Perovskite cell and preparation method thereof, laminated cell and photovoltaic module
By using the solution method on the electron transport layer of a perovskite battery, and forming a tin oxide layer with atomic layer deposition technology, the sputtering damage and island-like growth problems caused by magnetron sputtering are solved, and the anti-sputtering ability and electrical properties of the battery are improved.
Patent Information
- Application Number
- CN202510335123.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-20
- Publication Date
- 2025-06-10
AI Technical Summary
When perovskite batteries prepare transparent conductive oxide electrode layers by magnetron sputtering, they are prone to damage to the electron transport layer and the perovskite layer due to the damage of high-energy sputtering particles. The atomic layer deposition method leads to island growth and nucleation delays under undesirable self-limiting surface reactions, affecting the continuity and energy level matching of the film.
A dielectric layer is prepared on the electron transport layer by solution method. The dielectric layer materials include tungsten oxide, zinc oxide and aluminum-doped zinc oxide. The solvent contains hydroxyl groups to promote the reaction of the tin source precursor and the dielectric layer material, form an intermediate to avoid island growth, and form a tin oxide layer by depositing atomic layer on the side of the dielectric layer away from the electron transport layer.
The film quality of the tin oxide layer is improved, the anti-sputtering damage ability of the electron transport layer is enhanced, the battery performance and open circuit voltage are improved, and the energy level matching between the tin oxide layer and the electron transport layer is promoted.
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Figure CN120129440A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of photovoltaics, and in particular to a perovskite battery and a preparation method thereof, a tandem battery, and a photovoltaic module. Background Art
[0002] Perovskite solar cells (PSCs) are promising for use as top sub-cells in tandem solar cells (e.g., perovskite and silicon tandem solar cells) in building integrated photovoltaics (BIPV). To facilitate the passage of light, a transparent conductive oxide (TCO) electrode layer needs to be provided at the top of the cell. Magnetron sputtering is the most widely used method for preparing the transparent conductive oxide (TCO) electrode layer, and the transparent conductive oxide prepared by magnetron sputtering has low resistivity and broadband transparency. However, perovskite (PVK) and the electron transport layer (such as C60, PCBM, etc.) are soft materials and are easily irreversibly damaged by high-energy sputtering particles during the process of preparing the transparent conductive oxide at the top of the cell by magnetron sputtering. Therefore, an indium tin oxide layer is often prepared by atomic layer deposition (ALD) on the electron transport layer as a buffer layer to avoid the damage of magnetron sputtering to the electron transport layer and the perovskite layer.
[0003] However, research shows that ALD relies on self-limiting surface reactions closely related to surface groups on the deposition substrate. According to research, when the substrate does not react with the ALD reactants, the material prepared by ALD becomes island growth, which is also called substrate-inhibited growth. However, the material layer prepared by the island growth mode is not conducive to the continuous growth of the thin film. In the island growth mode, the ALD process in the nucleation stage is not ideal, which prevents layer-by-layer growth and results in nucleation delay.
[0004] In addition, SnO 2 also has a problem of poor energy level matching with common electron transport materials. Therefore, using the atomic layer deposition method to obtain an island structure of SnO 2 on a non-reactive substrate such as fullerenes and their derivatives not only has limited anti-sputtering damage ability but also limits the hole-blocking transport ability. Summary of the Invention
[0005] Based on this, it is necessary to provide a perovskite battery and a preparation method thereof, a tandem battery, and a photovoltaic module that can improve the anti-sputtering damage ability of the electron transport layer.
[0006] An embodiment of the present application provides a method for preparing a perovskite battery, including the following steps:
[0007] Providing a substrate, and forming a perovskite layer on the substrate;
[0008] Forming an electron transport layer on a side of the perovskite layer facing away from the substrate;
[0009] Using a solution method, a dielectric layer is formed on the side of the electron transport layer facing away from the perovskite layer. The solvent used in the solution method contains hydroxyl groups. The material of the dielectric layer includes one or more of tungsten oxide, zinc oxide, and aluminum-doped zinc oxide;
[0010] Using atomic layer deposition, a tin oxide layer is formed on the surface of the dielectric layer facing away from the electron transport layer.
[0011] In one embodiment, the material of the electron transport layer includes one or two of C60 and fullerene derivatives.
[0012] In one embodiment, the step of forming the tin oxide layer by atomic layer deposition includes: alternately introducing a tin source precursor and an oxygen source precursor.
[0013] In one embodiment, the solvent for forming the dielectric layer by the solution method includes one or more of isopropyl alcohol, ethanol, n-propanol, methanol, 1-propanol, and 2-butanol.
[0014] In one embodiment, the particle size of the material of the dielectric layer is 5 nm to 50 nm.
[0015] In one embodiment, the steps of preparing the dielectric layer by the solution method include: spin-coating a raw material solution on the side of the electron transport layer facing away from the perovskite layer, the raw material solution including the material of the dielectric layer and the solvent, and annealing.
[0016] In one embodiment, the annealing temperature is 80 °C to 120 °C, and the annealing time is 5 minutes to 15 minutes.
[0017] This application also provides a perovskite battery prepared according to the above preparation method.
[0018] Furthermore, this application also provides a tandem battery including the perovskite battery as described above.
[0019] Even further, this application also provides a photovoltaic module, and its power supply device includes the perovskite battery as described above or the tandem battery as described above.
[0020] The preparation method of the perovskite battery provided by one embodiment of this application, by preparing a dielectric layer on the electron transport layer using the solution method, since the solvent used contains hydroxyl groups, a certain amount of hydroxyl groups will exist on the surface of the material of the specific dielectric layer, which can react with the tin source precursor to form an intermediate, avoiding island growth, improving the film quality of the tin oxide prepared by atomic layer deposition, enhancing the anti-sputtering damage ability of the electron transport layer, and improving the battery performance.
[0021] Furthermore, the introduction of the dielectric layer makes the energy levels of the tin oxide layer and the electron transport layer more matched, which is more conducive to charge transport and can increase the open circuit voltage of the battery containing this electron transport layer. Description of the Drawings
[0022] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.
[0023] Figure 1 The perovskite battery structure provided by the present application.
[0024] Description of the Reference Numerals:
[0025] 10: Perovskite battery; 110: First conductive layer; 120: Hole transport layer; 130: Perovskite layer; 140: Electron transport layer; 150: Dielectric layer; 160: Tin oxide layer; 170: Second conductive layer. Specific Embodiments
[0026] The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive. Of course, they are only examples and are not intended to limit the present application. In addition, the present application may repeat reference numerals and / or letters in different examples. This repetition is for the purpose of simplicity and clarity and does not itself indicate the relationship between the various embodiments and / or settings discussed.
[0027] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features. In the description of the application, "a plurality" means at least two, such as two, three, etc., unless otherwise specifically defined. In the description of the present application, "several" means at least one, such as one, two, etc., unless otherwise specifically defined.
[0028] Unless otherwise specified, all percentages, fractions, and ratios are calculated based on the total mass of the composition of the present application. Unless otherwise specified, all masses of the listed components are given as the content of the active substance, and therefore they do not include solvents or by-products that may be contained in commercially available materials. The term "mass percentage content" in this article can be represented by the symbol "%".
[0029] The purpose of the terms used herein is only to describe specific embodiments and is not a limitation of the present application. As used herein, the singular forms "a", "an" and "the" are also intended to include the plural forms unless the context clearly dictates otherwise. It should also be understood that the terms "comprising" and / or "including", when used in this specification, identify the presence of the described features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups. As used herein, the term "and / or" includes any and all combinations of the related listed items.
[0030] Unless stated to the contrary, the singular form of a term may include the plural form and should not be construed as being one in number.
[0031] As used herein, "comprising", "including", "containing", "having" or other variants are intended to cover non-closed inclusion, and no distinction is made between these terms. The term "including" means that other steps and components can be added without affecting the final result. The term "including" also includes the terms "consisting of" and "consisting essentially of". The compositions and methods / processes of the present application comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps or limitations described herein. No distinction is made between the terms "efficacy", "performance", "effect", and "function" herein.
[0032] The terms "preferably", "more preferably", etc. in the present application refer to embodiments of the present application that can provide certain beneficial effects in certain cases. However, in the same or other cases, other embodiments may also be preferred. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not available, nor is it intended to exclude other embodiments from the scope of the present application.
[0033] When a numerical range is disclosed herein, the above range is considered continuous and includes the minimum and maximum values of the range, as well as every value therebetween. Further, when the range refers to integers, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.
[0034] The present application also provides a method for preparing a perovskite solar cell, comprising the following steps:
[0035] Providing a substrate and forming a perovskite layer on the substrate;
[0036] Forming an electron transport layer on the side of the perovskite layer facing away from the substrate;
[0037] By using a solution method, a dielectric layer is formed on the side of the electron transport layer away from the perovskite layer. The solvent used in the solution method contains hydroxyl groups, and the material of the dielectric layer includes one or more of tungsten oxide, zinc oxide, and aluminum-doped zinc oxide;
[0038] By using atomic layer deposition, a tin oxide layer is formed on the surface of the dielectric layer away from the electron transport layer.
[0039] In the preparation method of the perovskite battery provided by an embodiment of the present application, by using a solution method to prepare a dielectric layer on the electron transport layer, since the solvent used contains hydroxyl groups, a certain amount of hydroxyl groups will exist on the surface of a specific dielectric layer material, which can react with the tin source precursor to form an intermediate, avoiding island growth, improving the film quality of the tin oxide prepared by atomic layer deposition, enhancing the anti-sputtering damage ability of the electron transport layer, and improving the battery performance.
[0040] Furthermore, the introduction of the dielectric layer makes the energy levels of the tin oxide layer and the electron transport layer more matched, which is more conducive to charge transport and can increase the open-circuit voltage of the battery containing this electron transport layer.
[0041] In a specific example, the perovskite battery further includes forming a hole transport layer on the side of the perovskite layer close to the substrate.
[0042] In a specific example, the perovskite battery further includes forming a first conductive layer on the side of the hole transport layer away from the perovskite layer.
[0043] It can be understood that the substrate is a transparent substrate, and a first conductive layer, a hole transport layer, a perovskite layer, an electron transport layer, a dielectric layer, a tin oxide layer, and a second conductive layer are sequentially prepared on the above transparent substrate.
[0044] Furthermore, the material of the first conductive layer is deposited on the above transparent substrate to prepare the first conductive layer. Specifically, the method for preparing the first conductive layer can be, but is not limited to, magnetron sputtering.
[0045] Even further, a hole transport layer is formed on the above first conductive layer. The method for forming the hole transport layer can be, but is not limited to, one or more of spin coating, blade coating, evaporation coating, printing, spraying, spray pyrolysis, and slot die coating.
[0046] The method for forming the perovskite layer on the above hole transport layer includes, but is not limited to, one or more of spin coating, blade coating, evaporation coating, printing, spraying, spray pyrolysis, and slot die coating.
[0047] In a specific example, an electron transport layer is formed on the above-mentioned perovskite layer. The specific method for forming the above-mentioned electron transport layer may but is not limited to physical vapor deposition. Specifically, the method of physical vapor deposition may but is not limited to thermal evaporation. The material of the electron transport layer includes one or both of C60 and fullerene derivatives.
[0048] In a specific example, when forming the dielectric layer by the solution method, the solvent includes one or more of isopropyl alcohol, ethanol, n-propanol, methanol, 1-propanol, and 2-butanol.
[0049] In a specific example, the steps of preparing the dielectric layer by the solution method include: spin-coating a raw material solution on the side of the electron transport layer facing away from the perovskite layer. The raw material solution includes the material of the dielectric layer and a solvent, and annealing.
[0050] Furthermore, the raw material solution includes the material of the dielectric layer and the solvent in a ratio of (0.01~1) g : (10~50) ml.
[0051] In a specific example, the above solution method may but is not limited to coating, doctor blading, or spin coating. Further, the solution method is spin coating, and the spin coating speed is 2000 rmp~4000 rmp. Specifically, the spin coating speed may but is not limited to 2000 rmp, 2200 rmp, 2400 rmp, 2600 rmp, 2800 rmp, 3000 rmp, 3200 rmp, 3400 rmp, 3600 rmp, 3800 rmp, or 4000 rmp. The spin coating time is 10 s~60 s, and the spin coating time may but is not limited to 10 s, 20 s, 30 s, 40 s, 50 s, or 60 s.
[0052] In a specific example, the particle size of the material of the dielectric layer is 5 nm~50 nm. It can be understood that the particle size of the material of the dielectric layer may but is not limited to 5 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm. It can be understood that the material of the dielectric layer is zinc oxide and aluminum-doped zinc oxide, the particle size of the material of the dielectric layer is 8 nm~16 nm, the material of the dielectric layer is tungsten oxide, and the particle size of the material of the dielectric layer is further 12 nm~16 nm. It can be understood that the nanoparticle solution has polydispersity, and the particles will overlap and compress during the spin coating and crystallization process. By controlling the spin coating speed, temperature, and solution concentration, its thickness can reach the expected value.
[0053] In a specific example, the annealing temperature is 80°C~120°C, and the annealing time is 5 minutes~15 minutes.
[0054] The annealing temperature can be, but is not limited to, 80°C, 90°C, 100°C, 110°C or 120°C, and the annealing time can be, but is not limited to, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes.
[0055] In a specific example, the tin oxide layer is prepared by atomic layer deposition on the above-mentioned dielectric layer. The steps of forming the tin oxide layer by atomic layer include: alternately introducing a tin source precursor and an oxygen source precursor.
[0056] The above-mentioned tin source precursor can be, but is not limited to, one or more of tin tetrakis(dimethylamino), diethyltin, stannous dichloride, and stannic chloride.
[0057] In a specific example, the second conductive layer is prepared by physical vapor deposition on the above-mentioned tin oxide layer.
[0058] As Figure 1 shown is the structure of the perovskite solar cell 10 provided by the present application, including a first conductive layer 110, a hole transport layer 120, a perovskite layer 130, an electron transport layer 140, a dielectric layer 150, a tin oxide layer 160, and a second conductive layer 170 stacked in sequence.
[0059] In a specific example, the perovskite solar cell 10 further includes a hole transport layer 120 provided on the second surface of the perovskite layer 130. Further, the material of the hole transport layer 120 can be, but is not limited to, including self-assembled monolayer materials including [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), and [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid (MeO-4PACz) one or more of them. The thickness of the hole transport layer 120 is 1 nm to 200 nm. Further, the thickness of the hole transport layer 120 is 1 nm to 50 nm. Specifically, the thickness of the hole transport layer 120 can be, but is not limited to, 1 nm, 3 nm, 5 nm, 7 nm, 11 nm, 13 nm, 15 nm, 7 nm, 19 nm, 21 nm, 23 nm, 25 nm, 27 nm, 29 nm, 31 nm, 33 nm, 35 nm, 37 nm, 39 nm, 41 nm, 43 nm, 45 nm, 47 nm or 50 nm.
[0060] Further, the perovskite cell 10 further includes a first conductive layer 110 disposed on the surface of the hole transport layer 120 facing away from the perovskite layer 130. Optionally, the first conductive layer 110 can be, but is not limited to, one or more of indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), fluorine-doped tin oxide (FTO), indium-doped cadmium oxide (ICO), aluminum zinc oxide (AZO), and boron-doped zinc oxide layer (BZO).
[0061] The thickness of the first conductive layer 110 is 10 nm to 1000 nm. Specifically, the thickness of the first conductive layer 110 can be, but is not limited to, 10 nm, 60 nm, 120 nm, 180 nm, 240 nm, 300 nm, 360 nm, 420 nm, 480 nm, 540 nm, 6000 nm, 660 nm, 720 nm, 780 nm, 840 nm, 900 nm, 960 nm, or 1000 nm.
[0062] In a specific example, the chemical formula of the perovskite layer 130 material is ABX 3 , where A is a monovalent cation. Specifically, A includes, but is not limited to, cesium ion (Cs + ), rubidium ion (Rb + ), methylammonium ion (CH 3 NH 3 , MA + ), and formamidinium ion (CH 2 (NH 2 ) 2 + , FA + ), one or more of them; B is a divalent cation, including, but not limited to, lead ion (Pb 2+ ), copper ion (Cu 2+ ), zinc ion (Zn 2+ ), gallium ion (Ga 2+ ), tin ion (Sn 2+ ), and calcium ion (Ca 2+ ), one or more of them; X is a monovalent anion, including, but not limited to, iodine (I - ), bromine (Br - ), chlorine (Cl - ), fluorine (F - ), and thiocyanate ion (SCN -) or more of those in. The thickness of the perovskite layer 130 is 10 nm to 100 μm. Further, the thickness of the perovskite layer 130 is 100 nm to 10 μm. The thickness of the perovskite layer 130 can be, but is not limited to, 100 nm, 300 nm, 500 nm, 800 nm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 10 μm.
[0063] In a specific example, the bandgap of the perovskite layer 130 is 0.9 eV to 3 eV. Further, the bandgap of the perovskite layer 130 can be, but is not limited to, 0.9 eV, 1 eV, 1.1 eV, 1.2 eV, 1.3 eV, 1.4 eV, 1.5 eV, 1.6 eV, 1.7 eV, 1.8 eV, 1.9 eV, 2 eV, 2.1 eV, 2.2 eV, 2.3 eV, 2.4 eV, 2.5 eV, 2.6 eV, 2.7 eV, 2.8 eV, 2.9 eV, or 3 eV.
[0064] In a specific example, the material of the electron transport layer 140 includes one or two of C60 and fullerene derivatives. The fullerene derivatives are specifically [6,6]-phenyl-C61-butyric acid methyl ester and [6,6]-phenyl-C71-butyric acid methyl ester (PCBM). Further, the thickness of the electron transport layer is 1 nm to 100 μm. Understandably, the thickness of the electron transport layer is 1 nm to 100 nm. Specifically, the thickness of the electron transport layer can be, but is not limited to, 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.
[0065] In a specific example, the thickness of the dielectric layer 150 is 1 nm to 500 nm. Further, the thickness of the dielectric layer 150 is 1 nm to 50 nm. Specifically, the thickness of the dielectric layer 150 can be, but is not limited to, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm.
[0066] Further, the thickness of the tin oxide layer 160 is 1 nm to 500 nm. Further still, the thickness of the tin oxide layer 160 is 1 nm to 50 nm. Specifically, the thickness of the tin oxide layer 160 can be, but is not limited to, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm.
[0067] In a specific example, the perovskite cell 10 further includes a second conductive layer 170 disposed on the tin oxide layer 160. Optionally, the second conductive layer 170 includes one or both of a transparent conductive layer and a metal conductive layer. Specifically, the second conductive layer 170 includes a transparent conductive layer and a metal conductive layer, wherein the metal conductive layer does not completely cover the surface of the transparent conductive layer.
[0068] Optionally, the material of the transparent conductive layer may include, but is not limited to, one or more of indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), fluorine-doped tin oxide (FTO), indium-doped cadmium oxide (ICO), aluminum zinc oxide (AZO), and boron-doped zinc oxide layer (BZO). The material of the metal conductive layer may include, but is not limited to, one or more of gold (Au), silver (Ag), aluminum (Al), and copper (Cu). The thickness of the transparent conductive layer is 10 nm to 1000 nm. Specifically, the thickness of the transparent conductive layer may be, but is not limited to, 10 nm, 60 nm, 100 nm, 120 nm, 180 nm, 240 nm, 300 nm, 360 nm, 420 nm, 480 nm, 540 nm, 600 nm, 660 nm, 720 nm, 780 nm, 840 nm, 900 nm, 960 nm, or 1000 nm. The thickness of the metal conductive layer is 100 nm to 500 nm. Specifically, the thickness of the metal conductive layer may be, but is not limited to, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm.
[0069] Furthermore, the present application also provides a tandem cell, including the perovskite cell 10 as described above.
[0070] Even further, the present application also provides a photovoltaic module, and its power supply device includes the perovskite cell 10 as described above or the tandem cell as described above.
[0071] The following further elaborates on the present application with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application. For the experimental methods without specific conditions in the following embodiments, the guidance given in the present application is preferably referred to, and it can also be in accordance with the experimental manuals or conventional conditions in the art, or in accordance with the conditions recommended by the manufacturers, or referring to the experimental methods known in the art.
[0072] In the following specific embodiments, regarding the measurement parameters of raw material components, without special instructions, there may be slight deviations within the weighing accuracy range. Regarding temperature and time parameters, acceptable deviations caused by instrument test accuracy or operation accuracy are allowed. "Normal temperature" refers to 25°C; "atmospheric pressure" refers to 100 KPa or 101 KPa. Tungsten oxide nanoparticle ink was purchased from Sigma-Aldrich, with the product number 793353, zinc oxide was purchased from Sigma-Aldrich, with the product number 808253, aluminum-doped zinc oxide was purchased from Sigma-Aldrich, with the product number 808237, and aluminum oxide was purchased from Sigma-Aldrich, with the product number 702129.
[0073] Example 1
[0074] This example provides a method for preparing a perovskite solar cell, including the following steps:
[0075] (1) Provide an ITO glass sheet with a glass thickness of 0.7 μm and an ITO layer thickness of 120 nm;
[0076] (2) Deposit a hole transport layer of 2PACz with a thickness of 5 nm on the ITO glass sheet by spin coating;
[0077] (3) Deposit a perovskite layer Cs 0.05 (FA 0.8 MA 0.2 ) 0.95 Pb(I 0.8 Br 0.2 ) 3 , with a bandgap of approximately 1.68 eV and a thickness of 500 nm;
[0078] (4) Prepare a C60 layer with a thickness of 20 nm by thermal evaporation;
[0079] (5) Prepare a WO 3 layer: Take 2.5 wt% of WO 3 nanoparticle ink; Dissolve the WO 3 nanoparticle ink in IPA solvent at a volume ratio of 3:20, stir until completely dissolved to obtain a solution, and filter the solution with a 0.22 μm needle filter to obtain a filtrate; In the glove box, use a pipette to take an appropriate amount of the filtrate and drop it on the C60 layer, and spin coat at a rotation speed of 3000 rmp for 30 s to obtain a thickness of 10 nm; Anneal on a hot plate at 100°C for 10 minutes;
[0080] (6) Alternately introduce a tin source gas and an oxygen source gas. Specifically, introduce tetra(dimethylamino)tin (TDMA-Sn) as the tin source and react with the hydroxyl groups on the surface of the tungsten oxide layer to form an intermediate product Wo-O-Sn(NMe 2 )3 , introduce N 2 Purge and remove the excessive tin source gas and by-products, and then introduce water vapor as the oxygen source gas to react with the intermediate product to generate SnO 2 , and finally introduce N 2 Purge and remove the excessive tin source gas, oxygen source gas and by-products, and prepare SnO by atomic layer deposition 2 , with a thickness of 15 nm;
[0081] (7) Prepare the ITO layer by sputtering method, with a thickness of 100 nm;
[0082] (8) Prepare the Ag metal grid line layer by thermal evaporation method, with a thickness of 200 nm, and complete the preparation of the battery.
[0083] Example 2
[0084] The steps of Example 2 are basically the same as those of Example 1, except that in step (4), the electron transport layer prepared by thermal evaporation is different. In step (4), the PCBM layer is prepared by spin coating method; the PCBM solution (CB, 15 mg / mL) is spin coated at a speed of 2000 rpm for 30 s.
[0085] Example 3
[0086] The steps of Example 3 are basically the same as those of Example 1, except that in step (5), the annealing temperature is different, and it is set to anneal on a hot plate at 80 °C for 10 minutes.
[0087] Example 4
[0088] The steps of Example 4 are basically the same as those of Example 1, except that in step (5), the annealing temperature is different, and it is set to anneal on a hot plate at 120 °C for 12 minutes.
[0089] Example 5
[0090] The steps of Example 5 are basically the same as those of Example 1, except that in step (5), zinc oxide is spin coated.
[0091] Example 6
[0092] The steps of Example 6 are basically the same as those of Example 1, except that in step (5), aluminum-doped zinc oxide is spin coated.
[0093] Comparative Example 1
[0094] The steps of Comparative Example 1 are basically the same as those of Example 1, except that the tungsten oxide layer is not provided.
[0095] Comparative Example 2
[0096] The steps of Comparative Example 2 are basically the same as those of Example 1, except that in step (5), alumina is spin-coated.
[0097] Comparative Example 3
[0098] The steps of Comparative Example 3 are basically the same as those of Example 1, except that the method for preparing tungsten oxide is different, and it is set to prepare a tungsten oxide thin film by thermal evaporation.
[0099] The perovskite solar cells prepared in the above examples and comparative examples were tested under the conditions of 25 °C, AM 1.5G, and 1000 W / m 2 The electrical properties of the perovskite solar cells prepared in the above examples and comparative examples are shown in Table 1 below.
[0100] Table 1
[0101]
[0102] In Comparative Example 1, no dielectric layer was set, and the tin source in tin oxide did not react with the material of the electron transport layer, resulting in island-like growth of the tin oxide layer, poor film continuity, a decrease in the electrical properties of the solar cell, and a significant decrease in the fill factor. In Comparative Example 2, when it was replaced with other oxides, the electrical properties of the solar cell decreased, and the photoelectric conversion efficiency and fill factor decreased significantly. In Comparative Example 3, since the solution method was not used for preparation, due to fewer surface hydroxyl groups, it could not react sufficiently with the tin source, and not enough reaction sites were formed, resulting in island-like growth of tin oxide, and poor quality of the tin oxide thin film, which caused a decrease in the electrical properties of the solar cell, and a significant decrease in the photoelectric conversion efficiency and fill factor.
[0103] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.
[0104] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.
[0105] The above-described embodiments merely represent several implementation manners of the present application, facilitating a specific and detailed understanding of the technical solution of the present application. However, it should not be construed as a limitation on the scope of patent protection of the application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can be made, and these all fall within the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning, or limited experiments based on the technical solution provided by the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the content of the appended claims, and the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a perovskite battery, characterized in that: The following steps are involved: providing a substrate on which a perovskite layer is formed; forming an electron transport layer on a side of the perovskite layer facing away from the substrate; A solution method is used to form a dielectric layer on the side of the electron transport layer away from the perovskite layer, wherein the solvent used in the solution method contains hydroxyl groups, and the material of the dielectric layer includes one or more of tungsten oxide, zinc oxide, and aluminum-doped zinc oxide; Atomic layer deposition is used to form a tin oxide layer on a surface of the dielectric layer on a side away from the electron transport layer.
2. The preparation method according to claim 1, characterized in that The material of the electron transport layer includes one or two of C60 and fullerene derivatives.
3. The preparation method according to claim 1, characterized in that: The step of forming the tin oxide layer by atomic layer includes: alternately introducing a tin source precursor and an oxygen source precursor.
4. The preparation method according to claim 1, characterized in that: The solvent in the dielectric layer formed by a solution method includes one or more of isopropanol, ethanol, n-propanol, methanol, 1-propanol and 2-butanol.
5. The preparation method according to claim 1, characterized in that: The particle size of the material of the dielectric layer is 5nm~50nm.
6. The preparation method according to any one of claims 1 to 5, characterized in that: The step of preparing the dielectric layer by solution method comprises: spin coating a raw material solution on a side of the electron transport layer away from the perovskite layer, the raw material solution comprising the material of the dielectric layer and the solvent, and annealing.
7. The preparation method according to claim 6, characterized in that: The annealing temperature is 80°C to 120°C, and the annealing time is 5 minutes to 15 minutes.
8. A perovskite battery, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 7.
9. A laminated battery, characterized in that: Comprising the perovskite cell as claimed in claim 8.
10. A photovoltaic module, characterized in that: The power supply device thereof comprises the perovskite battery as claimed in claim 8 or the stacked battery as claimed in claim 9.