X晶体材料层上形成第二电荷传输层(102);在所述第二电荷传输层(102)上形成第二电极(101);其中,所述第一电荷传输层(104)和第二电荷传输层(102)分别为电子传输层和所述空穴传输层,或者所述第一电荷传输层(104)和第二电荷传输层(102)分别为空穴传输层和电子传输层。
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"Stabilizing perovskite-substrate interfaces for high-performance perovskite modules", SCIENCE, vol. 373, 2021, pages 902 |
See also references of EP4236651A4 |
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