WO2024060806A1 - 二氧化锡薄膜及其制备方法和应用 - Google Patents

二氧化锡薄膜及其制备方法和应用 Download PDF

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WO2024060806A1
WO2024060806A1 PCT/CN2023/107021 CN2023107021W WO2024060806A1 WO 2024060806 A1 WO2024060806 A1 WO 2024060806A1 CN 2023107021 W CN2023107021 W CN 2023107021W WO 2024060806 A1 WO2024060806 A1 WO 2024060806A1
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oxygen source
tin
source
perovskite
oxygen
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PCT/CN2023/107021
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French (fr)
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张富
丁蕾
何永才
何博
杨莹
刘童
张华�
李勃超
顾小兵
徐希翔
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隆基绿能科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application belongs to the technical field of solar cells, and specifically relates to a tin dioxide film and a preparation method and application thereof.
  • the perovskite cell/silicon-based heterojunction double-terminal stacked cell increases the absorption range of the solar spectrum and can theoretically obtain a photoelectric conversion efficiency greater than 30% (>silicon cell limit efficiency 29.4%).
  • the highest efficiency certified so far is 29.8%, further confirming the great potential of perovskite/silicon stacked solar cells in breaking through the efficiency limit of silicon cells. Therefore, it is considered to be the mainstream product of high-efficiency solar cells in the future.
  • it is also particularly important to prepare high-quality electron transport layers.
  • C60 and tin dioxide (SnO 2 ) are usually used together as electron transport layers.
  • tin dioxide also acts as a buffer layer.
  • ALD atomic layer deposition
  • TDMASn tetrakis(dimethylamino)tin
  • this application provides a tin dioxide electron transport layer and a preparation method thereof.
  • this application involves the following aspects:
  • a method for preparing a tin dioxide film including the following steps:
  • a tin dioxide film is deposited on the substrate through atomic layer deposition technology
  • the deposition process includes the step of using a first oxygen source and a second oxygen source alternately as the oxygen source to react with the tin metal organic source;
  • the first oxygen source is selected from one or both of water and hydrogen peroxide
  • the second oxygen source is selected from ozone, oxygen, nitric oxide, nitrogen dioxide, plasma-activated ozone, plasma-activated oxygen, plasma-activated nitric oxide, or plasma-activated nitrogen dioxide.
  • the first oxygen source is water
  • the second oxygen source is ozone
  • the tin metal organic source is selected from one or more of alkyl tin, tin alkoxide salt, Sn (NR1R2) 4 , wherein R1 and R2 are each independently selected from a C1-C4 alkyl group, Tetrakis(dimethylamino)tin is preferred.
  • the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source includes a plurality of the following cycles:
  • the first oxygen source and the second oxygen source are used alternately between two adjacent cycles.
  • the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source it also includes using only the first oxygen source and the tin metal organic source.
  • the number of cycles is 50-500.
  • the inert gas is nitrogen.
  • the nitrogen purging time is 5-15 s, and the nitrogen flow rate is 20-90 sccm.
  • the tin metal organic source is introduced through an inert gas as a carrier gas, with a flow rate of 20-90sccm and an introduction time of 0.1-2s;
  • the first oxygen source is introduced through an inert gas as a carrier gas, with a flow rate of 20-90sccm and an introduction time of 0.1-1.5s;
  • the second oxygen source is introduced directly, with a flow rate of 20-90sccm and an introduction time of 0.1-1.5s.
  • the thickness of the tin dioxide film is 5-50 nm, preferably 10-20 nm.
  • the substrate is one of C60, C70, and PCBM.
  • a tin dioxide electron transport layer is prepared by any one of the above preparation methods.
  • a tin dioxide buffer layer is prepared by any one of the above preparation methods.
  • a perovskite solar cell includes the above-mentioned tin dioxide electron transport layer and/or tin dioxide buffer layer.
  • the perovskite solar cell includes a hole transport layer, a perovskite photoactive layer, an electrical insulation layer, a first electron transport layer and a second electron transport layer stacked in sequence, wherein the first electron transport layer
  • the transport layer is the tin dioxide electron transport layer.
  • the second electron transport layer is one of C60, C70, and PCBM.
  • the perovskite solar cell is selected from one of an inorganic perovskite cell, an organic perovskite cell, and an organic-inorganic hybrid perovskite cell.
  • a perovskite tandem solar cell comprises a crystalline silicon bottom cell, an intermediate composite layer and a perovskite top cell which are stacked in sequence, wherein the perovskite top cell is any one of the above-mentioned perovskite solar cells.
  • the crystalline silicon bottom battery is selected from one of PERC battery, TOPCon battery, HJT battery, IBC battery and HBC battery.
  • This application changes the defects of the original single oxygen source by using the second oxygen source plus the first oxygen source to alternately provide the oxygen source, and uses the strong oxidizing property of the second oxygen source to reduce the defects in the prepared tin oxide crystal structure. Obtain a more perfect crystal structure, improve film formation quality, and ultimately improve the filling factor and electron transmission capability of the device.
  • Figure 1 is a structural diagram of a perovskite/silicon stacked solar cell at both ends;
  • Figure 2 shows the reflection properties of SnO2 thin films under various oxygen source preparation conditions.
  • atomic layer deposition is a method of forming a deposited film by alternately pulse-pulsing a gas phase precursor into a reactor and chemically adsorbing and reacting on the deposition substrate. It is a method that can deposit substances into a single-atom film. A method of plating layer by layer on the surface of a substrate. In the atomic layer deposition process, the chemical reaction of a new layer of atomic film is directly related to the previous layer. This way, only one layer of atoms is deposited in each reaction.
  • a conventional ALD apparatus may include a reactor chamber, a substrate holder, a gas flow system including gas inlets for providing precursors and reactants to the substrate surface, and an exhaust system for removing used gases.
  • the growth mechanism relies on the adsorption of precursors on the active sites of the substrate, and conditions are preferably maintained such that no more than a monolayer is formed on the substrate, thus self-terminating the process.
  • Exposure of the substrate to the first precursor is typically followed by a purge stage or other removal process (e.g., evacuating or "pumping down") in which any excess of the first precursor as well as any reaction by-products are removed from the reaction chamber .
  • a second reactant or precursor is then introduced into the reaction chamber where it reacts with the first precursor, and this reaction produces the desired film on the substrate.
  • the reaction is terminated when all available first precursor species adsorbed on the substrate have reacted with the second precursor.
  • a second purge or other removal stage is then performed, which removes any remaining second precursor and possible reaction by-products in the reaction chamber. This cycle can be repeated to grow the film to the desired thickness.
  • ALD atomic layer deposition
  • substrate may refer to any underlying material or materials upon which devices, circuits, or films may be formed or upon which devices, circuits, or films may be formed.
  • a “film” may refer to any continuous or discontinuous structure, material or materials deposited by the methods disclosed herein.
  • a “membrane” may include a 2D material, nanorods, nanotubes, nanolaminates or nanoparticles, or even part or all of a molecular layer or part or all of Atomic layers or clusters of atoms and/or molecules.
  • a “film” may also include one or more materials or layers that have pinholes, but are still at least partially continuous.
  • a "metalorganic source” refers to an organic compound containing metal
  • a tin metalorganic source refers to an organic compound containing tin
  • an "electron transport layer” refers to a layer through which electrons can flow easily and which typically reflects holes (holes are the absence of electrons that are moveable carriers of positive charge in semiconductors).
  • buffer layer refers to a layer that plays an interface adjustment role. It can be located between the electron transmission layer and the cathode or between the electron transmission and the light absorption layer. On the one hand, it can make the energy levels on the electron transmission path more consistent. It accelerates electron extraction and transmission, passivates interface defect states, and reduces interface recombination current; on the other hand, it can also protect the perovskite absorption layer, thereby improving battery stability.
  • this application provides a preparation method of tin dioxide (SnO 2 ) thin film, which includes the following steps:
  • a tin dioxide film is deposited on the substrate through atomic layer deposition technology
  • the deposition process includes the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source.
  • the first oxygen source is selected from one or both of water and hydrogen peroxide. That is, the first oxygen source can be one or two, for example, it can be water or hydrogen peroxide, or water and hydrogen peroxide can be used simultaneously or separately.
  • the second oxygen source is selected from one of ozone, oxygen, nitric oxide, nitrogen dioxide, plasma-activated ozone, plasma-activated oxygen, plasma-activated nitric oxide, and plasma-activated nitrogen dioxide.
  • the second oxygen source may be one, two, three or more.
  • the first oxygen source and the second oxygen source can be combined in any way.
  • the first oxygen source is water
  • the second oxygen source is ozone
  • the first oxygen source is hydrogen peroxide
  • the second oxygen source is ozone
  • the first oxygen source is water
  • the second oxygen source is oxygen
  • the tin metal organic source is selected from one or more of alkyltin, tin alkoxide salt, and Sn(NR1R2) 4 , wherein R1 and R2 are each independently selected from a C1-C4 alkyl group.
  • the tin metal organic source is Sn(NR1R2) 4 , where R1 and R2 are each independently selected from C1-C4 alkyl groups.
  • the tin metal organic source is tetrakis(dimethylamino)tin (TDMASn).
  • the first oxygen source is water
  • the second oxygen source is ozone
  • the tin metal organic source is tetrakis(dimethylamino)tin (TDMASn).
  • the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source means that after the first oxygen source reacts with the tin metal organic source, the second oxygen source reacts with the tin metal organic source. After the reaction occurs, or the second oxygen source reacts with the tin metal organic source, the first oxygen source reacts with the tin metal organic source.
  • the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source includes a plurality of the following cycles:
  • the first oxygen source and the second oxygen source are used alternately between two adjacent cycles.
  • first oxygen source and the second oxygen source alternately between two adjacent cycles means that if the first oxygen source is used to react with the tin metal organic source in the first cycle, then the first oxygen source is used in the second cycle
  • the second oxygen source reacts with the tin metal organic source
  • the third cycle uses the first oxygen source to react with the tin metal organic source.
  • the first oxygen source or the second oxygen source used in different cycles may be the same or different.
  • the second oxygen source used in the second cycle is ozone
  • the second oxygen source must be used in the fourth cycle, but the second oxygen source can use ozone, or any one or more other second oxygen sources can be used Source, for example, oxygen can be used as the second oxygen source.
  • the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source it may also include using only the first oxygen source and the tin metal organic source. Multiple cyclic steps in which a reaction occurs. That is, before the step of using the first oxygen source and the second oxygen source alternately as the oxygen source to react with the tin metal organic source, it may also include the first oxygen source as a single oxygen source to react with the tin metal organic source. cycle.
  • the number of single oxygen source cycles may be 50-500.
  • the inert gas can be any inert gas known in the art, such as nitrogen, argon, etc., as long as the purging function of the present application can be achieved.
  • Parameters related to the purging of the inert gas such as purging time, flow rate, etc., parameters related to the introduction of the tin metal organic source, such as introduction time, flow rate, etc., as well as the first oxygen source and the second oxygen source.
  • Parameters related to the introduction of the oxygen source can be adjusted by those in the art based on actual needs based on operating methods known in the art.
  • the inert gas is nitrogen.
  • the nitrogen purging time is 5-15 s, and the nitrogen flow rate is 20-90 sccm.
  • the tin metal organic source is introduced using an inert gas as a carrier gas, the flow rate is 20-90 sccm, and the introduction time is 0.1-2 s; the first oxygen source is introduced using an inert gas as a carrier gas.
  • the second oxygen source is introduced directly, the flow rate is 20-90 sccm, and the introduction time is 0.1-1.5s; the second oxygen source is directly introduced, the flow rate is 20-90 sccm, and the introduction time is 0.1-1.5s.
  • Step 1 Introduce a tin metal-organic source, such as TDMASn, to the substrate.
  • a tin metal-organic source such as TDMASn
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the first oxygen source, such as water.
  • Step 4 Nitrogen purge.
  • Step 5 Introduce the tin metal organic source, TDMASn.
  • Step 6 Nitrogen purge.
  • Step 7 Introduce a second oxygen source, such as ozone or oxygen.
  • Step 8 Nitrogen purge.
  • step 8 After completing step 8, perform step 1 to start a new cycle.
  • Step 1 Introduce a metal organic source of tin, such as TDMASn, to the substrate.
  • a metal organic source of tin such as TDMASn
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the first oxygen source, such as water.
  • Step 4 Nitrogen purge.
  • Step 5 Introduce a second oxygen source, such as ozone or oxygen.
  • Step 6 Nitrogen purge.
  • step 6 After completing step 6, perform step 1 to start a new cycle.
  • the number of cycles can be adjusted according to the thickness of the tin dioxide film that needs to be deposited.
  • the number of cycles is 50-500, for example, it can be 50, 60, 70, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210 ,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450,460 ,470,480,490,500.
  • the thickness of the tin dioxide film is 5-50nm, for example, it can be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, 35nm, 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42n m. 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, preferably 10-20nm.
  • the substrate is one of C60, C70, and PCBM.
  • the method of alternately providing the oxygen source by the first oxygen source and the second oxygen source changes the defect of the original single deionized water as the oxygen source.
  • the strong oxidizing property of the second oxygen source is used to promote the conversion of Sn 2+ formed in the ALD reaction process into Sn 4+ , so as to reduce the defects in the prepared tin oxide crystal structure, obtain a more perfect crystal structure, improve the film quality, and ultimately improve the FF of the device.
  • This application also provides a tin dioxide electron transport layer or a tin dioxide buffer layer prepared by the above method.
  • the SnO 2 thin film prepared by the method of the present application has lower reflection, which can reduce the loss of light in this film layer.
  • the film prepared in this way has higher mobility and lower resistivity, which further illustrates that the prepared SnO 2 film has higher quality and good electron transport capability.
  • This application also provides a perovskite solar cell including the above-mentioned tin dioxide electron transport layer or tin dioxide buffer layer, which covers any perovskite solar cell including a tin dioxide electron transport layer or a calcium carbonate solar cell including a tin dioxide buffer layer. Titanium ore solar cells.
  • the perovskite solar cell includes a hole transport layer, a perovskite photoactive layer, an electrical insulation layer, a first electron transport layer and a second electron transport layer stacked in sequence, wherein the first electron transport layer is the above-mentioned tin dioxide electron transport layer.
  • the second electron transport layer is one of C60, C70, and PCBM, made from From a perspective, C60 and tin dioxide can work together as an electron transport layer.
  • the perovskite solar cell may be an inorganic perovskite cell, an organic perovskite cell, or an organic-inorganic hybrid perovskite cell.
  • the present application is a perovskite tandem solar cell, which includes a crystalline silicon bottom cell, an intermediate composite layer and a perovskite top cell that are stacked in sequence, wherein the perovskite top cell is any one of the above-mentioned perovskites.
  • Solar battery is selected from one of PERC battery, TOPCon battery, HJT battery, IBC battery and HBC battery.
  • the intermediate composite layer may be one of tunnel junction, IZO, ITO, and AZO.
  • the transparent electrode may be one of IZO, ITO, and AZO.
  • the structure of a perovskite tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • the crystalline silicon bottom battery can be one of PERC battery, TOPCon battery, HJT battery, IBC battery and HBC battery.
  • the intermediate composite layer may be one of tunnel junction, IZO, ITO, and AZO.
  • the transparent electrode may be one of IZO, ITO, and AZO.
  • the metal electrode may be one of Ag, Au, and Cu.
  • the anti-reflection layer may be one of MgF 2 , LiF, and SiO 2 .
  • the perovskite top battery may be one of an inorganic perovskite battery, an organic perovskite battery, and an organic-inorganic hybrid perovskite battery.
  • the perovskite top cell includes a hole transport layer (HTL), a perovskite photoactive layer (PVSK), a LiF electrical insulation layer, a C60 electron transport layer (ETL), a tin dioxide electron transport layer, and a transparent electrode layer , metal electrode layer, anti-reflection layer.
  • HTL hole transport layer
  • PVSK perovskite photoactive layer
  • ETL C60 electron transport layer
  • tin dioxide electron transport layer a tin dioxide electron transport layer
  • transparent electrode layer metal electrode layer, anti-reflection layer.
  • the HTL layer may be one of 2PACz, Me-4PACz, MeO-2PACz, and NiOx.
  • the HTL layer can be prepared by spin coating, with a thickness of 10 to 30 nm.
  • the perovskite photoactive layer is usually prepared by preparing precursors of each element in proportion, forming a film by spin coating, and then performing heating and annealing, with a thickness of 1 to 3 ⁇ m.
  • the LiF electrical insulation layer can be prepared by thermal evaporation deposition, with a thickness of 1 to 5 nm.
  • the C60 electron transport layer can be prepared by thermal evaporation deposition, with a thickness of 15 to 20 nm.
  • the structure of the tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • Crystalline silicon batteries use HJT batteries
  • the perovskite light-absorbing layer is prepared by spin coating on the hole transport layer.
  • the precursor solution is configured according to the ratio of Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 ) 3 , and then the precursor solution is spin-coated on the air on the hole transport layer, followed by annealing at 120°C for 15 minutes.
  • the thickness of the prepared perovskite film is 1 ⁇ m;
  • a LiF charge insulating layer is thermally evaporated and deposited on the perovskite light-absorbing layer, with a film thickness of about 1 nm;
  • ALD technology was used to prepare SnO 2 electron transport layer and buffer layer on the C60 electron transport layer. Includes the following steps:
  • Step 1 Introduce a metal organic source of tin, TDMASn, to the substrate.
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the first oxygen source, water.
  • Step 4 Nitrogen purge.
  • Step 5 Introduce the tin metal organic source, TDMASn.
  • Step 6 Nitrogen purge.
  • Step 7 Introduce the second oxygen source, ozone.
  • Step 8 Nitrogen purge.
  • step 8 After completing step 8, perform step 1 to start a new cycle.
  • the introduction time is 0.1s and the carrier gas flow rate is 50sccm. Then it is purged with pure nitrogen.
  • the purge time is 12s and the nitrogen flow rate is 50sccm. is 50 sccm; then the oxygen source is introduced for 0.1 s, and the flow rate is 50 sccm; and then pure nitrogen is purged, the purge time is 12 s, and the nitrogen flow rate is 50 sccm; the metal organic source is TDMASn, and the oxygen source is deionized Water or ozone.
  • the oxygen source is deionized water, nitrogen is used as the carrier gas and is introduced into the reaction chamber.
  • the oxygen source is ozone, there is no need for the carrier gas to be directly introduced into the ozone gas.
  • the chamber temperature is set to 90°C, and a SnO 2 film with a thickness of approximately 15 nm is deposited in 140 cycles.
  • PVD is used to deposit an ITO transparent electrode on the SnO2 electron transport layer and buffer layer, with a thickness of about 100nm.
  • a metallic Ag electrode is deposited on the transparent electrode by thermal evaporation, with a thickness of about 300 nm.
  • Electron beam evaporation of MgF 2 is used as an anti-reflection layer on the metal electrode, with a thickness of about 100 nm.
  • the structure of the tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • Crystalline silicon batteries use HJT batteries
  • a hole transport layer precursor solution by spin coating on the composite layer, and heat and anneal at 100°C for 5 minutes.
  • the layer material is MeO-2PACz, and the film thickness is about 20nm;
  • the perovskite light-absorbing layer is prepared by spin coating on the hole transport layer.
  • the precursor solution is configured according to the ratio of Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 ) 3 , and then the precursor solution is spin-coated on the air on the hole transport layer, followed by annealing at 120°C for 15 minutes.
  • the thickness of the prepared perovskite film is 1 ⁇ m;
  • a LiF charge insulating layer is thermally evaporated and deposited on the perovskite light-absorbing layer, with a film thickness of about 1 nm;
  • ALD technology was used to prepare SnO 2 electron transport layer and buffer layer on the C60 electron transport layer. Including the following steps:
  • Step 1 Introduce a tin metal-organic source, TDMASn, to the substrate.
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the first oxygen source, water.
  • Step 4 Nitrogen purge.
  • step 1 After completing step 4, perform step 1 to start a new cycle. After 80 cycles, proceed to step 5.
  • Step 5 Introduce the tin metal organic source, TDMASn.
  • Step 6 Nitrogen purge.
  • Step 7 Introduce the second oxygen source, ozone.
  • Step 8 Nitrogen purge.
  • Step 9 Introduce the tin metal organic source, TDMASn.
  • Step 10 Nitrogen purge.
  • Step 11 Introduce the first oxygen source, water.
  • Step 12 Nitrogen purge.
  • step 5 After completing step 12, perform step 5 to start a new cycle.
  • the introduction time is 0.1s and the carrier gas flow rate is 50 sccm. Then it is purged with pure nitrogen.
  • the purge time is 12 s and the nitrogen flow rate is 50 sccm.
  • oxygen is introduced.
  • the source time is 0.1s, the flow rate is 50sccm; then purge with pure nitrogen, the purge time is 12s, the nitrogen flow rate is 50sccm; the metal organic source is TDMASn, and the oxygen source is deionized water or ozone.
  • nitrogen When it is deionized water, nitrogen is used as the carrier gas and is introduced into the reaction chamber.
  • the oxygen source is ozone, there is no need for the carrier gas to be directly introduced into the ozone gas.
  • the chamber temperature is set to 90°C, and a SnO 2 film with a thickness of approximately 15 nm is deposited in 60 cycles.
  • PVD is used to deposit an ITO transparent electrode on the SnO2 electron transport layer and buffer layer, with a thickness of about 100nm.
  • a metallic Ag electrode is deposited on the transparent electrode by thermal evaporation, with a thickness of about 300 nm.
  • Electron beam evaporation of MgF 2 is used as an anti-reflection layer on the metal electrode, with a thickness of about 100 nm.
  • the structure of the tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • Crystalline silicon batteries use HJT batteries
  • a hole transport layer precursor solution by spin coating on the composite layer, and heat and anneal at 100°C for 5 minutes.
  • the layer material is MeO-2PACz, and the film thickness is about 20nm;
  • the perovskite light-absorbing layer is prepared by spin coating on the hole transport layer.
  • the precursor solution is configured according to the ratio of Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 ) 3 , and then the precursor solution is spin-coated on the air on the hole transport layer, followed by annealing at 120°C for 15 minutes.
  • the thickness of the prepared perovskite film is 1 ⁇ m;
  • a LiF charge insulating layer is thermally evaporated and deposited on the perovskite light-absorbing layer, with a film thickness of about 1 nm;
  • ALD technology was used to prepare SnO 2 electron transport layer and buffer layer on the C60 electron transport layer. Includes the following steps:
  • Step 1 Introduce a tin metal-organic source, TDMASn, to the substrate.
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the first oxygen source, water.
  • Step 4 Nitrogen purge.
  • Step 5 Introduce the tin metal organic source, TDMASn.
  • Step 6 Nitrogen purge.
  • Step 7 Introduce the second oxygen source, oxygen.
  • Step 8 Nitrogen purge.
  • step 8 After completing step 8, perform step 1 to start a new cycle.
  • the introduction time is 0.1s and the carrier gas flow rate is 50 sccm. Then it is purged with pure nitrogen.
  • the purge time is 12 s and the nitrogen flow rate is 50 sccm.
  • oxygen is introduced.
  • the source time is 0.1s, the flow rate is 50sccm; then pure nitrogen is used for purging, the purging time is 12s, and the nitrogen flow rate is 50sccm; the metal organic source is TDMASn, and the oxygen source is deionized water and oxygen.
  • nitrogen When the oxygen source When it is deionized water, nitrogen is used as the carrier gas and is introduced into the reaction chamber.
  • the oxygen source is oxygen, there is no need for the carrier gas to be directly introduced into the oxygen gas. Chamber The temperature is set to 90°C, and 140 cycles deposit a SnO 2 film with a thickness of approximately 15 nm.
  • PVD is used to deposit an ITO transparent electrode on the SnO2 electron transport layer and buffer layer, with a thickness of about 100nm.
  • a metal Ag electrode is deposited on the transparent electrode by thermal evaporation, with a thickness of about 300 nm.
  • Electron beam evaporation of MgF 2 is used as an anti-reflection layer on the metal electrode, with a thickness of about 100 nm.
  • the structure of the tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • Crystalline silicon batteries use HJT batteries
  • a hole transport layer precursor solution by spin coating on the composite layer, and heat and anneal at 100°C for 5 minutes.
  • the layer material is MeO-2PACz, and the film thickness is about 20nm;
  • the perovskite light-absorbing layer is prepared by spin coating on the hole transport layer.
  • the precursor solution is configured according to the ratio of Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 ) 3 , and then the precursor solution is spin-coated on the air on the hole transport layer, followed by annealing at 120°C for 15 minutes.
  • the thickness of the prepared perovskite film is 1 ⁇ m;
  • a LiF charge insulating layer is thermally evaporated and deposited on the perovskite light-absorbing layer, with a film thickness of about 1 nm;
  • ALD technology was used to prepare SnO 2 electron transport layer and buffer layer on the C60 electron transport layer.
  • the specific process steps are based on the route for preparing SnO 2 in Example 1, replacing the oxygen source with a single deionized water. Includes the following steps:
  • Step 1 Introduce a tin metal-organic source, TDMASn, to the substrate.
  • Step 2 Nitrogen purge.
  • Step 3 Introduce the oxygen source, water.
  • Step 4 Nitrogen purge.
  • step 4 After completing step 4, perform step 1 to start a new cycle.
  • PVD is used to deposit an ITO transparent electrode on the SnO2 electron transport layer and buffer layer, with a thickness of about 100nm.
  • a metallic Ag electrode is deposited on the transparent electrode by thermal evaporation, with a thickness of about 300 nm.
  • Electron beam evaporation of MgF 2 is used as an anti-reflection layer on the metal electrode, with a thickness of about 100 nm.
  • the structure of the tandem solar cell is shown in Figure 1, which includes a crystalline silicon bottom cell, a perovskite top cell, an intermediate composite layer, a transparent electrode, a metal electrode, and an anti-reflection layer.
  • Crystalline silicon batteries use HJT batteries
  • the perovskite light-absorbing layer is prepared by spin coating on the hole transport layer.
  • the precursor solution is configured according to the ratio of Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 ) 3 , and then the precursor solution is spin-coated on the air on the hole transport layer, followed by annealing at 120°C for 15 minutes.
  • the thickness of the prepared perovskite film is 1 ⁇ m;
  • a LiF charge insulating layer is thermally evaporated and deposited on the perovskite light-absorbing layer, with a film thickness of about 1 nm;
  • ALD technology was used to prepare the SnO 2 electron transport layer and buffer layer on the C60 electron transport layer.
  • the specific process steps are as follows: Based on the route for preparing SnO 2 in Example 1, the oxygen source was replaced with a single ozone. Includes the following steps:
  • Step 1 Introduce a tin metal-organic source, TDMASn, to the substrate.
  • Step 2 Nitrogen purge.
  • Step 3 Introduce an oxygen source, ozone.
  • Step 4 Nitrogen purge.
  • step 4 After completing step 4, perform step 1 to start a new cycle.
  • PVD is used to deposit an ITO transparent electrode on the SnO2 electron transport layer and buffer layer, with a thickness of about 100nm.
  • a metallic Ag electrode is deposited on the transparent electrode by thermal evaporation, with a thickness of about 300 nm.
  • Electron beam evaporation of MgF 2 is used as an anti-reflection layer on the metal electrode, with a thickness of about 100 nm.
  • Example 1 and Comparative Examples 1-2 The performance data of SnO2 prepared in Example 1 and Comparative Examples 1-2 are shown in Table 1 and Figure 2, where the carrier concentration, mobility, and resistivity are measured using a Hall effect tester, and the refractive index is measured using an ellipsometer. The reflectivity test is measured using an ultraviolet-visible spectrophotometer.
  • the SnO 2 film prepared by alternating water and ozone has lower reflection, which can reduce the loss of light in this film layer.
  • the films prepared in this way have higher mobility and lower resistivity, which further illustrates that the prepared SnO 2 films have higher quality and good electron transport capabilities.
  • the methods of the above embodiments can be implemented by means of software plus the necessary general hardware platform. Of course, it can also be implemented by hardware, but in many cases the former is better. implementation.
  • the technical solution of the present application can be embodied in the form of a software product in essence or that contributes to the existing technology.
  • the computer software product is stored in a storage medium (such as ROM/RAM, disk, CD), including several instructions to cause a terminal (which can be a mobile phone, computer, server, air conditioner, or network device, etc.) to execute the methods described in various embodiments of this application.

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Abstract

一种二氧化锡薄膜的制备方法，包括以下步骤：通过原子层沉积技术在衬底上沉积二氧化锡薄膜，其中在沉积过程中，包含使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤；所述第一氧源选自水、过氧化氢中的一种或两种，所述第二氧源选自臭氧、氧气、一氧化氮、二氧化氮、等离子体活化的臭氧、等离子体活化的氧气、等离子体活化的一氧化氮、或等离子体活化的二氧化氮中的一种或两种以上。通过采用第二氧源加第一氧源交替式提供氧源的方式改变了原来单一氧源的缺陷，利用第二氧源较强的氧化性降低所制备氧化锡晶体结构中的缺陷，获得较完美的晶体结构，提升成膜质量，最终提升器件的填充因子和电子传输能力。

Description

二氧化锡薄膜及其制备方法和应用
本申请要求在2022年09月23日提交中国专利局、申请号为202211164098.5、名称为“二氧化锡薄膜及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于太阳能电池技术领域，具体地，涉及一种二氧化锡薄膜及其制备方法和应用。
背景技术
钙钛矿电池/硅基异质结两端叠层电池增加了对于太阳光谱的吸收范围，理论上可获得大于30％(＞硅电池极限效率29.4％)的光电转换效率。其中目前被认证的最高效率为29.8％，更进一步证实了钙钛矿/硅叠层太阳电池在突破硅电池极限效率方面所表现出的巨大潜力。因此被认为是未来高效太阳电池的主流产品。然而要实现高效稳定的钙钛矿/硅叠层太阳电池，制备高质量的电子传输层也显得尤为重要。
钙钛矿/硅两端叠层太阳电池中，通常采用C60和二氧化锡(SnO2)共同作为电子传输层，除此之外，二氧化锡还充当缓冲层的作用。然而在叠层电池中，二氧化锡通常采用原子层沉积(ALD)技术去制备，原子层沉积技术是将金属有机源与氧源脉冲交替式地通入到反应腔室中，并通过自限制反应成膜的过程。该制备过程中普遍采用去离子水作为单一氧源，采用四(二甲氨基)锡(TDMASn)作为Sn金属有机源，其中Sn为+4价。去离子水作为氧源时，在氧化锡成膜过程中，会导致在二氧化锡薄膜中形成更多缺陷，进而俘获器件中的电子，导致器件性能出现更大的损耗，尤其对器件的填充因子(FF)造成较大影响。
申请内容
针对现有技术存在的问题，本申请提供一种二氧化锡电子传输层及其制备方法。
具体来说，本申请涉及如下方面：
一种二氧化锡薄膜的制备方法，包括以下步骤：
通过原子层沉积技术在衬底上沉积二氧化锡薄膜，
其中在沉积过程中，包含使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤；
所述第一氧源选自水、过氧化氢中的一种或两种，
所述第二氧源选自臭氧、氧气、一氧化氮、二氧化氮、等离子体活化的臭氧、等离子体活化的氧气、等离子体活化的一氧化氮、或等离子体活化的二氧化氮中的一种或两种以上。
任选地，所述第一氧源为水，所述第二氧源为臭氧。
任选地，所述锡金属有机源选自烷基锡、醇锡盐、Sn(NR1R2)4中的一种或两种以上，其中R1和R2各自独立地选自C1-C4的烷基，优选为四(二甲氨基)锡。
任选地，使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤包括多个以下循环：
引入所述锡金属有机源并用惰性气体吹扫，然后引入所述第一氧源或所述第二氧源并用惰性气体吹扫，
其中两个相邻循环之间将所述第一氧源和所述第二氧源交替使用。
任选地，其中在沉积过程中，在所述使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤之前，还包含仅使用第一氧源与锡金属有机源发生反应的多个循环步骤。
任选地，所述循环的数量为50-500。
任选地，所述惰性气体为氮气。
任选地，氮气吹扫步骤中，氮气吹扫时间5-15s，氮气流量为20-90sccm。
任选地，所述锡金属有机源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-2s；所述第一氧源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-1.5s；所述第二氧源直接引入，流量为20-90sccm，通入时间为0.1-1.5s。
任选地，所述二氧化锡薄膜的厚度为5-50nm，优选为10-20nm。
任选地，所述衬底为C60、C70、PCBM中的一种。
一种二氧化锡电子传输层，其通过任一种上述的制备方法制备得到。
一种二氧化锡缓冲层，其通过任一种上述的制备方法制备得到。
一种钙钛矿太阳能电池，其包括上述的二氧化锡电子传输层和/或二氧化锡缓冲层。
任选地，所述钙钛矿太阳能电池包括依次层叠设置的空穴传输层、钙钛矿光活性层、电绝缘层、第一电子传输层和第二电子传输层，其中所述第一电子传输层为所述二氧化锡电子传输层。
任选地，所述第二电子传输层为C60、C70、PCBM中的一种。
任选地，所述钙钛矿太阳能电池选自无机钙钛矿电池、有机钙钛矿电池、有机-无机杂化钙钛矿电池中的一种。
一种钙钛矿叠层太阳能电池，其包括依次层叠设置的晶体硅底电池、中间复合层和钙钛矿顶电池，其中所述钙钛矿顶电池为任一种上述的钙钛矿太阳能电池。
任选地，所述晶体硅底电池选自PERC电池、TOPCon电池、HJT电池、IBC电池、HBC电池中的一种。
本申请通过采用第二氧源加第一氧源交替式提供氧源的方式改变了原来单一氧源的缺陷，利用第二氧源较强的氧化性降低所制备氧化锡晶体结构中的缺陷，获得较完美的晶体结构，提升成膜质量，最终提升器件的填充因子和电子传输能力。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例的描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1是钙钛矿/硅两端叠层太阳电池结构图；
图2为各个氧源制备条件下SnO2薄膜的反射性能。
具体实施例
下面结合实施例进一步说明本申请，应当理解，实施例仅用于进一步说明和阐释本申请，并非用于限制本申请。
除非另外定义，本说明书中有关技术的和科学的术语与本领域内的技术人员所通常理解的意思相同。虽然在实验或实际应用中可以应用与此间所述相似或相同的方法和材料，本文还是在下文中对材料和方法做了描述。在相冲突的情况下，以本说明书包括其中定义为准，另外，材料、方法和例子仅供说明，而不具限制性。以下结合具体实施例对本申请作进一步的说明，但不用来限制本申请的范围。
在本文中，原子层沉积技术(ALD)是通过将气相前驱体脉冲交替地通入反应器并在沉积基体上化学吸附并反应而形成沉积膜的一种方法，是可以将物质以单原子膜形式一层一层的镀在衬底表面的方法。在原子层沉积过程中，新一层原子膜的化学反应是直接与之前一层相关联的，这种方式使每次反应只沉积一层原子。常规ALD设备可包括反应器室、衬底固持器、包括用于将前体和反应物提供到衬底表面的气体入口的气体流动系统，以及用于去除所使用的气体的排气系统。生长机制依赖于前体在衬底的活性位点上的吸附，并且优选地维持条件，使得不超过单层形成在衬底上，从而自终止工艺。将衬底暴露于第一前体通常后接吹扫阶段或其它去除工艺(例如，抽成真空或“抽气”)，其中任何过量的第一前体以及任何反应副产物从反应室中去除。然后将第二反应物或前体引入反应室中，此时其与第一前体反应，并且这一反应在衬底上产生所需膜。当吸附在衬底上的所有可用的第一前体物种已与第二前体反应时，反应终止。然后执行第二吹扫或其它去除阶段，其除去反应室中的任何剩余的第二前体和可能的反应副产物。可重复这一循环以使膜生长到所需厚度。
ALD优于其它沉积工艺的公认优点之一是其自饱和并且均一，只要温度在ALD窗(其高于前体的冷凝温度并且低于前体的热分解温度)内并且在每个脉冲中提供足够的反应物剂量以使表面饱和即可。因此，温度和气体供应都可不需完全均一以获得均一沉积。
在本文中，“衬底”可以指可使用的或上面可形成装置、电路或膜的任何一种或多种下层材料。
在本文中，“膜”可以指通过本文所公开的方法沉积的任何连续或不连续的结构、材料或多种材料。举例来说，“膜”可以包括2D材料、纳米棒、纳米管、纳米层合物或纳米颗粒，或甚至部分或全部分子层或部分或全部 原子层或原子和/或分子的簇。“膜”还可以包含具有针孔的一种或多种材料或层，但仍然至少部分地连续。
在本文中，“金属有机源”是指含有金属的有机化合物，锡金属有机源是指含有锡的有机化合物。
在本文中，“电子传输层”是指电子可以容易地流过并且通常会反射空穴(空穴是在半导体中被认为是正电荷的可移动载流子的电子的缺失)的层。
在本文中，“缓冲层”是指起到界面调节作用的层，可位于电子传输层和阴极之间或电子传输与光吸收层之间，一方面可以使电子传输路径上的能级更加匹配,加快电子抽取和传输,钝化界面缺陷态,减少界面复合电流；另一方面,还可以起到保护钙钛矿吸收层的作用,进而提高电池稳定性。
针对现有技术存在的问题，本申请提供一种二氧化锡(SnO2)薄膜的制备方法，其包括以下步骤：
通过原子层沉积技术在衬底上沉积二氧化锡薄膜，
其中在沉积过程中，包含使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤。
其中所述第一氧源选自水、过氧化氢中的一种或两种。即第一氧源可以是一种或两种，比如可以为水，可以为过氧化氢，也可以水和过氧化氢同时或分别使用。
所述第二氧源选自臭氧、氧气、一氧化氮、二氧化氮、等离子体活化的臭氧、等离子体活化的氧气、等离子体活化的一氧化氮、等离子体活化的二氧化氮中的一种或两种以上。第二氧源可以是一种、两种、三种或更多种。第一氧源和第二氧源可以任意组合。
在一个具体的实施方式中，所述第一氧源为水，所述第二氧源为臭氧。
在一个具体的实施方式中，所述第一氧源为过氧化氢，所述第二氧源为臭氧。
在一个具体的实施方式中，所述第一氧源为水，所述第二氧源为氧气。
所述锡金属有机源选自烷基锡、醇锡盐、Sn(NR1R2)4中的一种或两种以上，其中R1和R2各自独立地选自C1-C4的烷基。
在一个具体的实施方式中，所述锡金属有机源为Sn(NR1R2)4，其中 R1和R2各自独立地选自C1-C4的烷基。
在一个具体的实施方式中，所述锡金属有机源为四(二甲氨基)锡(TDMASn)。
在一个具体的实施方式中，所述第一氧源为水，所述第二氧源为臭氧，所述锡金属有机源为四(二甲氨基)锡(TDMASn)。
使用第一氧源和第二氧源两种氧源交替作为氧源与锡金属有机源发生反应，是指第一氧源与锡金属有机源发生反应之后，第二氧源与锡金属有机源发生反应，或者第二氧源与锡金属有机源发生反应之后，第一氧源与锡金属有机源发生反应。
具体地，使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤包括多个以下循环：
引入所述锡金属有机源并用惰性气体吹扫，然后引入所述第一氧源或所述第二氧源并用惰性气体吹扫，
其中两个相邻循环之间将所述第一氧源和所述第二氧源交替使用。
两个相邻循环之间将所述第一氧源和所述第二氧源交替使用是指如果第一个循环中使用第一氧源与锡金属有机源发生反应，则第二循环则使用第二氧源与锡金属有机源发生反应，第三个循环使用第一氧源与锡金属有机源发生反应。在这些循环中，只要所述第一氧源和所述第二氧源交替使用即可，不同循环所使用的第一氧源或第二氧源可以相同也可以不同。例如，如果第二循环中使用的第二氧源是臭氧，则第四循环中必须使用第二氧源，但是第二氧源可以使用臭氧，也可以使用任何一种或多种其它第二氧源，例如可以使用氧气作为第二氧源。
进一步地，在沉积过程中，在所述使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤之前，还可以包含仅使用第一氧源与锡金属有机源发生反应的多个循环步骤。即，在所述使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤之前，还可以包括第一氧源作为单一氧源与锡金属有机源发生反应的多个循环。
该单一氧源循环的数量可以为50-500。
所述惰性气体可以是本领域已知的任何惰性气体，例如氮气、氩气等，只要能实现本申请的吹扫功能即可。
所述惰性气体的吹扫相关的参数，比如吹扫时间，流量等，所述锡金属有机源的引入相关的参数，如引入时间、流量等，以及所述第一氧源和所述第二氧源的引入相关的参数，如引入时间、流量等，本领域人员可以根据实际需要基于本领域已知的操作方法进行调整。
在一个具体的实施方式中，所述惰性气体为氮气。
在一个具体的实施方式中，氮气吹扫步骤中，氮气吹扫时间5-15s，氮气流量为20-90sccm。
在一个具体的实施方式中，所述锡金属有机源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-2s；所述第一氧源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-1.5s；所述第二氧源直接引入，流量为20-90sccm，通入时间为0.1-1.5s。
在一个具体的实施方式中，包括以下步骤：
步骤1：向衬底引入锡金属有机源，例如TDMASn。
步骤2：氮气吹扫。
步骤3：引入第一氧源，例如水。
步骤4：氮气吹扫。
步骤5：引入锡金属有机源，TDMASn。
步骤6：氮气吹扫。
步骤7：引入第二氧源，例如臭氧或氧气。
步骤8：氮气吹扫。
完成步骤8以后再执行步骤1以开始一个新的循环。
在一个具体的实施方式中，包括以下步骤：
步骤1：向衬底引入锡金属有机源，例如TDMASn。
步骤2：氮气吹扫。
步骤3：引入第一氧源，例如水。
步骤4：氮气吹扫。
步骤5：引入第二氧源，例如臭氧或氧气。
步骤6：氮气吹扫。
完成步骤6以后再执行步骤1以开始一个新的循环。
其中循环的数量可以根据需要沉积的二氧化锡薄膜的厚度进行调整。
在一个具体的实施方式中，循环的数量为50-500，例如可以为50、60、70、90、100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、290、300、310、320、330、340、350、360、370、380、390、400、410、420、430、440、450、460、470、480、490、500。
在一个具体的实施方式中，所述二氧化锡薄膜的厚度为5-50nm，例如可以为5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm、30nm、31nm、32nm、33nm、34nm、35nm、36nm、37nm、38nm、39nm、40nm、41nm、42nm、43nm、44nm、45nm、46nm、47nm、48nm、49nm、50nm，优选为10-20nm。
在一个具体的实施方式中，所述衬底为C60、C70、PCBM中的一种。
采用第一氧源和第二氧源交替提供氧源的方式改变了原来单一的去离子水作为氧源的缺陷，利用第二氧源强的氧化性去促使ALD反应过程中所形成的Sn2+转化为Sn4+，以降低所制备氧化锡晶体结构中的缺陷，获得较完美的晶体结构，提升成膜质量，最终提升器件的FF。
本申请还提供由上述方法制备得到的二氧化锡电子传输层或二氧化锡缓冲层。
采用本申请方法制备的SnO2薄膜具有更低的反射，即可减少光在此膜层中的损失。此外，此方式制备的薄膜具有较高的迁移率和较低的电阻率，这进一步说明，所制备的SnO2薄膜具有更高的质量和良好的电子传输能力。
本申请还提供包括上述二氧化锡电子传输层或二氧化锡缓冲层的钙钛矿太阳能电池，其涵盖任何包括二氧化锡电子传输层的钙钛矿太阳能电池或者包括二氧化锡缓冲层的钙钛矿太阳能电池。
在一个具体的实施方式中，所述钙钛矿太阳能电池包括依次层叠设置的空穴传输层、钙钛矿光活性层、电绝缘层、第一电子传输层和第二电子传输层，其中所述第一电子传输层为上述的二氧化锡电子传输层。
所述第二电子传输层为C60、C70、PCBM中的一种，从性能优异的 角度而言，C60和二氧化锡可以共同作为电子传输层。
所述钙钛矿太阳能电池可以为无机钙钛矿电池、有机钙钛矿电池、有机-无机杂化钙钛矿电池中的一种。
本申请一种钙钛矿叠层太阳能电池，其包括依次层叠设置的晶体硅底电池、中间复合层和钙钛矿顶电池，其中所述钙钛矿顶电池为任一种上述的钙钛矿太阳能电池。其中，所述晶体硅底电池选自PERC电池、TOPCon电池、HJT电池、IBC电池、HBC电池中的一种。
所述中间复合层可以是隧穿结、IZO、ITO、AZO中的一种。所述透明电极可以是IZO、ITO、AZO中的一种。
在一个具体的实施方式中，钙钛矿叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。其中，所述晶体硅底电池可以是PERC电池、TOPCon电池、HJT电池、IBC电池、HBC电池中的一种。所述中间复合层可以是隧穿结、IZO、ITO、AZO中的一种。所述透明电极可以是IZO、ITO、AZO中的一种。所述金属电极可以是Ag、Au、Cu中的一种。所述减反层可以是MgF2、LiF、SiO2中的一种。所述钙钛矿顶电池可以是无机钙钛矿电池、有机钙钛矿电池、有机-无机杂化钙钛矿电池中的一种。
进一步地，钙钛矿顶电池包括空穴传输层(HTL)、钙钛矿光活性层(PVSK)、LiF电绝缘层、C60电子传输层(ETL)、二氧化锡电子传输层、透明电极层、金属电极层、减反层。
所述HTL层可以是2PACz、Me-4PACz、MeO-2PACz、NiOx中的一种。所述HTL层可以采用旋涂法制备得到，厚度为10～30nm。
所述钙钛矿光活性层的化学通式为AB(XnY1-n)3，其中A通常为CH3NH3、C4H9NH3、NH2＝CHNH2或Cs等一价阳离子；B通常为Pb、Sn等二价金属离子；X、Y通常为Cl、Br或I等卤素阴离子；n＝1、2、3。其中，所述钙钛矿光活性层通常将各元素的前驱体按比例配制，采用旋涂法成膜，随后进行加热退火制备得到，厚度为1～3μm。
所述LiF电绝缘层可以采用热蒸发沉积制备得到，厚度为1～5nm。
所述C60电子传输层可以采用热蒸发沉积制备得到，厚度为15～20nm。
实施例
实施例1
叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。
叠层太阳电池及氧化锡层制备方式如下：
晶体硅电池选用HJT电池；
在所述HJT电池n面采用PVD沉积ITO复合层；
在所述复合层上旋涂制备空穴传输层前驱体溶液，100℃加热退火5min，所述层材料为MeO-2PACz，薄膜厚度为20nm左右；
在所述空穴传输层上旋涂制备钙钛矿吸光层，具体地，按照Cs0.05FA0.8MA0.15Pb(I0.75Br0.25)3比例配置前驱体溶液，然后将前驱体溶液旋涂在空穴传输层上，随后120℃退火15min，所制备的钙钛矿薄膜厚度为1μm；
在所述钙钛矿吸光层上热蒸发沉积LiF电荷绝缘层，薄膜厚度为1nm左右；
在所述LiF电荷绝缘层上采用热蒸发沉积C60电子传输层，薄膜厚度为15nm左右；
在所述C60电子传输层上采用ALD技术制备SnO2电子传输层及缓冲层。包括以下步骤：
步骤1：向衬底引入锡金属有机源，TDMASn。
步骤2：氮气吹扫。
步骤3：引入第一氧源，水。
步骤4：氮气吹扫。
步骤5：引入锡金属有机源，TDMASn。
步骤6：氮气吹扫。
步骤7：引入第二氧源，臭氧。
步骤8：氮气吹扫。
完成步骤8以后再执行步骤1以开始一个新的循环。
具体的步骤如下：
将金属有机源通过氮气作为载气通入反应腔室，通入的时间为0.1s，载气流量为50sccm；然后以纯氮气进行吹扫，吹扫时间12s，氮气流量 为50sccm；然后通入氧源时间为0.1s，流量为50sccm；再以纯氮气进行吹扫，吹扫时间为12s，氮气流量为50sccm；所述金属有机源为TDMASn，所述氧源为去离子水或臭氧，当氧源为去离子水时，通过氮气作为载气被通入到反应腔体，当氧源为臭氧时，不需要载气直接通入臭氧气体。腔室温度设置为90℃，140个循环沉积厚度大约为15nm左右的SnO2薄膜。
在所述SnO2电子传输层及缓冲层上采用PVD沉积ITO透明电极，厚度为100nm左右。
在所述透明电极上采用热蒸发沉积金属Ag电极，厚度为300nm左右。
在所述金属电极上采用电子束蒸镀MgF2作为减反层，厚度为100nm左右。
实施例2
叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。
叠层太阳电池及氧化锡层制备方式如下：
晶体硅电池选用HJT电池；
在所述HJT电池n面采用PVD沉积ITO复合层；
在所述复合层上旋涂制备空穴传输层前驱体溶液，100℃加热退火5min，所述层材料为MeO-2PACz，薄膜厚度为20nm左右；
在所述空穴传输层上旋涂制备钙钛矿吸光层，具体地，按照Cs0.05FA0.8MA0.15Pb(I0.75Br0.25)3比例配置前驱体溶液，然后将前驱体溶液旋涂在空穴传输层上，随后120℃退火15min，所制备的钙钛矿薄膜厚度为1μm；
在所述钙钛矿吸光层上热蒸发沉积LiF电荷绝缘层，薄膜厚度为1nm左右；
在所述LiF电荷绝缘层上采用热蒸发沉积C60电子传输层，薄膜厚度为15nm左右；
在所述C60电子传输层上采用ALD技术制备SnO2电子传输层及缓冲层。包括以下步骤为:
步骤1：向衬底引入锡金属有机源，TDMASn。
步骤2：氮气吹扫。
步骤3：引入第一氧源，水。
步骤4：氮气吹扫。
完成步骤4以后再执行步骤1以开始一个新的循环。80个循环之后，执行步骤5。
步骤5：引入锡金属有机源，TDMASn。
步骤6：氮气吹扫。
步骤7：引入第二氧源，臭氧。
步骤8：氮气吹扫。
步骤9：引入锡金属有机源，TDMASn。
步骤10：氮气吹扫。
步骤11：引入第一氧源，水。
步骤12：氮气吹扫。
完成步骤12以后再执行步骤5以开始一个新的循环。
具体的步骤如下：
将金属有机源通过氮气作为载气通入反应腔室，通入的时间为0.1s，载气流量为50sccm；然后以纯氮气进行吹扫，吹扫时间12s，氮气流量为50sccm；然后通入氧源时间为0.1s，流量为50sccm；再以纯氮气进行吹扫，吹扫时间为12s，氮气流量为50sccm；所述金属有机源为TDMASn，所述氧源为去离子水或臭氧，当氧源为去离子水时，通过氮气作为载气被通入到反应腔体，当氧源为臭氧时，不需要载气直接通入臭氧气体。腔室温度设置为90℃，60个循环沉积厚度大约为15nm左右的SnO2薄膜。
在所述SnO2电子传输层及缓冲层上采用PVD沉积ITO透明电极，厚度为100nm左右。
在所述透明电极上采用热蒸发沉积金属Ag电极，厚度为300nm左右。
在所述金属电极上采用电子束蒸镀MgF2作为减反层，厚度为100nm左右。
实施例3
叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。
叠层太阳电池及氧化锡层制备方式如下：
晶体硅电池选用HJT电池；
在所述HJT电池n面采用PVD沉积ITO复合层；
在所述复合层上旋涂制备空穴传输层前驱体溶液，100℃加热退火5min，所述层材料为MeO-2PACz，薄膜厚度为20nm左右；
在所述空穴传输层上旋涂制备钙钛矿吸光层，具体地，按照Cs0.05FA0.8MA0.15Pb(I0.75Br0.25)3比例配置前驱体溶液，然后将前驱体溶液旋涂在空穴传输层上，随后120℃退火15min，所制备的钙钛矿薄膜厚度为1μm；
在所述钙钛矿吸光层上热蒸发沉积LiF电荷绝缘层，薄膜厚度为1nm左右；
在所述LiF电荷绝缘层上采用热蒸发沉积C60电子传输层，薄膜厚度为15nm左右；
在所述C60电子传输层上采用ALD技术制备SnO2电子传输层及缓冲层。包括以下步骤：
步骤1：向衬底引入锡金属有机源，TDMASn。
步骤2：氮气吹扫。
步骤3：引入第一氧源，水。
步骤4：氮气吹扫。
步骤5：引入锡金属有机源，TDMASn。
步骤6：氮气吹扫。
步骤7：引入第二氧源，氧气。
步骤8：氮气吹扫。
完成步骤8以后再执行步骤1以开始一个新的循环。
具体的步骤如下：
将金属有机源通过氮气作为载气通入反应腔室，通入的时间为0.1s，载气流量为50sccm；然后以纯氮气进行吹扫，吹扫时间12s，氮气流量为50sccm；然后通入氧源时间为0.1s，流量为50sccm；再以纯氮气进行吹扫，吹扫时间为12s，氮气流量为50sccm；所述金属有机源为TDMASn，所述氧源为去离子水和氧气，当氧源为去离子水时，通过氮气作为载气被通入到反应腔体，当氧源为氧气时，不需要载气直接通入氧气气体。腔室 温度设置为90℃，140个循环沉积厚度大约为15nm左右的SnO2薄膜。
在所述SnO2电子传输层及缓冲层上采用PVD沉积ITO透明电极，厚度为100nm左右。
在所述透明电极上采用热蒸发沉积金属Ag电极，厚度为300nm左右。
在所述金属电极上采用电子束蒸镀MgF2作为减反层，厚度为100nm左右。
对比例1
叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。
叠层太阳电池及氧化锡层制备方式如下：
晶体硅电池选用HJT电池；
在所述HJT电池n面采用PVD沉积ITO复合层；
在所述复合层上旋涂制备空穴传输层前驱体溶液，100℃加热退火5min，所述层材料为MeO-2PACz，薄膜厚度为20nm左右；
在所述空穴传输层上旋涂制备钙钛矿吸光层，具体地，按照Cs0.05FA0.8MA0.15Pb(I0.75Br0.25)3比例配置前驱体溶液，然后将前驱体溶液旋涂在空穴传输层上，随后120℃退火15min，所制备的钙钛矿薄膜厚度为1μm；
在所述钙钛矿吸光层上热蒸发沉积LiF电荷绝缘层，薄膜厚度为1nm左右；
在所述LiF电荷绝缘层上采用热蒸发沉积C60电子传输层，薄膜厚度为15nm左右；
在所述C60电子传输层上采用ALD技术制备SnO2电子传输层及缓冲层。具体工艺步骤是在实施例1制备SnO2的路线基础上，将氧源替换为单一的去离子水。包括以下步骤：
步骤1：向衬底引入锡金属有机源，TDMASn。
步骤2：氮气吹扫。
步骤3：引入氧源，水。
步骤4：氮气吹扫。
完成步骤4以后再执行步骤1以开始一个新的循环。
在所述SnO2电子传输层及缓冲层上采用PVD沉积ITO透明电极，厚度为100nm左右。
在所述透明电极上采用热蒸发沉积金属Ag电极，厚度为300nm左右。
在所述金属电极上采用电子束蒸镀MgF2作为减反层，厚度为100nm左右。
对比例2
叠层太阳电池的结构如图1所示，其包括晶体硅底电池、钙钛矿顶电池、中间复合层、透明电极、金属电极、减反层。
叠层太阳电池及氧化锡层制备方式如下：
晶体硅电池选用HJT电池；
在所述HJT电池n面采用PVD沉积ITO复合层；
在所述复合层上旋涂制备空穴传输层前驱体溶液，100℃加热退火5min，所述层材料为MeO-2PACz，薄膜厚度为20nm左右；
在所述空穴传输层上旋涂制备钙钛矿吸光层，具体地，按照Cs0.05FA0.8MA0.15Pb(I0.75Br0.25)3比例配置前驱体溶液，然后将前驱体溶液旋涂在空穴传输层上，随后120℃退火15min，所制备的钙钛矿薄膜厚度为1μm；
在所述钙钛矿吸光层上热蒸发沉积LiF电荷绝缘层，薄膜厚度为1nm左右；
在所述LiF电荷绝缘层上采用热蒸发沉积C60电子传输层，薄膜厚度为15nm左右；
在所述C60电子传输层上采用ALD技术制备SnO2电子传输层及缓冲层，具体工艺步骤如下：在实施例1制备SnO2的路线基础上，将氧源替换为单一的臭氧。包括以下步骤：
步骤1：向衬底引入锡金属有机源，TDMASn。
步骤2：氮气吹扫。
步骤3：引入氧源，臭氧。
步骤4：氮气吹扫。
完成步骤4以后再执行步骤1以开始一个新的循环。
在所述SnO2电子传输层及缓冲层上采用PVD沉积ITO透明电极，厚度为100nm左右。
在所述透明电极上采用热蒸发沉积金属Ag电极，厚度为300nm左右。
在所述金属电极上采用电子束蒸镀MgF2作为减反层，厚度为100nm左右。
实施例1和对比例1-2所制备SnO2的性能数据如表1和图2所示，其中载流子浓度、迁移率、电阻率采用霍尔效应测试仪测得，其中折射率采用椭偏仪测定。反射率测试，采用紫外可见分光光度计测试得到。
表1 SnO2薄膜的电学和光学性能数据
从图2所示的反射光谱可以看出，水和臭氧交替的方式制备的SnO2薄膜具有更低的反射，即可减少光在此膜层中的损失。此外，此方式制备的薄膜具有较高的迁移率和较低的电阻率，这进一步说明，所制备的SnO2薄膜具有更高的质量和良好的电子传输能力。
对实施例1-3和对比例1-2所制备的叠层太阳电池进行直流电流-电压(I-V)测试。测试结果如表2所示：
表2太阳能电池性能数据比较
从实施例1-3和对比例1、2的I-V测试结果可知，采用单一氧源ALD制备氧化锡时，器件FF较低且离散性大，说明电荷传输的阻力增大，氧化锡薄膜质量较差；采用去离子水和臭氧交替作为氧源的时候，可以提升氧化锡薄膜质量，晶体生长结构更为规整，提高电子传输能力，所制备器件FF明显提升。
需要说明的是，对于方法实施例，为了简单描述，故将其都表述为一系列的动作组合，但是本领域技术人员应该知悉，本申请实施例并不受所描述的动作顺序的限制，因为依据本申请实施例，某些步骤可以采用其他顺序或者同时进行。其次，本领域技术人员也应该知悉，说明书中所描述的实施例均属于优选实施例，所涉及的动作并不一定都是本申请实施例所必须的。
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者装置不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者装置所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括该要素的过程、方法、物品或者装置中还存在另外的相同要素。
通过以上的实施方式的描述，本领域的技术人员可以清楚地了解到上述实施例方法可借助软件加必需的通用硬件平台的方式来实现，当然也可以通过硬件，但很多情况下前者是更佳的实施方式。基于这样的理解，本申请的技术方案本质上或者说对现有技术做出贡献的部分可以以软件产品的形式体现出来，该计算机软件产品存储在一个存储介质(如ROM/RAM、磁碟、光盘)中，包括若干指令用以使得一台终端(可以是手机，计算机，服务器，空调器，或者网络设备等)执行本申请各个实施例所述的方法。
上面结合附图对本申请的实施例进行了描述，但是本申请并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本申请的启示下，在不脱离本申请宗旨和权利要求所保护的范围情况下，还可做出很多形式，这些均属于本申请的保护之内。

Claims (19)

  1. 一种二氧化锡薄膜的制备方法，其中，包括以下步骤：
    通过原子层沉积技术在衬底上沉积二氧化锡薄膜，
    其中在沉积过程中，包含使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤；
    所述第一氧源选自水、过氧化氢中的一种或两种，
    所述第二氧源选自臭氧、氧气、一氧化氮、二氧化氮、等离子体活化的臭氧、等离子体活化的氧气、等离子体活化的一氧化氮、或等离子体活化的二氧化氮中的一种或两种以上。
  2. 根据权利要求1所述的制备方法，其中，所述第一氧源为水，所述第二氧源为臭氧。
  3. 根据权利要求1所述的制备方法，其中，所述锡金属有机源选自烷基锡、醇锡盐、Sn(NR1R2)4中的一种或两种以上，其中R1和R2各自独立地选自C1-C4的烷基，优选为四(二甲氨基)锡。
  4. 根据权利要求1所述的制备方法，其中，使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤包括多个以下循环：
    引入所述锡金属有机源并用惰性气体吹扫，然后引入所述第一氧源或所述第二氧源并用惰性气体吹扫，
    其中两个相邻循环之间将所述第一氧源和所述第二氧源交替使用。
  5. 根据权利要求1所述的制备方法，其中，其中在沉积过程中，在所述使用第一氧源和第二氧源交替作为氧源与锡金属有机源发生反应的步骤之前，还包含仅使用第一氧源与锡金属有机源发生反应的多个循环步骤。
  6. 根据权利要求4所述的制备方法，其中，所述循环的数量为50-500。
  7. 根据权利要求4所述的制备方法，其中，所述惰性气体为氮气。
  8. 根据权利要求6所述的制备方法，其中，氮气吹扫步骤中，氮气吹扫时间5-15s，氮气流量为20-90sccm。
  9. 根据权利要求4所述的制备方法，其中，所述锡金属有机源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-2s；所述第一氧源通过惰性气体作为载气进行引入，流量为20-90sccm，通入时间为0.1-1.5s；所述第二氧源直接引入，流量为20-90sccm，通入时间为0.1-1.5s。
  10. 根据权利要求1所述的制备方法，其中，所述二氧化锡薄膜的厚度为5-50nm，优选为10-20nm。
  11. 根据权利要求1所述的制备方法，其中，所述衬底为C60、C70、PCBM中的一种。
  12. 一种二氧化锡电子传输层，其通过权利要求1-11中任一项所述的制备方法制备得到。
  13. 一种二氧化锡缓冲层，其通过权利要求1-11中任一项所述的制备方法制备得到。
  14. 一种钙钛矿太阳能电池，其包括权利要求12所述的二氧化锡电子传输层和/或权利要求13所述的二氧化锡缓冲层。
  15. 根据权利要求14所述的钙钛矿太阳能电池，其中，所述钙钛矿太阳能电池包括依次层叠设置的空穴传输层、钙钛矿光活性层、电绝缘层、第一电子传输层和第二电子传输层，其中所述第一电子传输层为所述二氧化锡电子传输层。
  16. 根据权利要求15的钙钛矿太阳能电池，其中，所述第二电子传输层为C60、C70、PCBM中的一种。
  17. 根据权利要求15的钙钛矿太阳能电池，其中，所述钙钛矿太阳能电池选自无机钙钛矿电池、有机钙钛矿电池、有机-无机杂化钙钛矿电池中的一种。
  18. 一种钙钛矿叠层太阳能电池，其包括依次层叠设置的晶体硅底电池、中间复合层和钙钛矿顶电池，其中，所述钙钛矿顶电池为权利要求14-17中任一项所述的钙钛矿太阳能电池。
  19. 根据权利要求18的钙钛矿叠层太阳能电池，其中，所述晶体硅底电池选自PERC电池、TOPCon电池、HJT电池、IBC电池、HBC电池中的一种。
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CN115584483A (zh) * 2022-09-23 2023-01-10 隆基绿能科技股份有限公司 二氧化锡薄膜及其制备方法和应用
CN115440890A (zh) * 2022-09-28 2022-12-06 隆基绿能科技股份有限公司 一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池

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