WO2024066474A1 - 一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池 - Google Patents

一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池 Download PDF

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WO2024066474A1
WO2024066474A1 PCT/CN2023/099522 CN2023099522W WO2024066474A1 WO 2024066474 A1 WO2024066474 A1 WO 2024066474A1 CN 2023099522 W CN2023099522 W CN 2023099522W WO 2024066474 A1 WO2024066474 A1 WO 2024066474A1
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tin
transport layer
electron transport
source
solar cell
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French (fr)
Inventor
顾小兵
丁蕾
王永磊
何永才
董鑫
何博
李勃超
李巧艳
张富
徐希翔
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Longi Green Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • 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 relates to the technical field of solar cells, and in particular to a perovskite solar cell and a manufacturing method thereof, and a stacked solar cell.
  • Perovskite solar cells belong to the third generation of solar cells, also known as new concept solar cells. Because the perovskite materials they use have a series of advantages such as high absorption coefficient, high carrier mobility, large diffusion length, and adjustable band gap, they have received widespread attention in the field of solar cells.
  • the material of the electron transport layer included in the existing perovskite solar cell is tin oxide (chemical formula SnO 2 , also known as tin dioxide), resulting in poor electron transport capability of the electron transport layer, which is not conducive to improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the purpose of the present application is to provide a perovskite solar cell and a method for manufacturing the same, and a stacked solar cell, which are used to enhance the electron transport capability of an electron transport layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell including the electron transport layer.
  • the present application provides a perovskite solar cell, which comprises: a light absorption layer, a hole transport layer and an electron transport layer.
  • the hole transport layer is formed on one side of the light absorption layer.
  • the electron transport layer is formed on the side of the light absorption layer away from the hole transport layer.
  • the material of the electron transport layer comprises tin oxide and tin oxide.
  • the stoichiometric ratio of tin element and oxygen element in the tin oxide is greater than 1:2 and less than or equal to 1:1.
  • the perovskite solar cell provided in the present application includes a light absorption layer, and a hole transport layer and an electron transport layer respectively formed on two opposite sides of the light absorption layer. Based on this, in the actual working process, the light absorption layer will generate electron and hole pairs after absorbing photons. Among them, the holes that have not been recombined move in the direction close to the hole transport layer and are conducted to the corresponding electrode via the hole transport layer. The electrons that have not been recombined move in the direction close to the electron transport layer and are conducted to the corresponding electrode via the electron transport layer, thereby forming a photocurrent.
  • the materials of the above-mentioned electron transport layer include tin oxide and tin oxide. Because the valence of tin in tin oxide is +4 and the valence of oxygen is -2, the stoichiometric ratio of tin element and oxygen element in tin oxide is 1:2. In addition, the stoichiometric ratio of tin element and oxygen element in the above-mentioned tin oxide is greater than 1:2, and is less than or equal to 1:1. It can be understood that the proportion of oxygen element in the above-mentioned tin oxide is lower than the proportion of oxygen element in tin oxide.
  • the material of the electron transport layer included in the perovskite solar cell provided in the present application includes not only tin oxide, but also the above-mentioned tin oxide.
  • the Sn/O ratio in the electron transport layer in the present application can be increased, thereby increasing the oxygen vacancy concentration in the electron transport layer.
  • the conductive principle of the above-mentioned electron transport layer is that the outer electrons of the tin element form chemical bonds with the outer electrons of the oxygen element, when there is a lack of oxygen in the electron transport layer, the outer electrons of the tin element form free electrons to achieve conductivity.
  • the oxygen vacancy concentration in the electron transport layer included in the perovskite solar cell provided by the present application increases, the more free electrons are formed in the electron transport layer, thereby improving the electron transport capacity of the electron transport layer, accelerating the separation of electrons and holes at the interface where the light absorption layer and the electron transport layer are in contact, reducing the interface recombination loss of electrons, and thus helping to improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the tin oxide includes stannous oxide (chemical formula: SnO).
  • the valence of tin in stannous oxide is +2 and the valence of oxygen is -2. Based on this, in the case where tin oxide includes stannous oxide, it is possible to dope Sn 2+ in tin oxide, thereby producing a mixed valence electron transport layer, which is beneficial to increase the concentration of oxygen vacancies in the electron transport layer.
  • the ratio of tin element in stannous oxide is the same as the ratio of oxygen element, which is convenient for adjusting the ratio of tin source and oxygen source for manufacturing stannous oxide, and reducing the difficulty of manufacturing tin oxide.
  • the chemical properties of stannous oxide at room temperature and pressure are relatively stable, which can improve the working stability of perovskite solar cells including the electron transport layer.
  • the stoichiometric ratio of tin oxide to stannous oxide in the electron transport layer is as follows: The range is: 5:1 to 50:1.
  • the greater the ratio of the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer the higher the content of tin oxide in the electron transport layer, and the lower the content of stannous oxide therein.
  • the concentration of oxygen vacancies in the electron transport layer is smaller.
  • the smaller the ratio of the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer the greater the concentration of oxygen vacancies in the electron transport layer.
  • the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer ranges from 5:1 to 50:1
  • the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer is moderate, which can prevent the oxygen vacancy concentration in the electron transport layer from being low due to the large stoichiometric ratio, and ensure that the electron transport layer has appropriate electron transport capacity.
  • it can also prevent the electron transport layer from becoming a P-type oxide semiconductor layer due to the small stoichiometric ratio, which causes the electrons generated in the light absorption layer to increase the recombination rate in the electron transport layer, ensuring that the perovskite solar cell has a high photoelectric conversion efficiency.
  • the electron transport layer includes a first tin-containing oxide layer and a second tin-containing oxide layer alternately stacked.
  • the material of the first tin-containing oxide layer is tin oxide.
  • the material of the second tin-containing oxide layer is tin oxide.
  • the second tin-containing oxide layer whose material is tin oxide has a higher concentration of oxygen vacancies, so compared with the first tin-containing oxide layer, the second tin-containing oxide layer has a higher electron transport capacity.
  • the first tin-containing oxide layer whose material is tin oxide and the second tin-containing oxide layer whose material is tin oxide are alternately stacked, which is conducive to making the oxygen vacancies in the electron transport layer uniformly distributed along the thickness direction perpendicular to the electron transport layer, and then it is conducive to making the electron transport capacity of each part of the electron transport layer along the direction perpendicular to its thickness roughly the same, preventing the occurrence of inconsistent transmission rates of electrons in each part of the electron transport layer along the direction perpendicular to the thickness, ensuring that the electrons generated by each part of the light absorbing layer along the direction perpendicular to the thickness can be effectively transmitted by the electron transport layer, and further improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the electron transport layer is a mixed material layer of tin oxide and tin oxide.
  • more implementation schemes can be provided for the distribution of tin oxide and tin oxide in the electron transport layer, thereby improving the applicability of the perovskite solar cell provided by the present application in different application scenarios.
  • the thickness of the electron transport layer is 10nm to 200nm.
  • the thickness range of the electron transport layer is relatively large, and the formation conditions such as the formation time of the electron transport layer can be strictly controlled to manufacture an electron transport layer of fixed thickness, while ensuring that the electrons generated by the light absorption layer and not recombined are conducted to the corresponding electrodes, thereby reducing the difficulty of manufacturing the electron transport layer.
  • the present application further provides a stacked solar cell.
  • the stacked solar cell includes a bottom cell and a top cell located on the bottom cell.
  • the top cell is the perovskite solar cell provided in the first aspect and various implementations thereof.
  • the present application further provides a method for manufacturing a perovskite solar cell, the method for manufacturing a perovskite solar cell comprising:
  • a substrate is provided.
  • a hole transport layer, a light absorption layer and an electron transport layer are sequentially formed on a substrate. Or, an electron transport layer, a light absorption layer and a hole transport layer are sequentially formed on a substrate.
  • the material of the electron transport layer includes tin oxide and tin oxide.
  • the stoichiometric ratio of tin element to oxygen element in the tin oxide is greater than 1:2 and less than or equal to 1:1.
  • beneficial effects of the third aspect of the present application can be analyzed by referring to the beneficial effects of the first aspect and its various implementation methods, and will not be repeated here.
  • forming the electron transport layer includes the following steps:
  • the tin source and the first oxygen source are alternately introduced into the reaction chamber X times.
  • X is a positive integer greater than or equal to 1.
  • the valence of tin in the tin source is +2.
  • the first oxygen source includes at least one of water and alcohol.
  • the tin source and the second oxygen source are alternately introduced into the reaction chamber Y times.
  • Y is a positive integer greater than or equal to 1.
  • the second oxygen source includes at least one of oxygen, ozone and hydrogen peroxide.
  • Z is a positive integer greater than or equal to 1.
  • the above-mentioned tin source and the first oxygen source are alternately introduced into the reaction chamber X times, and a tin-containing oxide layer with a certain thickness can be formed.
  • the above-mentioned tin source and the second oxygen source are alternately introduced into the reaction chamber Y times, and another tin-containing oxide layer can be formed thereon.
  • the tin source in these two operations is a +2-valent tin source, and the oxidizability of the first oxygen source and the second oxygen source is different, and the first oxygen source reacts with the +2-valent tin source to form stannous oxide, and the second oxygen source can oxidize +2-valent tin to a higher +4-valent tin, etc., the materials of the above-mentioned two tin-containing oxide layers are different. Based on this, after cycling the above-mentioned operation Z times, an electron transport layer formed by alternating the two tin-containing oxide layers Z times can be obtained.
  • the beneficial effects in this case can refer to the beneficial effects analysis of the electron transport layer including the first tin-containing oxide layer and the second tin-containing oxide layer alternately stacked as described above, which will not be repeated here.
  • forming the electron transport layer includes the steps of: alternately introducing a tin source and a mixture consisting of a first oxygen source and a second oxygen source into a reaction chamber until an electron transport layer having a target thickness is formed; wherein the valence of tin in the tin source is +2.
  • the first oxygen source includes at least one of water and alcohol.
  • the second oxygen source includes at least one of oxygen, ozone and hydrogen peroxide.
  • the formation process of one of the sublayers included in the electron transport layer is described by taking the example of first introducing a tin source into the reaction chamber: after introducing a +2-valent tin source into the reaction chamber, a mixture of a first oxygen source and a second oxygen source is introduced into the reaction chamber.
  • the material of each sublayer formed by the +2-valent tin source and the first oxygen source and the second oxygen source with different oxidizing properties includes not only tin oxide, but also tin oxide.
  • the electron transport layer formed in this way is a mixed material layer formed by a mixture of tin oxide and tin oxide. Accordingly, the beneficial effects in this case can refer to the beneficial effect analysis of the electron transport layer being a mixed material layer formed by a mixture of tin oxide and tin oxide as described above, which will not be repeated here.
  • forming the electron transport layer includes the following steps:
  • the first tin source and the oxygen source are alternately introduced into the reaction chamber X times.
  • X is a positive integer greater than or equal to 1.
  • the valence of tin in the first tin source is +2.
  • the oxygen source includes at least one of water and alcohol.
  • the second tin source and the oxygen source are alternately introduced into the reaction chamber Y times.
  • Y is a positive integer greater than or equal to 1.
  • the valence of tin in the second tin source is +4.
  • Z is greater than or A positive integer equal to 1.
  • the above-mentioned first tin source and oxygen source are alternately introduced into the reaction chamber X times, and a tin-containing oxide layer with a certain thickness can be formed.
  • the above-mentioned second tin source and oxygen source are alternately introduced into the reaction chamber Y times, and another tin-containing oxide layer can be formed thereon.
  • the oxygen source in these two operations is a weakly oxidizing oxygen source, and the valence of tin in the first tin source and the second tin source is different, and the valence of tin in the material obtained by the reaction of the first tin source and the second tin source with the weakly oxidizing oxygen source is basically unchanged without using plasma or other methods to assist the reaction, the materials of the above-mentioned two tin-containing oxide layers are different.
  • an electron transport layer formed by alternating the two tin-containing oxide layers Z times can be obtained.
  • the beneficial effects in this case can refer to the beneficial effect analysis of the electron transport layer including the first tin-containing oxide layer and the second tin-containing oxide layer alternately stacked as described above, which will not be repeated here.
  • the material formed by the reaction of the +2-valent tin source and the first oxygen source is stannous oxide.
  • the valence of tin is higher than +2 and less than or equal to +4.
  • the material formed by the reaction of the +2-valent first tin source and the oxygen source with weaker oxidizability is stannous oxide.
  • the valence of tin in the material formed by the reaction of the +4-valent second tin source and the above-mentioned oxygen source is higher than +2 and less than or equal to +4.
  • the valence of tin in the above-mentioned material is greater than or equal to +2 and less than +4.
  • One of the valences is tin oxide. Therefore, when 1 ⁇ X ⁇ 10, 30 ⁇ Y ⁇ 50, the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer ranges from 5:1 to 50:1.
  • the beneficial effects in this case can be referred to the beneficial effects of the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer described above, which ranges from 5:1 to 50:1, and will not be repeated here.
  • the beneficial effects corresponding to 1 ⁇ X ⁇ 10, and 30 ⁇ Y ⁇ 50 are the same as the above beneficial effects, which will not be repeated here.
  • forming the electron transport layer includes the steps of: alternately introducing a mixture of a first tin source and a second tin source, and an oxygen source into a reaction chamber until an electron transport layer with a target thickness is formed.
  • the valence of tin in the first tin source is +2.
  • the valence of tin in the second tin source is +4.
  • the oxygen source includes at least one of water and alcohol. The beneficial effect in this case is The beneficial effects of alternately introducing the tin source and the mixture of the first oxygen source and the second oxygen source into the reaction chamber can be referred to the analysis described above, which will not be repeated here.
  • forming an electron transport layer comprises the steps of: alternately introducing a tin source and an oxygen source into a reaction chamber Z times until an electron transport layer having a target thickness is formed. Wherein, during the X times of alternate introduction, plasma discharge is performed while introducing the tin source into the reaction chamber.
  • Z is a positive integer greater than 1.
  • X is a positive integer less than Z and greater than or equal to 1.
  • the valence of the tin in the tin source is +2.
  • the oxygen source comprises at least one of water and alcohol.
  • plasma discharge is performed while a +2-valent tin source is introduced into the reaction chamber.
  • a large number of active free radicals can be generated by the introduction of plasma, thereby enhancing the reactivity of the +2-valent tin source.
  • the tin in the +2-valent tin source can be oxidized to tin with a higher valence, so that the material of the sublayer formed after one alternation includes tin oxide and other tin valences greater than +2 valences and less than or equal to +4 valences containing tin oxides.
  • a weakly oxidizing oxygen source is introduced into the reaction chamber, and stannous oxide can be formed, thereby manufacturing a material including an electron transport layer of tin mixed valence, providing more implementation schemes for forming an electron transport layer, and improving the applicability of the manufacturing method provided by the present application in different application scenarios.
  • the method for manufacturing a perovskite solar cell further includes: purging the reaction chamber with a protective gas.
  • the excess oxygen source in the reaction chamber can be purged out of the reaction chamber to ensure that the ratio of the tin source to the oxygen source in an alternating reaction meets the requirements of the preset scheme, thereby improving the manufacturing accuracy.
  • the excess reaction byproducts in the reaction chamber can be purged out of the reaction chamber to prevent the reaction byproducts from affecting the film quality of the manufactured electron transport layer, thereby further improving the electron transport capacity of the electron transport layer.
  • the method for manufacturing a perovskite solar cell before introducing the oxygen source into the reaction chamber, also includes: purging the reaction chamber with a protective gas.
  • the excess tin source in the reaction chamber can be purged out of the reaction chamber to ensure that the ratio of the tin source and the oxygen source in an alternating reaction meets the requirements of the preset scheme, thereby improving the manufacturing accuracy.
  • the excess reaction byproducts in the reaction chamber can be purged out of the reaction chamber to prevent the reaction byproducts from affecting the film quality of the manufactured electron transport layer, thereby further improving the electron transport capacity of the electron transport layer.
  • the reaction temperature for forming the electron transport layer is 50°C to 250°C.
  • the reaction temperature for forming the electron transport layer is moderate, which prevents the incomplete reaction of the tin source and the oxygen source due to the low reaction temperature from affecting the formation quality of the electron transport layer, and can also prevent the manufacturing efficiency of the electron transport layer from being low due to the low reaction rate caused by the low reaction temperature, thereby improving the yield and rate of the perovskite solar cell.
  • it can also prevent the compatibility between the electron transport layer and the light absorption layer from being deteriorated due to the high reaction temperature, ensuring that the above-mentioned electron transport layer has high applicability in perovskite solar cells.
  • FIG1 is a schematic longitudinal cross-sectional view of a first structure of a perovskite solar cell provided in an embodiment of the present application;
  • FIG2 is a schematic longitudinal cross-sectional view of a second structure of a perovskite solar cell provided in an embodiment of the present application;
  • FIG3 is a schematic longitudinal cross-sectional view of a third structure of a perovskite solar cell provided in an embodiment of the present application.
  • FIG4 is a schematic longitudinal cross-sectional view of a fourth structure of a perovskite solar cell provided in an embodiment of the present application.
  • FIG5 is a schematic cross-sectional view of a structure of an electron transport layer included in a perovskite solar cell provided in an embodiment of the present application;
  • FIG6 is a schematic longitudinal cross-sectional view of a structure of a stacked solar cell provided in an embodiment of the present application.
  • FIG7 is a schematic longitudinal cross-sectional view of another structure of a stacked solar cell provided in an embodiment of the present application.
  • FIG8 is a flow chart of a method for manufacturing a perovskite solar cell provided in an embodiment of the present application.
  • Reference numerals: 11 is a light absorbing layer, 12 is a hole transport layer, 13 is an electron transport layer, 131 is a light absorbing layer, 132 is a first tin-containing oxide layer, 14 is a first electrode, 15 is a first transparent conductive layer, 16 is a passivation anti-reflection layer, 17 is a silicon substrate, 18 is a first intrinsic silicon layer, 19 is a P-type doped silicon layer, 20 is a second intrinsic silicon layer, 21 is an N-type doped silicon layer, 22 is a second transparent conductive layer, 23 is a third transparent conductive layer, 24 is a second electrode, and 25 is a third electrode.
  • the layer/element when a layer/element is referred to as being "on" another layer/element, the layer/element may be directly on the other layer/element, or there may be an intermediate layer/element between them. In addition, if a layer/element is "on” another layer/element in one orientation, then when the orientation is reversed, the layer/element may be "under” the other layer/element.
  • the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
  • first and second are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, a feature defined as “first” or “second” may explicitly or implicitly include one or more of the features.
  • “multiple” means two or more, unless otherwise clearly and specifically defined.
  • "Several” means one or more, unless otherwise clearly and specifically defined.
  • connection may be detachable or integral; it may be mechanical or electrical; it may be directly connected or indirectly connected through an intermediate medium; it may be the internal connection of two elements or the interaction relationship between two elements.
  • Perovskite solar cells belong to the third generation of solar cells, also known as new concept solar cells. Because the perovskite material used has a series of advantages such as high absorption coefficient, high carrier mobility, large diffusion length, and adjustable band gap, it has received widespread attention in the field of solar cells. At present, the photoelectric conversion efficiency of perovskite solar cells has exceeded 25.5%, which is comparable to the performance of mature thin-film solar cells. More importantly, perovskite solar cells can also be processed at low temperatures, which gives it a great competitive advantage in the next generation of low-cost photovoltaic processes that need to solve the stretchability problem. In addition, low-temperature processability also makes perovskite solar cells compatible with flexible wearable electronic devices.
  • the structure of an effective perovskite solar cell generally includes a hole transport layer, a light absorption layer, an electron transport layer, a transparent conductive layer and an electrode.
  • the material of the light absorption layer is a perovskite material.
  • the above-mentioned electron transport layer and hole transport layer selectively transfer electrons and holes to the transparent conductive layer or electrode, respectively. Based on this, in the actual application process, when the perovskite solar cell is irradiated by sunlight, the light absorption layer first absorbs photons to generate electron-hole pairs.
  • the uncompounded electrons and holes are collected by the electron transport layer and the hole transport layer, respectively, that is, the electrons are transferred from the light absorption layer to the electron transport layer, and finally collected by the electrode.
  • the holes are transferred from the light absorption layer to the hole transport layer, and finally collected by the electrode to generate a photocurrent.
  • the materials of the above-mentioned electron transport layer and the manufacturing method of the electron transport layer have always been the research hotspots of perovskite solar cells.
  • the materials of the existing electron transport layer are usually TiO2 and SnO2 .
  • the dense mesoporous TiO2 electron transport layer can effectively extract electrons, which makes it favored by the vast majority of researchers.
  • the manufacturing temperature of the dense mesoporous TiO2 electron transport layer exceeds 400°C, making it difficult to be compatible with perovskite solar cells with low-temperature processing characteristics.
  • the dense mesoporous TiO2 electron transport layer has photocatalytic properties, which reduces the utilization rate of light by the light absorption layer, thereby limiting its application in perovskite solar cells.
  • SnO2 has high electron mobility, its manufacturing temperature is lower than 180°C, and its corresponding -4.0eV conduction band bottom can achieve energy level matching with the light absorption layer of the perovskite material, making it the most potential.
  • Alternative electron transport materials are preferred electron transport materials.
  • the electron transport layer formed by SnO2 material has poor electron transport ability, which is not conducive to improving the photoelectric conversion efficiency of perovskite solar cells.
  • the embodiment of the present application provides a perovskite solar cell.
  • the perovskite solar cell includes: a light absorption layer 11, a hole transport layer 12 and an electron transport layer 13.
  • the above-mentioned hole transport layer 12 is formed on one side of the light absorption layer 11.
  • the electron transport layer 13 is formed on the side of the light absorption layer 11 away from the hole transport layer 12.
  • the material of the electron transport layer 13 includes tin oxide and tin oxide.
  • the stoichiometric ratio of tin element and oxygen element in the tin oxide is greater than 1:2 and less than or equal to 1:1.
  • the molecular formula of the material of the above-mentioned light absorbing layer is ABX 3.
  • a and B are cations of different sizes, and X is an anion bonded to both.
  • the cation B coordinates with the anion X to form a regular octahedral symmetrical structure, and the cation A is located at the center of the eight regular octahedra, and the cation B is located at the center of the regular octahedron.
  • the material of the light absorbing layer can be an inorganic perovskite material, an organic perovskite material, or an organic-inorganic hybrid perovskite material.
  • the material of the light absorbing layer can be CsPbI 2 Br, MAPbBr 3 , FAPbI 3 or Cs 1-yz FA y MA z PbI 3-x Br x (wherein, FA is methyl ether, MA is methylamine, 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ y+z ⁇ 1), etc.
  • the thickness of the light absorbing layer can be set according to actual needs, and no specific limitation is made here.
  • the two relative surfaces of the light absorbing layer 11 can be flat polished surfaces.
  • the side of the light absorbing layer opposite to the light receiving surface is a velvet surface
  • the side opposite to the backlight surface is a polished surface.
  • the velvet structure has a light trapping effect, so when the surface of the light absorbing layer is a velvet surface, more light can be refracted into the light absorbing layer.
  • the polished surface has relatively good reflection characteristics, after the light reaches the side of the light absorbing layer opposite to the backlight surface, it can be at least partially reflected back into the light absorbing layer and reused by the light absorbing layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the two relative surfaces of the light absorbing layer 11 can also be velvet.
  • the side of the light absorbing layer 11 in contact with the bottom cell is a velvet surface, which can refract more light into the bottom cell and improve the photoelectric conversion efficiency of the bottom cell.
  • the material of the hole transport layer can be an organic hole transport material.
  • organic hole transport material for example: 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (can be abbreviated as Sprio-OMeTAD), 2,2,7,7-tetrakis(N,N-di-p-tolyl)amino-9,9-spirobifluorene (can be abbreviated as spiro-TTB), trifluoromannose (can be abbreviated as TATM), (2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl)phosphine (can be abbreviated as MeO-2PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (can be abbreviated as Me-4PACz) or (2-(9-
  • the thickness of the electron transport layer can be set according to actual needs.
  • the thickness of the electron transport layer can be 10nm to 200nm.
  • the thickness range of the electron transport layer is relatively large.
  • the formation conditions such as the formation time of the electron transport layer can be strictly controlled to manufacture an electron transport layer of fixed thickness, thereby reducing the difficulty of manufacturing the electron transport layer.
  • the materials of the electron transport layer include tin oxide and tin oxide.
  • the specific stoichiometric ratio of tin element and oxygen element in tin oxide the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer, and the distribution of tin oxide and tin oxide in the electron transport layer can be set according to actual needs, as long as they can be applied to the perovskite solar cell provided in the embodiment of the present application.
  • the perovskite solar cell provided in the embodiment of the present application may be a trans structure, that is, the hole transport layer 12, the light absorption layer 11 and the electron transport layer 13 are stacked in sequence from top to bottom.
  • the perovskite solar cell provided in the embodiment of the present application may also be a formal structure, that is, the electron transport layer 13, the light absorption layer 11 and the hole transport layer 12 are stacked in sequence from top to bottom.
  • the perovskite solar cell provided in the embodiment of the present application further includes a first electrode 14 and a first transparent conductive layer 15.
  • the first electrode 14 is formed on the side of the hole transport layer 12 away from the light absorption layer 11, and is used to guide out the holes collected by the hole transport layer.
  • the first transparent conductive layer 15 is formed on the side of the electron transport layer 13 away from the light absorption layer 11, and is used to guide out the electrons collected by the electron transport layer.
  • the material of the first electrode may be a conductive material such as aluminum, gold, silver, copper, tungsten, etc.
  • the material of the first transparent conductive layer may be any one of indium tin oxide, fluorine-doped tin oxide, indium-doped zinc oxide, indium tungsten oxide, aluminum-doped zinc oxide, or boron-doped zinc oxide, or a combination of at least two thereof.
  • the thickness of the first transparent conductive layer may be set according to actual needs and is not specifically limited here.
  • the light absorption layer 11 absorbs photons and generates electron and hole pairs.
  • the holes that have not been recombined move in the direction close to the hole transport layer 12 and are conducted to the corresponding electrode via the hole transport layer 12.
  • the electrons that have not been recombined move in the direction close to the electron transport layer 13 and are conducted to the corresponding electrode via the electron transport layer 13, thereby forming a photocurrent.
  • the material of the above-mentioned electron transport layer 13 includes tin oxide and tin oxide.
  • the stoichiometric ratio of tin element and oxygen element in tin oxide is 1:2.
  • the stoichiometric ratio of tin element and oxygen element in the above-mentioned tin oxide is greater than 1:2, and less than or equal to 1:1. It can be understood that the ratio of oxygen in the above-mentioned tin oxide is lower than the ratio of oxygen in tin oxide.
  • the material of the electron transport layer 13 included in the perovskite solar cell provided in the embodiment of the present application includes not only tin oxide, but also the above-mentioned tin oxide.
  • the Sn/O ratio in the electron transport layer 13 in the embodiment of the present application can be increased, thereby increasing the oxygen vacancy concentration in the electron transport layer 13.
  • the conductive principle of the above-mentioned electron transport layer 13 is that the outer electrons of the tin element form a chemical bond with the outer electrons of the oxygen element, when there is a lack of oxygen in the electron transport layer 13, the outer electrons of the tin element form free electrons to achieve conductivity.
  • the oxygen vacancy concentration in the electron transport layer 13 included in the perovskite solar cell provided in the embodiment of the present application increases, the more free electrons are formed in the electron transport layer 13, thereby improving the electron transport capacity of the electron transport layer 13, accelerating the separation of electrons and holes at the interface where the light absorption layer 11 and the electron transport layer 13 are in contact, reducing the interface recombination loss of electrons, and thus helping to improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the specific types of the above tin oxides are related to the stoichiometric ratio of the tin element and the oxygen element in the tin oxide.
  • the specific types of tin oxides can be divided into the following two cases according to the specific stoichiometric ratio of the tin element and the oxygen element in the tin oxide:
  • the first type the stoichiometric ratio of tin element and oxygen element in the tin oxide may be 1: 1.
  • the tin oxide is stannous oxide
  • the material of the electron transport layer includes tin oxide and stannous oxide.
  • the stoichiometric ratio of the tin element and the oxygen element in the tin oxide can be a decimal greater than 1:2 and less than 1:1.
  • the valence of a portion of the tin in the tin oxide can be +4, and the valence of another portion of the tin can be +2.
  • the tin oxide is tritin tetroxide or pentatin hexaoxide.
  • tin oxide includes stannous oxide and tritin tetroxide.
  • the valence of tin in stannous oxide is +2 and the valence of oxygen is -2. Based on this, in the case where tin oxide includes stannous oxide, it is possible to dope Sn 2+ in tin oxide, thereby producing a mixed valence electron transport layer, which is beneficial to increase the concentration of oxygen vacancies in the electron transport layer. Moreover, compared with the numerical value of the stoichiometric ratio of tin and oxygen including decimals in tin oxide, the ratio of tin element in stannous oxide is the same as the ratio of oxygen element, which is convenient for adjusting the ratio of tin source and oxygen source for manufacturing stannous oxide, and reducing the difficulty of manufacturing tin oxide. In addition, the chemical properties of stannous oxide at room temperature and pressure are relatively stable, which can improve the working stability of perovskite solar cells including the electron transport layer.
  • the specific stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer can be set according to actual needs.
  • the stoichiometric ratio of tin oxide and stannous oxide in the above-mentioned electron transport layer can range from 5:1 to 50:1. It can be understood that the greater the ratio of the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer, the higher the content of tin oxide in the electron transport layer, and the lower the content of stannous oxide therein.
  • the concentration of oxygen vacancies in the electron transport layer is smaller.
  • the smaller the ratio of the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer the greater the concentration of oxygen vacancies in the electron transport layer.
  • the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer ranges from 5:1 to 50:1
  • the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer is moderate, which can prevent the oxygen vacancy concentration in the electron transport layer from being low due to the large stoichiometric ratio, and ensure that the electron transport layer has appropriate electron transport capacity.
  • the perovskite solar cell has a higher photoelectric conversion efficiency.
  • the electron transport layer 13 includes a first tin-containing oxide layer 131 and a second tin-containing oxide layer 132 alternately stacked.
  • the material of the first tin-containing oxide layer 131 is tin oxide.
  • the material of the second tin-containing oxide layer 132 is tin oxide.
  • the film layer in the electron transport layer that contacts the light absorption layer may be a first tin-containing oxide layer or a second tin-containing oxide layer.
  • the film layer in contact with the first electrode of the electron transport layer may be a first tin-containing oxide layer or a second tin-containing oxide layer.
  • the number and thickness of the first tin-containing oxide layer and the second tin-containing oxide layer included in the electron transport layer may be determined according to the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer, the total thickness of the electron transport layer, and actual needs, and are not specifically limited here.
  • the number of layers of the first tin oxide layer may be greater than or equal to 30 and less than or equal to 50.
  • the number of layers of the second tin oxide layer may be greater than or equal to 1 and less than or equal to 10.
  • the second tin-containing oxide layer whose material is tin oxide has a higher concentration of oxygen vacancies, so compared with the first tin-containing oxide layer, the second tin-containing oxide layer has a higher electron transport capacity.
  • the first tin-containing oxide layer whose material is tin oxide and the second tin-containing oxide layer whose material is tin oxide are alternately stacked, which is conducive to making the oxygen vacancies in the electron transport layer uniformly distributed along the thickness direction perpendicular to the electron transport layer, and then it is conducive to making the electron transport capacity of each part of the electron transport layer along the direction perpendicular to its thickness roughly the same, preventing the occurrence of inconsistent transmission rates of electrons in each part of the electron transport layer along the direction perpendicular to the thickness, ensuring that the electrons generated by each part of the light absorbing layer along the direction perpendicular to the thickness can be effectively transmitted by the electron transport layer, and further improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the above-mentioned electron transport layer is a mixed material layer of tin oxide and tin oxide.
  • more implementation schemes can be provided for the distribution of tin oxide and tin oxide in the electron transport layer, which improves the applicability of the perovskite solar cell provided in the embodiment of the present application in different application scenarios.
  • the perovskite solar cell provided in the embodiment of the present application further includes a passivation anti-reflection layer 16 to passivate the light-receiving surface of the perovskite solar cell. Passivation reduces the recombination rate of carriers on the light-receiving side and improves the photoelectric conversion efficiency of the perovskite solar cell.
  • the passivation anti-reflection layer 16 can also allow more light to be refracted from the light-receiving surface of the perovskite solar cell to the inside of the battery, thereby improving the utilization rate of light energy by the perovskite solar cell.
  • the formation position of the above-mentioned passivation anti-reflection layer 16 is related to the specific structure of the perovskite solar cell.
  • the passivation anti-reflection layer 16 is formed on the side of the hole transport layer 12 away from the light absorption layer 11.
  • the passivation anti-reflection layer 16 is formed on the side of the electron transport layer 13 away from the light absorption layer 11.
  • the material of the passivation anti-reflection layer can be magnesium fluoride, silicon nitride, silicon oxide or lithium fluoride, etc.
  • the thickness of the passivation anti-reflection layer can be set according to actual needs and is not specifically limited here.
  • the embodiment of the present application also provides a stacked solar cell.
  • the stacked solar cell includes a bottom cell and a top cell located on the bottom cell.
  • the top cell is the perovskite solar cell provided in the above embodiment.
  • the bottom cell can be a heterojunction cell, a passivated emitter back cell, a tunneling oxide passivated contact cell, a cross-finger back contact cell or a cross-finger back contact heterojunction cell, etc.
  • the bottom cell and the top cell in the stacked solar cell are connected in series.
  • the hole transport layer 12 included in the perovskite solar cell can be arranged above the bottom cell.
  • the positive electrode of the top cell is coupled with the negative electrode of the bottom cell to achieve the series connection of the two.
  • the electron transport layer 13 included in the perovskite solar cell can also be arranged above the bottom cell.
  • the negative electrode of the top cell is coupled with the positive electrode of the bottom cell to achieve the series connection of the two.
  • the bottom cell may include a silicon substrate 17, a first intrinsic silicon layer 18, a P-type doped silicon layer 19, a second intrinsic silicon layer 20 and an N-type doped silicon layer 21.
  • the second intrinsic silicon layer 20 and the N-type doped silicon layer 21 are sequentially stacked on the light-receiving surface of the silicon substrate 17 in a direction away from the silicon substrate 17.
  • the first intrinsic silicon layer 18 and the P-type doped silicon layer 19 are sequentially stacked on the backlight surface of the silicon substrate 17.
  • the electron transport layer 13 included in the perovskite solar cell is disposed above the bottom cell, the first intrinsic silicon layer 18 and the P-type doped silicon layer 19 are sequentially stacked on the light-receiving surface of the silicon substrate 17 in a direction away from the silicon substrate 17.
  • the second intrinsic silicon layer 20 and the N-type doped silicon layer 21 are sequentially stacked on the backlight surface of the silicon substrate 17 in a direction away from the silicon substrate 17.
  • the stacked solar cell further includes a second electrode 24, a third electrode 25, a second transparent conductive layer 22, and a third transparent conductive layer 23.
  • the second transparent conductive layer 22 is formed on the side of the hole transport layer 12 away from the light absorption layer 11.
  • the third transparent conductive layer 23 is formed on the backlight side of the bottom cell.
  • the second electrode 24 is formed on the light receiving side of the perovskite solar cell.
  • the third electrode 25 is formed on the third transparent conductive layer 23.
  • the materials of the second electrode 24 and the second electrode 24 can refer to the materials of the first electrode described above.
  • the materials of the second transparent conductive layer 22 and the third transparent conductive layer 23 can refer to the materials of the first transparent conductive layer described above.
  • the beneficial effects of the stacked solar cell provided in the embodiment of the present application can be analyzed by referring to the beneficial effects of the perovskite solar cell provided in the above embodiment, and will not be repeated here.
  • the embodiment of the present application further provides a method for manufacturing a perovskite solar cell, and the method for manufacturing a perovskite solar cell comprises the following steps:
  • the substrate may be a transparent conductive substrate on which no other structures are formed.
  • the substrate may be a tin oxide transparent conductive glass substrate.
  • the substrate may also be a substrate on which some film layers are formed.
  • the specific structure of the substrate on which some film layers are formed may be set according to the actual application scenario, as long as it can be applied to the manufacturing method of the perovskite solar cell provided in the embodiment of the present application.
  • the substrate on which some film layers are formed may be the bottom battery described above.
  • a hole transport layer 12, a light absorption layer 11 and an electron transport layer 13 are sequentially formed on a substrate.
  • an electron transport layer 13, a light absorption layer 11 and a hole transport layer 12 are sequentially formed on a substrate.
  • the material of the electron transport layer 13 includes tin oxide and tin oxide. The stoichiometric ratio of tin element to oxygen element in tin oxide is greater than 1:2 and less than or equal to 1:1.
  • the manufacturing order of each film layer included in the perovskite solar cell can be determined according to whether the manufactured perovskite solar cell has a regular structure or a trans-structure.
  • an electron transport layer, a light absorption layer, and a hole transport layer can be sequentially formed on the substrate, so that the hole transport layer is close to the light-receiving surface of the perovskite solar cell.
  • the perovskite solar cell has a formal structure
  • a hole transport layer, a light absorption layer, and an electron transport layer can be sequentially formed on the substrate, so that the electron transport layer is close to the light-receiving surface of the perovskite solar cell.
  • the beneficial effects of the method for manufacturing a perovskite solar cell provided in the embodiment of the present application can be analyzed by referring to the beneficial effects of the perovskite solar cell provided in the above embodiment, and will not be repeated here.
  • an electron transport layer can be formed on a substrate by processes such as atomic layer deposition and plasma-assisted atomic layer deposition.
  • a light absorption layer can be formed on the electron transport layer by a solution method or other processes.
  • a hole transport layer can be formed on the light absorption layer by a spin coating or other processes.
  • the atomic layer deposition process is a thin film formation process using continuous chemical reactions in the gas phase, it can plate the material on the substrate surface layer by layer in the form of a single atomic film, so the use of the atomic layer deposition process to manufacture the electron transport layer can make the thickness of the formed electron transport layer uniform.
  • the atomic layer deposition process has a self-limiting mechanism, which can facilitate the control of the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer while improving the thickness accuracy of the electron transport layer, ensuring that the electron transport layer has a high electron transport capacity.
  • the manufacturing method of the perovskite solar cell preferably uses an atomic layer deposition process to manufacture the electron transport layer.
  • an atomic layer deposition process to manufacture the electron transport layer.
  • the stoichiometric ratio of tin and oxygen in the formed tin-containing oxide is different due to the different valence of tin in the above-mentioned tin source and the different oxidizing strength of the oxygen source.
  • the tin source and oxygen source included in the reaction raw materials can be divided into at least the following three cases for explanation:
  • the first type: the valence of tin in the tin source is +2.
  • the oxygen source includes a first oxygen source and a second oxygen source.
  • the first oxygen source includes at least one of water and alcohol.
  • the second oxygen source includes at least one of oxygen, ozone and hydrogen peroxide.
  • the above-mentioned water and alcohol have weak oxidizing properties, while oxygen, ozone and hydrogen peroxide have strong oxidizing properties.
  • the first oxygen source reacts with the +2-valent tin source to form stannous oxide.
  • the second oxygen source can oxidize +2-valent tin to higher +4-valent tin, etc., so that an electron transport layer including a mixed valence state of tin can be manufactured.
  • the tin source when the tin valence in the tin source is +2, the tin source can be dimethylamino-2-methyl-2-propoxytin(II), bis(N-ethoxy-2,2-dimethylpropionamido)tin(II) or bis(tert-pentyloxy)-tin(II).
  • the first oxygen source may be water alone, alcohol alone, or a mixed solution of water and alcohol.
  • the ratio of water to alcohol in the mixed solution may be set according to actual needs and is not specifically limited here.
  • the alcohol may be ethanol, propanol, etc.
  • the second oxygen source may include only any one of oxygen, ozone and hydrogen peroxide.
  • the second oxygen source may include any two of oxygen, ozone and hydrogen peroxide.
  • the second oxygen source may include oxygen, ozone and hydrogen peroxide.
  • the ratio of each component in the second oxygen source may be set according to actual needs, and is not specifically limited here.
  • the manner of introducing the tin source, the first oxygen source and the second oxygen source into the reaction chamber can be determined according to the distribution of tin oxide and tin oxide in the electron transport layer.
  • forming the electron transport layer includes the following steps: first, alternately introducing a tin source and a first oxygen source into the reaction chamber X times.
  • X is a positive integer greater than or equal to 1.
  • Y is a positive integer greater than or equal to 1.
  • the above operation is repeated Z times until an electron transport layer having a target thickness is formed.
  • Z is a positive integer greater than or equal to 1.
  • the tin source and the first oxygen source are alternately introduced into the reaction chamber X times to form a tin-containing oxide layer having a certain thickness.
  • the tin source and the second oxygen source are alternately introduced into the reaction chamber Y times to form another tin-containing oxide layer thereon.
  • the tin source in these two operations is a +2 valent tin source and the oxidizing properties of the first oxygen source and the second oxygen source are Different, at the same time, the first oxygen source reacts with the +2-valent tin source to form stannous oxide, and the second oxygen source can oxidize +2-valent tin to a higher +4-valent tin, etc., so the materials of the above two tin-containing oxide layers are different.
  • an electron transport layer formed by alternating the two tin-containing oxide layers Z times can be obtained.
  • the beneficial effects in this case can refer to the beneficial effects analysis of the electron transport layer including the first tin-containing oxide layer and the second tin-containing oxide layer alternately stacked as described above, which will not be repeated here.
  • the tin source when performing the first step, is introduced into the reaction chamber once, and the first oxygen source is introduced once as an alternation.
  • the first oxygen source may be introduced into the reaction chamber for a certain time first, and then the tin source is introduced into the reaction chamber for a certain time after the first oxygen source is stopped.
  • the tin source may be introduced into the reaction chamber for a certain time first, and then the first oxygen source is introduced into the reaction chamber for a certain time after the tin source is stopped.
  • the order of introducing the tin source and the second oxygen source can refer to the order of introducing the tin source and the first oxygen source in the first step described above, which will not be described in detail here.
  • the time for each alternating introduction of the tin source and the first oxygen source during the first step, and the time for each alternating introduction of the tin source and the second oxygen source during the second step can be set according to the actual application scenario.
  • the time for each alternating introduction of the tin source during the first step can be 10s to 20s
  • the time for the introduction of the first oxygen source can be 10s to 20s
  • the time for each alternating introduction of the tin source during the second step can be 10s to 20s
  • the time for the introduction of the second oxygen source can be 10s to 20s.
  • the specific values of X and Y can be determined according to the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer. Exemplarily, 1 ⁇ X ⁇ 10, 30 ⁇ Y ⁇ 50.
  • the material formed by the reaction of the +2-valent tin source and the first oxygen source is stannous oxide.
  • the valence of tin is higher than +2 and less than or equal to +4.
  • one of the valences of tin in the above-mentioned materials is greater than or equal to +2 and less than +4 is tin oxide.
  • the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer ranges from 5:1 to 50:1, and the beneficial effects in this case can be referred to the stoichiometric ratio of tin oxide and stannous oxide in the electron transport layer described above.
  • the range is 5:1 to 50:1 has a beneficial effect analysis, which will not be repeated here.
  • the specific value of Z can be determined according to the target thickness of the electron transport layer. For example: In the case where the target thickness of the electron transport layer is 30 nm, Z may be equal to 230.
  • the tin source and the second oxygen source may be introduced alternately into the reaction chamber Y times. Then, the tin source and the first oxygen source may be introduced alternately into the reaction chamber X times. Then, the above operation is repeated Z times until an electron transport layer having a target thickness is formed.
  • the operation step of introducing the tin source and the first oxygen source alternately into the reaction chamber X times and the operation step of introducing the tin source and the second oxygen source alternately into the reaction chamber Y times can be interchanged in the order of execution.
  • forming an electron transport layer includes the steps of: alternately introducing a tin source and a mixture consisting of a first oxygen source and a second oxygen source into a reaction chamber until an electron transport layer having a target thickness is formed.
  • introducing a tin source into the reaction chamber once, and introducing a mixture consisting of a first oxygen source and a second oxygen source once is an alternation.
  • the tin source may be introduced first, and then the above mixture may be introduced.
  • the above mixture may be introduced first, and then the tin source may be introduced.
  • the introduction time of the tin source and the above mixture, and the ratio of the first oxygen source and the second oxygen source in the mixture can be determined according to the stoichiometric ratio of tin element and oxygen element in tin oxide, and the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer, and are not specifically limited here.
  • the formation process of one of the sublayers included in the electron transport layer is described by taking the example of first introducing a tin source into the reaction chamber: after introducing a +2-valent tin source into the reaction chamber, a mixture of a first oxygen source and a second oxygen source is introduced into the reaction chamber.
  • the material of each sublayer formed by the +2-valent tin source and the first oxygen source and the second oxygen source with different oxidizing properties includes not only tin oxide, but also tin oxide.
  • the electron transport layer formed in this way is a mixed material layer formed by a mixture of tin oxide and tin oxide. Accordingly, the beneficial effects in this case can refer to the beneficial effect analysis of the electron transport layer being a mixed material layer formed by a mixture of tin oxide and tin oxide as described above, which will not be repeated here.
  • the tin source includes a first tin source and a second tin source.
  • the valence of tin in the first tin source is +2, and the valence of tin in the second tin source is +4.
  • the oxygen source includes at least one of water and alcohol.
  • the types of +2-valent tin sources can be referred to above.
  • the +4-valent tin source can be tetrakis(dimethylamino)tin or the like.
  • the manner of introducing the first tin source, the second tin source and the oxygen source into the reaction chamber can also be determined according to the distribution of tin oxide and tin oxide in the electron transport layer.
  • forming an electron transport layer includes the following steps: First, the first tin source and the oxygen source are alternately introduced into the reaction chamber X times. X is a positive integer greater than or equal to 1. Next, the second tin source and the oxygen source are alternately introduced into the reaction chamber Y times. Y is a positive integer greater than or equal to 1. Then the above operation is circulated Z times until an electron transport layer with a target thickness is formed. Z is a positive integer greater than or equal to 1. In this case, the first tin source and the oxygen source are alternately introduced into the reaction chamber X times, and a layer of tin-containing oxide layer with a certain thickness can be formed.
  • the second tin source and the oxygen source are alternately introduced into the reaction chamber Y times, and another layer of tin-containing oxide layer can be formed thereon.
  • the oxygen source in these two operations is a weakly oxidizing oxygen source, and the valence of tin in the first tin source and the second tin source is different, and the valence of tin in the material obtained by the reaction of the first tin source and the second tin source with the weakly oxidizing oxygen source is basically unchanged without using plasma or other methods to assist the reaction, the materials of the above two tin-containing oxide layers are different.
  • an electron transport layer formed by alternating the two tin-containing oxide layers Z times can be obtained.
  • the beneficial effects in this case can be referred to the beneficial effects analysis of the electron transport layer including the first tin-containing oxide layer and the second tin-containing oxide layer alternately stacked as described above, which will not be repeated here.
  • the first tin source is introduced into the reaction chamber once, and the oxygen source is introduced once as an alternation.
  • the oxygen source may be introduced into the reaction chamber for a certain time first, and then the first tin source is introduced into the reaction chamber for a certain time after the oxygen source is stopped.
  • the first tin source may be introduced into the reaction chamber for a certain time first, and then the oxygen source is introduced into the reaction chamber for a certain time after the first tin source is stopped.
  • the order of introducing the second tin source and the oxygen source can refer to the order of introducing the first tin source and the oxygen source in the first step described above, which will not be described in detail here.
  • the time for introducing the first tin source and the oxygen source in each alternation during the first step of the operation, and the time for introducing the second tin source and the oxygen source in each alternation during the second step of the operation can be adjusted according to the actual application scenario.
  • the first tin source may be introduced for 10 to 20 seconds, and the oxygen source may be introduced for 10 to 30 seconds in each alternation.
  • the second tin source may be introduced for 10 to 20 seconds, and the oxygen source may be introduced for 10 to 30 seconds in each alternation.
  • X and Y can be determined according to the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer. For example, 1 ⁇ X ⁇ 10, 30 ⁇ Y ⁇ 50. The beneficial effects in this case can be referred to above and will not be repeated here.
  • the specific value of Z can be determined according to the target thickness of the electron transport layer. For example, when the target thickness of the electron transport layer is 50 nm, Z can be equal to 380.
  • the second tin source and the oxygen source may be introduced alternately into the reaction chamber Y times. Then, the first tin source and the oxygen source may be introduced alternately into the reaction chamber X times. Then, the above operation is repeated Z times until an electron transport layer having a target thickness is formed.
  • the operation step of introducing the first tin source and the oxygen source alternately into the reaction chamber X times and the operation step of introducing the second tin source and the oxygen source alternately into the reaction chamber Y times can be interchanged in the order of execution.
  • forming the electron transport layer includes the steps of: alternately introducing a mixture consisting of a first tin source and a second tin source, and an oxygen source into the reaction chamber until an electron transport layer having a target thickness is formed.
  • a mixture of a first tin source and a second tin source is introduced into the reaction chamber once, and an oxygen source is introduced once for an alternation.
  • the above-mentioned mixture may be introduced first, and then the oxygen source may be introduced.
  • the oxygen source may be introduced first, and then the above-mentioned mixture may be introduced.
  • the introduction time of the above-mentioned mixture and the oxygen source, and the ratio of the first tin source and the second tin source in the mixture may be determined according to the stoichiometric ratio of the tin element and the oxygen element in the tin oxide, and the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer, and are not specifically limited here.
  • the third type the valence of the tin in the above-mentioned tin source is +2.
  • the oxygen source includes at least one of water and alcohol.
  • forming the electron transport layer includes the steps of: alternately introducing the tin source and the oxygen source into the reaction chamber Z times until an electron transport layer with a target thickness is formed. Wherein, during the X-times of alternating introduction, plasma discharge is performed while the tin source is introduced into the reaction chamber.
  • Z is a positive integer greater than 1.
  • X is a positive integer less than Z and greater than or equal to 1.
  • a plasma discharge is performed while a +2-valent tin source is introduced into the reaction chamber.
  • a large number of active free radicals can be generated through the introduction of plasma, thereby enhancing the +2-valent The reactivity of the tin source.
  • the tin in the +2-valent tin source can be oxidized to tin with a higher valence, so that the material of the sublayer formed after one alternation includes tin oxide and other tin oxides whose valence is greater than +2 and less than or equal to +4.
  • the size of the above X and Z can be determined according to the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer, and the target thickness of the electron transport layer. For example: when the stoichiometric ratio of tin oxide and tin oxide in the electron transport layer is 50:1 and Z is equal to 8250, X is equal to 165.
  • the specific time when the tin source is introduced for plasma discharge assistance can be determined based on the distribution of tin oxide and tin oxide in the electron transport layer, and is not specifically limited here.
  • the method for manufacturing a perovskite solar cell further includes: purging the reaction chamber with a protective gas.
  • the excess oxygen source in the reaction chamber can be purged out of the reaction chamber to ensure that the ratio of the tin source to the oxygen source in an alternating reaction meets the requirements of the preset scheme, thereby improving the manufacturing accuracy.
  • the excess reaction byproducts in the reaction chamber can be purged out of the reaction chamber to prevent the reaction byproducts from affecting the film quality of the manufactured electron transport layer, thereby further improving the electron transport capacity of the electron transport layer.
  • the method for manufacturing a perovskite solar cell before introducing the oxygen source into the reaction chamber, also includes: purging the reaction chamber with a protective gas.
  • the excess tin source in the reaction chamber can be purged out of the reaction chamber to ensure that the ratio of the tin source and the oxygen source in an alternating reaction meets the requirements of the preset scheme, thereby improving the manufacturing accuracy.
  • the excess reaction byproducts in the reaction chamber can be purged out of the reaction chamber to prevent the reaction byproducts from affecting the film quality of the manufactured electron transport layer, thereby further improving the electron transport capacity of the electron transport layer.
  • the purge time of the reaction chamber purged with the protective gas before the tin source is introduced into the reaction chamber can be set according to the actual application scenario, and are not specifically limited here.
  • the purge time can be 10s to 30s.
  • the protective gas can be nitrogen, helium, argon, etc.
  • the reaction temperature for forming the electron transport layer is 50°C to 250°C.
  • the reaction temperature for forming the electron transport layer is moderate, which prevents the incomplete reaction of the tin source and the oxygen source due to the low reaction temperature from affecting the formation quality of the electron transport layer, and can also prevent the manufacturing efficiency of the electron transport layer from being low due to the low reaction rate caused by the low reaction temperature, thereby improving the yield and rate of the perovskite solar cell.
  • it can also prevent the compatibility between the electron transport layer and the light absorption layer from being deteriorated due to the high reaction temperature, ensuring that the above-mentioned electron transport layer has high applicability in perovskite solar cells.
  • reaction temperature of the electron transport layer may also be set to other appropriate values according to different practical application scenarios, which is not specifically limited here.
  • the present application also provides the following specific embodiments to further illustrate the method for manufacturing the perovskite solar cell described in the present application.
  • the specific operation steps are as follows:
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Transparent conductive glass is used as a substrate.
  • the cleaned substrate is placed in the reaction chamber of the atomic layer deposition equipment and the vacuum is pumped to 0.1 Pa.
  • the temperature in the reaction chamber is maintained at 100°C, and 50sccm N2 is introduced as a tin source carrier gas.
  • Dimethylamino-2-methyl-2-propoxytin (II) is used as a tin source, and the tin source is maintained at 80°C.
  • the first oxygen source and the second oxygen source are divided into H2O source and O3 source, and the first oxygen source and the second oxygen source are maintained at room temperature.
  • the tin source is introduced into the reaction chamber for 12s, followed by N2 purge for 15s.
  • the O3 source is introduced into the reaction chamber for 12s, followed by N2 purge for 15s, as a first cycle.
  • the tin source is introduced into the reaction chamber for 12s, followed by N2 purge for 15s.
  • the H2O source is introduced into the reaction chamber for 12s, followed by N2 purge for 15s, as a second cycle.
  • the above second cycle is performed 5 times.
  • a light absorption layer with a material of (FAPbI 3 ) 0.87 (MAPbI 3 ) 0.13 and a thickness of 800 nm was formed on the electron transport layer.
  • a hole transport layer with a material of spiro-MeOTAD and a thickness of 150 nm was formed on the light absorption layer.
  • a first electrode with a material of gold and a thickness of 100 nm was formed on the hole transport layer to obtain a perovskite solar cell.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Transparent conductive glass was used as the substrate.
  • the cleaned substrate was placed in the reaction chamber of the atomic layer deposition equipment and the vacuum was pumped to 0.1 Pa.
  • the temperature in the reaction chamber was maintained at 120°C, and 50 sccm N 2 was introduced as the tin source carrier gas.
  • Tetrakis(dimethylamino)tin(IV) and dimethylamino were used at a temperature of 80°C.
  • -2-methyl-2-propoxytin (II) as the first tin source and the second tin source respectively.
  • H 2 O at room temperature is used as the oxygen source.
  • a tetrakis(dimethylamino)tin(IV) source is first introduced into the reaction chamber for 10s, followed by N 2 purge for 12s. Then, an H 2 O source is introduced into the reaction chamber for 10s, followed by N 2 purge for 12s, as a first cycle. After performing the above first cycle 30 times, a dimethylamino-2-methyl-2-propoxytin (II) source is first introduced into the reaction chamber for 10s, followed by N 2 purge for 12s. Then, an H 2 O source is introduced into the reaction chamber for 10s, followed by N 2 purge for 12s, as a second cycle. And the above second cycle is performed 3 times. By alternately performing the above first cycle and the second cycle 380 times, an electron transport layer with a target thickness of 50nm can be formed.
  • II dimethylamino-2-methyl-2-propoxytin
  • a light absorption layer made of Cs 0.05 FA 0.8 MA 0.15 PbI 3 and having a thickness of 1000 nm was formed on the electron transport layer.
  • a hole transport layer made of spiro-MeOTAD and having a thickness of 50 nm was formed on the light absorption layer.
  • a first electrode made of gold and having a thickness of 100 nm was formed on the hole transport layer to obtain a perovskite solar cell.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Transparent conductive glass was used as the substrate.
  • the cleaned substrate was placed in the reaction chamber of the atomic layer deposition equipment and vacuumed to 0.1 Pa.
  • the temperature in the reaction chamber was maintained at 120°C, and 50 sccm N 2 was introduced as the tin source carrier gas.
  • Dimethylamino-2-methyl-2-propoxytin (II) was used as the tin source, and the tin source was maintained at 80°C. H 2 O at room temperature was used as the oxygen source.
  • the dimethylamino-2-methyl-2-propoxytin (II) source was first introduced into the reaction chamber for 10s, followed by N 2 purge for 12s, and then the H 2 O source was introduced into the reaction chamber for 10s, followed by N 2 purge for 12s.
  • the plasma subsystem was set to follow the tin source introduction time to make pulse modulated radio frequency discharge, which was used as a first cycle.
  • a dimethylamino-2-methyl-2-propoxytin (II) source is introduced into the reaction chamber for 10 seconds, followed by N2 purge for 12 seconds, and then an H2O source is introduced into the reaction chamber for 10 seconds, followed by N2 purge for 12 seconds.
  • the pulse modulated radio frequency is set to no longer discharge, which is a second cycle.
  • the second cycle is executed 5 times.
  • an electron transport layer with a target thickness of 20 nm can be formed.
  • a light absorption layer made of Cs 0.05 FA 0.8 MA 0.15 PbI 3 and having a thickness of 1000 nm was formed on the electron transport layer.
  • a hole transport layer made of spiro-MeOTAD and having a thickness of 50 nm was formed on the light absorption layer.
  • a first electrode made of gold and having a thickness of 100 nm was formed on the hole transport layer to obtain a perovskite solar cell.
  • the present application also provides the following comparative example for manufacturing a perovskite solar cell, and the specific operation steps are as follows:
  • Transparent conductive glass is used as the substrate.
  • the cleaned substrate is placed in the reaction chamber of the atomic layer deposition equipment and the vacuum is pumped to 0.1 Pa.
  • the temperature in the reaction chamber is maintained at 120°C, and 50sccm N2 is introduced as the tin source carrier gas.
  • An atomic layer deposition process is adopted, with tetrakis(dimethylamino)tin(IV) as the tin source, and H2O or O3 as the oxygen source.
  • the tin source is first introduced into the reaction chamber for 10s to 20s, followed by N2 purge for 10s to 50s.
  • an oxygen source is introduced into the reaction chamber for 10s to 20s, and N2 purge time is 10s to 50s.
  • an electron transport layer with a target thickness of 20nm can be formed.
  • a light absorption layer made of Cs 0.05 FA 0.8 MA 0.15 PbI 3 and having a thickness of 1000 nm was formed on the electron transport layer.
  • a hole transport layer made of spiro-MeOTAD and having a thickness of 50 nm was formed on the light absorption layer.
  • a first electrode made of gold and having a thickness of 100 nm was formed on the hole transport layer to obtain a perovskite solar cell.
  • Table 1 tests the perovskite solar cells manufactured by the above-mentioned Example 1, Example 2, Example 3 and the comparative example, and compares the parameters of the above-mentioned four perovskite solar cells.

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Abstract

本申请公开了一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池，涉及太阳能电池技术领域，用于增强电子传输层具有的电子传输能力，利于提升包括该电子传输层的钙钛矿太阳能电池的光电转换效率。所述钙钛矿太阳能电池包括：光吸收层、空穴传输层和电子传输层。上述空穴传输层形成在光吸收层的一侧。电子传输层形成在光吸收层背离空穴传输层的一侧。电子传输层的材料包括氧化锡和锡氧化物。该锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。所述钙钛矿太阳能电池的制造方法用于制造所述钙钛矿太阳能电池。所述叠层太阳能电池包括的顶电池为所述钙钛矿太阳能电池。

Description

一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池
本申请要求在2022年9月28日提交中国专利局、申请号为202211194077.8、名称为“一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池”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
本申请涉及太阳能电池技术领域，尤其涉及一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池。
背景技术
钙钛矿太阳能电池属于第三代太阳能电池，也称作新概念太阳能电池。因为其采用的钙钛矿材料具有吸光系数高、载流子迁移率高和扩散长度大、带隙可调节等一系列优点，故在太阳能电池领域受到了广泛的关注。
但是，现有的钙钛矿太阳能电池包括的电子传输层的材料为氧化锡(化学式为SnO2，也可以称为二氧化锡)，导致电子传输层具有的电子传输能力不佳，不利于提高钙钛矿太阳能电池的光电转换效率。
发明内容
本申请的目的在于提供一种钙钛矿太阳能电池及其制造方法、叠层太阳能电池，用于增强电子传输层具有的电子传输能力，利于提升包括该电子传输层的钙钛矿太阳能电池的光电转换效率。
第一方面，本申请提供了一种钙钛矿太阳能电池，该钙钛矿太阳能电池包括：光吸收层、空穴传输层和电子传输层。上述空穴传输层形成在光吸收层的一侧。电子传输层形成在光吸收层背离空穴传输层的一侧。电子传输层的材料包括氧化锡和锡氧化物。该锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
采用上述技术方案的情况下，本申请提供的钙钛矿太阳能电池包括光吸收层、以及分别形成在光吸收层具有的相对两侧的空穴传输层和电子传输层。 基于此，在实际的工作过程中，光吸收层吸收光子后会产生电子和空穴对。其中，未发生复合的空穴沿着靠近空穴传输层的方向运动，并经由空穴传输层传导至相应电极。未发生复合的电子沿着靠近电子传输层的方向运动，并经由电子传输层传导至相应电极，从而形成光电流。其中，上述电子传输层的材料包括氧化锡和锡氧化物。因氧化锡中锡的化合价为+4价、氧的化合价为-2价，故氧化锡中锡元素和氧元素的化学计量比为1:2。另外，上述锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。可以理解的是，上述锡氧化物中氧元素的比例低于氧化锡中氧元素的比例，因此与现有技术中单纯采用氧化锡材料制成的电子传输层相比，在本申请提供的钙钛矿太阳能电池包括的电子传输层的材料不仅包括氧化锡，还包括上述锡氧化物的情况下，可以使得本申请中的电子传输层内Sn/O比例增大，从而增加了电子传输层内的氧空位浓度。基于此，因上述电子传输层的导电原理是锡元素的外层电子与氧元素的外层电子形成化学键，当电子传输层中缺少氧的时候，锡元素的外层电子就形成了自由电子，实现导电。在上述情况下，当本申请提供的钙钛矿太阳能电池包括的电子传输层内的氧空位浓度增大时，电子传输层内形成的自由电子越多，从而可以提高电子传输层具有的电子传输能力，加速了电子和空穴对在光吸收层和电子传输层相接触的界面分离，降低了电子的界面复合损耗，进而利于提升钙钛矿太阳能电池的光电转换效率。
作为一种可能的实现方式，上述锡氧化物包括氧化亚锡(化学式为SnO)。
采用上述技术方案的情况下，氧化亚锡内锡的化合价为+2价、氧的化合价为-2价。基于此，在锡氧化物包括氧化亚锡的情况下，可以实现在氧化锡中掺杂Sn2+，从而制造出混合价态的电子传输层，利于增加电子传输层内氧空位的浓度。并且，与锡氧化物包括锡和氧的化学计量比的数值包括小数相比，氧化亚锡中锡元素的比例和氧元素的比例相同，便于对制造氧化亚锡的锡源和氧源的比例进行调整，降低锡氧化物的制造难度。另外，氧化亚锡在常温常压下的化学性质较为稳定，可以提高包括该电子传输层的钙钛矿太阳能电池的工作稳定性。
在一种示例中，上述电子传输层内氧化锡和氧化亚锡的化学计量比的范 围为：5:1至50:1。
采用上述技术方案的情况下，可以理解的是，电子传输层内氧化锡和氧化亚锡的化学计量比的比值越大，电子传输层内氧化锡的含量越高，其内的氧化亚锡的含量越低。相应的，电子传输层内的氧空位的浓度越小。相反的，电子传输层内氧化锡和氧化亚锡的化学计量比的比值越小，电子传输层内氧空位的浓度越大。在上述情况下，当电子传输层内氧化锡和氧化亚锡的化学计量比的范围为5:1至50:1时，电子传输层内氧化锡和氧化亚锡的化学计量比值大小适中，可以防止因上述化学计量比值较大而导致电子传输层内的氧空位浓度较低，确保电子传输层具有适当的电子传输能力。同时，还可以防止因上述化学计量比值较小使得电子传输层成为P型氧化物半导体层而导致光吸收层产生的电子在电子传输层内的复合速率增大，确保钙钛矿太阳能电池具有较高的光电转换效率。
作为一种可能的实现方式，沿着光吸收层的厚度方向，上述电子传输层包括交替层叠的第一含锡氧化物层和第二含锡氧化物层。第一含锡氧化物层的材料为氧化锡。第二含锡氧化物层的材料为锡氧化物。
采用上述技术方案的情况下，与材料为氧化锡的第一含锡氧化物层相比，材料为锡氧化物的第二含锡氧化物层内具有较高浓度的氧空位，因此相比于第一含锡氧化物层，第二含锡氧化物层的电子传输能力更高。基于此，沿着光吸收层的厚度方向，材料为氧化锡的第一含锡氧化物层与材料为锡氧化物的第二含锡氧化物层交替层叠设置，利于使得电子传输层内的氧空位可以沿着垂直于电子传输层的厚度方向均匀分布，进而利于使得电子传输层沿垂直于其厚度的方向的各部分具有的电子传输能力大致相同，防止电子传输层沿垂直于厚度方向的各部分对电子的传输速率不一致现象的发生，确保光吸收层沿垂直于厚度方向的各部分产生的电子均能够被电子传输层有效传输，进一步提高钙钛矿太阳能电池的光电转换效率。
作为另一种可能的实现方式，上述电子传输层为氧化锡和锡氧化物混合而成的混合材料层。此时，利于使得电子传输层沿厚度方向的各部分具有的电子传输能力大致相同，防止电子传输层沿厚度方向的各部分对电子的传输速率不一致现象的发生，降低光吸收层产生的电子在电子传输层内与氧空位 发生复合的速率，进一步提高钙钛矿太阳能电池的光电转换效率。另外，还可以为氧化锡和锡氧化物在电子传输层内的分布提供了更多的实现方案，提高了本申请提供的钙钛矿太阳能电池在不同应用场景下的适用性。
作为一种可能的实现方式，上述电子传输层的厚度为10nm至200nm。此时，电子传输层的厚度范围较大，可以在确保将光吸收层产生、且未发生复合的电子传导至相应电极的前提下，可以降低为制造固定厚度的电子传输层而严格控制电子传输层的形成时间等形成条件，降低电子传输层的制造难度。
第二方面，本申请还提供了一种叠层太阳能电池。该叠层太阳能电池包括底电池、以及位于底电池上的顶电池。顶电池为上述第一方面及其各种实现方式提供的钙钛矿太阳能电池。
本申请中第二方面及其各种实现方式的有益效果，可以参考第一方面及其各种实现方式中的有益效果分析，此处不再赘述。
第三方面，本申请还提供了一种钙钛矿太阳能电池的制造方法，该钙钛矿太阳能电池的制造方法包括：
提供一基底。
在基底上依次形成空穴传输层、光吸收层和电子传输层。或，在基底上依次形成电子传输层、光吸收层和空穴传输层。其中，
电子传输层的材料包括氧化锡和锡氧化物。锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
本申请中第三方面具有的有益效果，可以参考第一方面及其各种实现方式中的有益效果分析，此处不再赘述。
作为一种可能的实现方式，形成电子传输层包括以下步骤：
向反应腔室内X次交替通入锡源和第一氧源。X为大于或等于1的正整数。锡源内锡的化合价为+2价。第一氧源包括水和醇中的至少一种。
向反应腔室内Y次交替通入上述锡源和第二氧源。Y为大于或等于1的正整数。第二氧源包括氧气、臭氧和双氧水中的至少一种。
循环Z次上述操作，直至形成具有目标厚度的电子传输层。Z为大于或等于1的正整数。
采用上述技术方案的情况下，向反应腔室内X次交替通入上述锡源和第一氧源，可以形成一层具有一定厚度的含锡的氧化物层。另外，向反应腔室内Y次交替通入上述锡源和第二氧源，可以在其上形成另一层含锡的氧化物层。可以理解的是，因这两次操作中的锡源为+2价锡源、且第一氧源和第二氧源的氧化性不同，同时第一氧源与+2价锡源反应可以形成氧化亚锡，第二氧源可以将+2价锡氧化为更高的+4价锡等，故上述两层含锡的氧化物层的材料不同。基于此，在循环Z此上述操作后，可以获得由上述两层含锡的氧化层交替层叠Z次设置的电子传输层。其中，该情况下具有的有益效果可以参考前文所述的电子传输层包括交替层叠设置的第一含锡氧化物层和第二含锡氧化物层的有益效果分析，此处不再赘述。
作为一种可能的实现方式，形成电子传输层包括步骤：向反应腔室内交替通入锡源、以及由第一氧源和第二氧源组成的混合物，直至形成具有目标厚度的电子传输层；其中，锡源内锡的化合价为+2价。第一氧源包括水和醇中的至少一种。第二氧源包括氧气、臭氧和双氧水中的至少一种。
采用上述技术方案的情况下，以先向反应腔室内通入锡源为例对电子传输层包括的其中一子层的形成过程进行说明：向反应腔室内通入+2价的锡源后，向该反应腔室内通入了第一氧源和第二氧源的混合物。此时，因第一氧源的氧化性较弱、且第二氧源的氧化性较强，故如前文所述，+2价的锡源与氧化性不同的第一氧源和第二氧源所形成的每一子层的材料不仅包括氧化锡，还包括锡氧化物。基于此，通过该方式形成的电子传输层为氧化锡和锡氧化物混合而成的混合材料层。相应的，该情况下具有的有益效果可以参考前文所述的电子传输层为氧化锡和锡氧化物混合而成的混合材料层的有益效果分析，此处不再赘述。
作为一种可能的实现方式，形成电子传输层包括以下步骤：
向反应腔室内X次交替通入第一锡源和氧源。X为大于或等于1的正整数。第一锡源内锡的化合价为+2价。氧源包括水和醇中的至少一种。
向反应腔室内Y次交替通入第二锡源和上述氧源。Y为大于或等于1的正整数。第二锡源内锡的化合价为+4价。
循环Z次上述操作，直至形成具有目标厚度的电子传输层。Z为大于或 等于1的正整数。
采用上述技术方案的情况下，向反应腔室内X次交替通入上述第一锡源和氧源，可以形成一层具有一定厚度的含锡的氧化物层。另外，向反应腔室内Y次交替通入上述第二锡源和氧源，可以在其上形成另一层含锡的氧化物层。可以理解的是，因这两次操作中的氧源为氧化性较弱的氧源、且第一锡源和第二锡源内锡的化合价不同，同时在不采用等离子体等方式辅助反应的情况下第一锡源和第二锡源与氧化性较弱的氧源反应所获得的材料内锡的化合价基本不变，故上述两层含锡的氧化物层的材料不同。基于此，在循环Z此上述操作后，可以获得由上述两层含锡的氧化层交替层叠Z次设置的电子传输层。其中，该情况下具有的有益效果可以参考前文所述的电子传输层包括交替层叠设置的第一含锡氧化物层和第二含锡氧化物层的有益效果分析，此处不再赘述。
示例性的，在上述两种情况下，1≤X≤10，30≤Y≤50。
采用上述技术方案的情况下，如前文所述，在第一种情况中，+2价锡源与第一氧源反应所形成的材料为氧化亚锡。而在+2价锡源与第二氧源反应所形成的材料中锡的化合价高于+2价、且小于等于+4价。另外，在第二种情况中，+2价第一锡源与氧化性较弱的氧源反应形成的材料为氧化亚锡。而+4价第二锡源与上述氧源反应所形成的材料中锡的化合价高于+2价、且小于等于+4价。基于此，上述材料中锡的化合价大于等于+2价、且小于+4价的一者为锡氧化物。因此当1≤X≤10，30≤Y≤50时，电子传输层内氧化锡和锡氧化物的化学计量比的范围为5:1至50:1，该情况下具有的有益效果可以参考前文所述的电子传输层内氧化锡和氧化亚锡的化学计量比的范围为5:1至50:1具有的有益效果分析，此处不再赘述。相应的，当第一氧源为氧化性较强的氧源、且第二氧源为氧化性较弱的氧源时，1≤X≤10、且30≤Y≤50对应的有益效果与上述有益效果相同，此处不再赘述。
作为一种可能的实现方式，形成电子传输层包括步骤：向反应腔室内交替通入由第一锡源和第二锡源组成的混合物、以及氧源，直至形成具有目标厚度的电子传输层。其中，第一锡源内锡的化合价为+2价。第二锡源内锡的化合价为+4价。氧源包括水和醇中的至少一种。该情况下具有的有益效 果可以参考前文所述的向反应腔室内交替通入锡源、以及由第一氧源和第二氧源组成的混合物的有益效果分析，此处不再赘述。
作为一种可能的实现方式，形成电子传输层包括步骤：向反应腔室内Z次交替通入锡源和氧源，直至形成具有目标厚度的电子传输层。其中，在X次交替通入过程中，向反应腔室内通入锡源的同时进行等离子体放电。Z为大于1的正整数。X为小于Z、且大于等于1的正整数。其中，锡源中内锡的化合价为+2价。氧源包括水和醇中的至少一种。
采用上述技术方案的情况下，在向反应腔室内通入+2价锡源的同时进行等离子体放电，可以通过等离子体的引入，产生大量活性自由基，增强了+2价锡源的反应活性。此时，即使再向反应腔室内通入氧化性较弱的氧源，也可以将+2价锡源中的锡氧化为具有更高价态的锡，从而可以使得一次交替后所形成的子层的材料包括氧化锡等锡的化合价大于+2价、且小于等于+4价的含锡的氧化物。而在反应腔室内通入锡源时不进行等离子放电的情况，再向反应腔室内通入氧化性较弱的氧源，可以形成氧化亚锡，从而制造出材料包括锡混合价态的电子传输层，为形成电子传输层提供了更多的实现方案，提高了本申请提供的制造方法在不同应用场景下的适用性。
作为一种可能的实现方式，向反应腔室内通入锡源前，钙钛矿太阳能电池的制造方法还包括：采用保护气体吹扫反应腔室。在此情况下，可以将反应腔室内多余的氧源吹扫至反应腔室外，确保一次交替反应中锡源和氧源的比例满足预设方案的要求，提高制造精度。同时，还可以在第一次交替后，将反应腔室内多余的反应副产物吹扫至反应腔室外，防止反应副产物影响所制造的电子传输层的成膜质量，进一步提高电子传输层具有的电子传输能力。
作为一种可能的实现方式，向反应腔室内通入氧源前，钙钛矿太阳能电池的制造方法还包括：采用保护气体吹扫反应腔室。在此情况下，可以将反应腔室内多余的锡源吹扫至反应腔室外，确保一次交替反应中锡源和氧源的比例满足预设方案的要求，提高制造精度。同时，还可以在第一次交替后，将反应腔室内多余的反应副产物吹扫至反应腔室外，防止反应副产物影响所制造的电子传输层的成膜质量，进一步提高电子传输层具有的电子传输能力。
作为一种可能的实现方式，形成电子传输层的反应温度为50℃至250℃。 在此情况下，形成电子传输层的反应温度大小适中，防止因反应温度较小而导致锡源和氧源反应不完全影响电子传输层的形成质量，还可以防止因反应温度较低使得反应速率较小而导致电子传输层的制造效率较低，提高钙钛矿太阳能电池的良率和速率。此外，还可以防止因反应温度较大而导致电子传输层与光吸收层之间的兼容性变差，确保上述电子传输层在钙钛矿太阳能电池中具有较高的可应用性。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本申请。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本申请实施例提供的钙钛矿太阳能电池的第一种结构的纵向剖视示意图；
图2为本申请实施例提供的钙钛矿太阳能电池的第二种结构的纵向剖视示意图；
图3为本申请实施例提供的钙钛矿太阳能电池的第三种结构的纵向剖视示意图；
图4为本申请实施例提供的钙钛矿太阳能电池的第四种结构的纵向剖视示意图；
图5为本申请实施例提供的钙钛矿太阳能电池包括的电子传输层的一种结构剖视示意图；
图6为本申请实施例提供的叠层太阳能电池的一种结构的纵向剖视示意图；
图7为本申请实施例提供的叠层太阳能电池的另一种结构的纵向剖视示意图；
图8为本申请实施例提供的钙钛矿太阳能电池的制造方法流程图。
附图标记：11为光吸收层，12为空穴传输层，13为电子传输层，131 为第一含锡氧化物层，132为第二含锡氧化物层，14为第一电极，15为第一透明导电层，16为钝化减反层，17为硅衬底，18为第一本征硅层，19为P型掺杂硅层，20为第二本征硅层，21为N型掺杂硅层，22为第二透明导电层，23为第三透明导电层，24为第二电极，25为第三电极。
具体实施例
以下，将参照附图来描述本申请的实施例。但是应该理解，这些描述只是示例性的，而并非要限制本申请的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本申请的概念。
在附图中示出了根据本申请实施例的各种结构示意图。这些图并非是按比例绘制的，其中为了清楚表达的目的，放大了某些细节，并且可能省略了某些细节。图中所示出的各种区域、层的形状以及它们之间的相对大小、位置关系仅是示例性的，实际中可能由于制造公差或技术限制而有所偏差，并且本领域技术人员根据实际所需可以另外设计具有不同形状、大小、相对位置的区域/层。
在本申请的上下文中，当将一层/元件称作位于另一层/元件“上”时，该层/元件可以直接位于该另一层/元件上，或者它们之间可以存在居中层/元件。另外，如果在一种朝向中一层/元件位于另一层/元件“上”，那么当调转朝向时，该层/元件可以位于该另一层/元件“下”。为了使本申请所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。“若干”的含义是一个或一个以上，除非另有明确具体的限定。
在本申请的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是 可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本申请中的具体含义。
钙钛矿太阳能电池属于第三代太阳能电池，也称作新概念太阳能电池。因为其采用的钙钛矿材料具有吸光系数高、载流子迁移率高和扩散长度大、带隙可调节等一系列优点，故在太阳能电池领域受到了广泛的关注。目前，钙钛矿太阳能电池的光电转换效率已经突破25.5％，已与成熟的薄膜太阳能电池性能相当。更重要的是，钙钛矿太阳能电池还可以进行低温处理，这就使得它在需要解决可拉伸问题的下一代低成本光伏工艺中，具有很大的竞争优势。并且，可低温加工性也使得钙钛矿太阳能电池与柔性可穿戴电子设备兼容。
有效的钙钛矿太阳能电池结构一般包括空穴传输层、光吸收层、电子传输层、透明导电层和电极。其中，光吸收层的材料为钙钛矿材料。另外，从载流子的角度看，上述电子传输层和空穴传输层分别选择性地将电子和空穴传输到透明导电层或电极上。基于此，在实际的应用过程中，钙钛矿太阳能电池接受太阳光照射时，光吸收层首先吸收光子产生电子-空穴对。其中，未复合的电子和空穴分别被电子传输层和空穴传输层收集，即电子从光吸收层传输到电子传输层，最后被电极收集。而空穴从光吸收层传输到空穴传输层，最后被电极收集，产生光电流。
具体的，上述电子传输层的材料、以及电子传输层的制造方式一直以来都是钙钛矿太阳能电池的研究热点。现有的电子传输层的材料通常为TiO2和SnO2。其中，致密的介孔TiO2电子传输层能够有效的提取电子，使其受到了绝大数多研究者的青睐。但是，致密的介孔TiO2电子传输层的制造温度超过400℃，使得其难以与具有低温加工特性的钙钛矿太阳能电池所兼容。并且致密的介孔TiO2电子传输层具有光催化特性，降低了光吸收层对光的利用率，进而限制了其在钙钛矿太阳能电池上的应用。而对于上述SnO2来说，SnO2的电子迁移率高、其制造温度低于180℃、且其对应的-4.0eV的导带底能够与钙钛矿材料的光吸收层实现能级匹配，使得其成为了最具潜力的 备选电子传输材料。但是，SnO2材料制造形成的电子传输层具有的电子传输能力不佳，不利于提升钙钛矿太阳能电池的光电转换效率。
为了解决上述技术问题，本申请实施例提供了一种钙钛矿太阳能电池。如图1所示，该钙钛矿太阳能电池包括：光吸收层11、空穴传输层12和电子传输层13。上述空穴传输层12形成在光吸收层11的一侧。电子传输层13形成在光吸收层11背离空穴传输层12的一侧。电子传输层13的材料包括氧化锡和锡氧化物。该锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
具体来说，从材料方面来讲，在一些示例中，上述光吸收层的材料的分子通式为ABX3。其中，A、B为大小不同的阳离子，X是与两者键合的阴离子。并且，阳离子B与阴离子X配位组成正八面体对称结构，而阳离子A位于八个正八面体的中心位置，阳离子B位于正八面体的中心位置。具体的，光吸收层的材料可以为无机钙钛矿材料，也可以为有机钙钛矿材料，还可以为有机-无机杂化钙钛矿材料。例如：光吸收层的材料可以为CsPbI2Br、MAPbBr3、FAPbI3或Cs1-y-zFAyMAzPbI3-xBrx(其中，FA为甲醚，MA为甲胺，0≤x≤3，0≤y≤1，0≤z≤1，且0≤y+z≤1)等。
从结构方面来讲，光吸收层的厚度可以根据实际需求进行设置，此处不做具体限定。此外，如图1所示，光吸收层11的两个相对的表面可以为平坦的抛光面。或者，光吸收层与受光面相对的一面为绒面，其与背光面相对的一面为抛光面。在此情况下，绒面结构具有陷光作用，因此当光吸收层的表面为绒面时，可以使得更多的光线折射至光吸收层内。并且，因抛光面具有相对良好的反射特性，因此在光线达到光吸收层与背光面相对的一面后可以至少部分被反射回光吸收层内，被光吸收层重新利用，从而可以提高钙钛矿太阳能电池的光电转换效率。又或者，如图2所示，光吸收层11的两个相对的表面也可以均为绒面。此时，如图6和图7所示，在将本申请实施例提供的钙钛矿太阳能电池作为叠层太阳能电池包括的顶电池时，光吸收层11与底电池相接触的一面为绒面，可以使得更多的光线折射至底电池内，提高底电池的光电转换效率。
对于上述空穴传输层来说，空穴传输层的材料可以为有机空穴传输材料 (例如：2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(可缩写为Sprio-OMeTAD)、2,2,7,7-四(N,N-二对甲苯基)氨基-9,9-螺二芴(可缩写为spiro-TTB)、三氟甘露糖(可缩写为TATM)、(2-(3,6-二甲氧基-9H-咔唑-9-基)乙基)膦(可缩写为MeO-2PACz)、[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸(可缩写为Me-4PACz)或(2-(9H-咔唑-9-基)乙基)膦酸(可缩写为2PACz)等)，也可以为无机空穴传输材料(例如：氧化钼、氧化镍或氧化亚铜等)。空穴传输层的厚度可以根据实际应用场景设置，只要能够应用至本申请实施例提供的钙钛矿太阳能电池中均可。
对于上述电子传输层来说，从规格方面来讲，电子传输层的厚度可以根据实际需求进行设置。示例性的，电子传输层的厚度可以为10nm至200nm。此时，电子传输层的厚度范围较大，可以在确保将光吸收层产生、且未发生复合的电子传导至相应电极的前提下，可以降低为制造固定厚度的电子传输层而严格控制电子传输层的形成时间等形成条件，降低电子传输层的制造难度。
从材料方面来讲，电子传输层的材料包括氧化锡和锡氧化物。其中，锡氧化物内锡元素和氧元素的具体化学计量比、电子传输层内氧化锡和锡氧化物的化学计量比、以及氧化锡和锡氧化物在电子传输层内的分布方式，可以根据实际需求进行设置，只要能够应用至本申请实施例提供的钙钛矿太阳能电池中均可。
需要说明的是，如图3所示，本申请实施例提供的钙钛矿太阳能电池可以为反式结构，即上述空穴传输层12、光吸收层11和电子传输层13自上而下依次层叠设置。或者，如图4所示，本申请实施例提供的钙钛矿太阳能电池也可以为正式结构，即上述电子传输层13、光吸收层11和空穴传输层12自上而下依次层叠设置。
在一些情况下，如图1所示，本申请实施例提供的钙钛矿太阳能电池还包括第一电极14和第一透明导电层15。其中，第一电极14形成在空穴传输层12背离光吸收层11的一侧，用于导出空穴传输层收集的空穴。第一透明导电层15形成在电子传输层13背离光吸收层11的一侧，用于导出电子传输层收集的电子。
具体的，上述第一电极的材料可以为铝、金、银、铜、钨等导电材料。上述第一透明导电层的材料可以为氧化铟锡、掺氟氧化锡、掺铟氧化锌、氧化铟钨、掺铝氧化锌或掺硼氧化锌中的任意一种或至少两种的组合。第一透明导电层的厚度可以根据实际需求进行设置，此处不做具体限定。
如图1所示，本申请实施例提供的钙钛矿太阳能电池在实际的工作过程中，光吸收层11吸收光子后会产生电子和空穴对。其中，未发生复合的空穴沿着靠近空穴传输层12的方向运动，并经由空穴传输层12传导至相应电极。未发生复合的电子沿着靠近电子传输层13的方向运动，并经由电子传输层13传导至相应电极，从而形成光电流。在此情况下，上述电子传输层13的材料包括氧化锡和锡氧化物。因氧化锡中锡的化合价为+4价、氧的化合价为-2价，故氧化锡中锡元素和氧元素的化学计量比为1:2。另外，上述锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。可以理解的是，上述锡氧化物中氧元素的比例低于氧化锡中氧元素的比例，因此与现有技术中单纯采用氧化锡材料制成的电子传输层相比，在本申请实施例提供的钙钛矿太阳能电池包括的电子传输层13的材料不仅包括氧化锡，还包括上述锡氧化物的情况下，可以使得本申请实施例中的电子传输层13内Sn/O比例增大，从而增加了电子传输层13内的氧空位浓度。基于此，因上述电子传输层13的导电原理是锡元素的外层电子与氧元素的外层电子形成化学键，当电子传输层13中缺少氧的时候，锡元素的外层电子就形成了自由电子，实现导电。在上述情况下，当本申请实施例提供的钙钛矿太阳能电池包括的电子传输层13内的氧空位浓度增大时，电子传输层13内形成的自由电子越多，从而可以提高电子传输层13具有的电子传输能力，加速了电子和空穴对在光吸收层11和电子传输层13相接触的界面分离，降低了电子的界面复合损耗，进而利于提升钙钛矿太阳能电池的光电转换效率。
可以理解的是，上述锡氧化物的具体种类与锡氧化物内锡元素和氧元素的化学计量比的大小相关。其中，可以根据锡氧化物内锡元素和氧元素的具体化学计量比将锡氧化物的具体种类分为以下两种情况进行说明：
第一种：锡氧化物内锡元素和氧元素的化学计量比可以为1:1。此时，锡氧化物为氧化亚锡、且电子传输层的材料包括氧化锡和氧化亚锡。
第二种：锡氧化物内锡元素和氧元素的化学计量比可以为大于1:2，且小于1:1的小数。此时，锡氧化物内一部分锡的化合价可以为+4价，另一部分锡的化合价可以为+2价。例如：锡氧化物为四氧化三锡或六氧化五锡等。又例如：锡氧化物包括氧化亚锡和四氧化三锡。
值得注意的是，氧化亚锡内锡的化合价为+2价、氧的化合价为-2价。基于此，在锡氧化物包括氧化亚锡的情况下，可以实现在氧化锡中掺杂Sn2+，从而制造出混合价态的电子传输层，利于增加电子传输层内氧空位的浓度。并且，与锡氧化物包括锡和氧的化学计量比的数值包括小数相比，氧化亚锡中锡元素的比例和氧元素的比例相同，便于对制造氧化亚锡的锡源和氧源的比例进行调整，降低锡氧化物的制造难度。另外，氧化亚锡在常温常压下的化学性质较为稳定，可以提高包括该电子传输层的钙钛矿太阳能电池的工作稳定性。
具体的，在锡氧化物包括氧化亚锡的情况下，电子传输层内氧化锡和氧化亚锡的具体化学计量比，可以根据实际需求进行设置。例如：上述电子传输层内氧化锡和氧化亚锡的化学计量比的范围可以为：5:1至50:1。可以理解的是，电子传输层内氧化锡和氧化亚锡的化学计量比的比值越大，电子传输层内氧化锡的含量越高，其内的氧化亚锡的含量越低。相应的，电子传输层内的氧空位的浓度越小。相反的，电子传输层内氧化锡和氧化亚锡的化学计量比的比值越小，电子传输层内氧空位的浓度越大。在上述情况下，当电子传输层内氧化锡和氧化亚锡的化学计量比的范围为5:1至50:1时，电子传输层内氧化锡和氧化亚锡的化学计量比值大小适中，可以防止因上述化学计量比值较大而导致电子传输层内的氧空位浓度较低，确保电子传输层具有适当的电子传输能力。同时，还可以防止因上述化学计量比值较小使得电子传输层成为P型氧化物半导体层而导致光吸收层产生的电子在电子传输层内的复合速率增大，确保钙钛矿太阳能电池具有较高的光电转换效率。
作为一种可能的实现方式，如图5所示，沿着光吸收层11的厚度方向，上述电子传输层13包括交替层叠的第一含锡氧化物层131和第二含锡氧化物层132。第一含锡氧化物层131的材料为氧化锡。第二含锡氧化物层132的材料为锡氧化物。
具体的，电子传输层中与光吸收层相接触的膜层可以为第一含锡氧化物层、也可以为第二含锡氧化物层。电子传输层与第一电极相接触的膜层可以为第一含锡氧化物层、也可以为第二含锡氧化物层。另外，电子传输层包括的第一含锡氧化物层和第二含锡氧化物层的层数和厚度可以根据电子传输层内氧化锡和锡氧化物的化学计量比、电子传输层的总厚度、以及实际需求进行确定，此处不做具体限定。
例如：在锡氧化物包括氧化亚锡、且电子传输层内氧化锡和氧化亚锡的化学计量比的范围为：5:1至50:1的情况下，第一含锡氧化物层的层数可以大于等于30层、且小于等于50层。第二含锡氧化物层的层数可以大于等于1层、且小于等于10层。
采用上述技术方案的情况下，与材料为氧化锡的第一含锡氧化物层相比，材料为锡氧化物的第二含锡氧化物层内具有较高浓度的氧空位，因此相比于第一含锡氧化物层，第二含锡氧化物层的电子传输能力更高。基于此，沿着光吸收层的厚度方向，材料为氧化锡的第一含锡氧化物层与材料为锡氧化物的第二含锡氧化物层交替层叠设置，利于使得电子传输层内的氧空位可以沿着垂直于电子传输层的厚度方向均匀分布，进而利于使得电子传输层沿垂直于其厚度的方向的各部分具有的电子传输能力大致相同，防止电子传输层沿垂直于厚度方向的各部分对电子的传输速率不一致现象的发生，确保光吸收层沿垂直于厚度方向的各部分产生的电子均能够被电子传输层有效传输，进一步提高钙钛矿太阳能电池的光电转换效率。
作为另一种可能的实现方式，上述电子传输层为氧化锡和锡氧化物混合而成的混合材料层。此时，利于使得电子传输层沿厚度方向的各部分具有的电子传输能力大致相同，防止电子传输层沿厚度方向的各部分对电子的传输速率不一致现象的发生，降低光吸收层产生的电子在电子传输层内与氧空位发生复合的速率，进一步提高钙钛矿太阳能电池的光电转换效率。另外，还可以为氧化锡和锡氧化物在电子传输层内的分布提供了更多的实现方案，提高了本申请实施例提供的钙钛矿太阳能电池在不同应用场景下的适用性。
作为一种可能的实现方式，如图3和图4所示，本申请实施例提供的钙钛矿太阳能电池还包括钝化减反层16，以对钙钛矿太阳能电池的受光面进行 钝化，降低载流子在受光面一侧的复合速率，提高钙钛矿太阳能电池的光电转换效率。此外，钝化减反层16还可以使得更多的光线由钙钛矿太阳能电池的受光面折射至电池内部，提高钙钛矿太阳能电池对光能的利用率。其中，上述钝化减反层16的形成位置根据钙钛矿太阳能电池的具体结构相关。例如：如前文所述，如图3所示，当钙钛矿太阳能电池为反式结构时，钝化减反层16形成在空穴传输层12背离光吸收层11的一侧。又例如：如图4所示，当钙钛矿太阳能电池为正式结构时，钝化减反层16形成在电子传输层13背离光吸收层11的一侧。
具体的，钝化减反层的材质可以为氟化镁、氮化硅、氧化硅或氟化锂等材料。钝化减反层的厚度可以根据实际需求进行设置，此处不做具体限定。
本申请实施例还提供了一种叠层太阳能电池。该叠层太阳能电池包括底电池、以及位于底电池上的顶电池。顶电池为上述实施例提供的钙钛矿太阳能电池。
具体的，上述底电池可以为异质结电池、钝化发射极背面电池、隧穿氧化层钝化接触电池、交叉指式背接触电池或交叉指式背接触异质结电池等。此外，可以理解的是，叠层太阳能电池中的底电池和顶电池串联。其中，如图6所示，可以通过将钙钛矿太阳能电池包括的空穴传输层12设置在底电池的上方。此时，通过顶电池的正极与底电池的负极耦合，以实现二者串联。或者，如图7所示，也可以通过将钙钛矿太阳能电池包括的电子传输层13设置在底电池的上方。此时，通过顶电池的负极与底电池的正极耦合，以实现二者串联。
如图6和图7所示，以底电池为硅异质结电池为例对叠层太阳能电池的具体结构进行说明。其中，底电池可以包括硅衬底17、第一本征硅层18、P型掺杂硅层19、第二本征硅层20和N型掺杂硅层21。
具体的，如图6所示，若通过将钙钛矿太阳能电池包括的空穴传输层12设置在底电池的上方，则沿远离硅衬底17的方向，第二本征硅层20和N型掺杂硅层21依次层叠设置在硅衬底17的受光面上。沿远离硅衬底17的方向，第一本征硅层18和P型掺杂硅层19依次层叠设置在硅衬底17的背光面上。
或者，如图7所示，若通过将钙钛矿太阳能电池包括的电子传输层13设置在底电池的上方，则沿远离硅衬底17的方向，第一本征硅层18和P型掺杂硅层19依次层叠设置在硅衬底17的受光面上。沿远离硅衬底17的方向，第二本征硅层20和N型掺杂硅层21依次层叠设置在硅衬底17的背光面上。
在一些情况下，如图6和图7所示，叠层太阳能电池还包括第二电极24、第三电极25、第二透明导电层22和第三透明导电层23。其中，第二透明导电层22形成在空穴传输层12背离光吸收层11的一侧。第三透明导电层23形成在底电池的背光面一侧。第二电极24形成在钙钛矿太阳能电池的受光面一侧。第三电极25形成在第三透明导电层23上。具体的，第二电极24和第二电极24的材料可以参考前文所述的第一电极的材料。第二透明导电层22和第三透明导电层23的材料可以参考前文所述的第一透明导电层的材料。
与现有技术相比，本申请实施例提供的叠层太阳能电池的有益效果，可以参考上述实施例提供的钙钛矿太阳能电池的有益效果分析，此处不再赘述。
如图8所示，本申请实施例还提供了一种钙钛矿太阳能电池的制造方法，该钙钛矿太阳能电池的制造方法包括以下步骤：
首先，提供一基底。该基底可以为其上未形成有其它结构的透明导电基底。例如：该基底可以为氧化锡透明导电玻璃基底。或者，该基底还可以为其上形成有一些膜层的基底。在此情况下，形成有一些膜层的基底的具体结构可以根据实际应用场景设置，只要能够应用至本申请实施例提供的钙钛矿太阳能电池的制造方法中均可。例如：如图6和图7所示，上述形成有一些膜层的基底可以为前文所述的底电池。
如图4所示，在基底上依次形成空穴传输层12、光吸收层11和电子传输层13。或者，如图3所示，在基底上依次形成电子传输层13、光吸收层11和空穴传输层12。其中，上述电子传输层13的材料包括氧化锡和锡氧化物。锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
具体的，可以根据所制造的钙钛矿太阳能电池为正式结构还是反式结构确定钙钛矿太阳能电池所包括的各膜层的制造顺序。
例如：在钙钛矿太阳能电池为反式结构的情况下，可以在基底上依次形成电子传输层、光吸收层和空穴传输层，从而使得空穴传输层靠近钙钛矿太阳能电池的受光面。
又例如：在钙钛矿太阳能电池为正式结构的情况下，可以在基底上依次形成空穴传输层、光吸收层和电子传输层，从而使得电子传输层靠近钙钛矿太阳能电池的受光面。
与现有技术相比，本申请实施例提供的钙钛矿太阳能电池的制造方法的有益效果，可以参考上述实施例提供的钙钛矿太阳能电池的有益效果分析，此处不再赘述。
在实际的应用过程中，以在基底上依次形成电子传输层、光吸收层和空穴传输层为例对制造钙钛矿太阳能电池的制造过程进行说明。首先，可以采用采用原子层沉积、通过等离子辅助的原子层沉积等工艺在基底上形成电子传输层。接着可以采用溶液法等工艺在电子传输层上形成光吸收层。最后，可以采用旋转涂覆等工艺在光吸收层上形成空穴传输层。其中，上述空穴传输层、光吸收层和电子传输层的材料等信息可以参考前文，此处不再赘述。
具体的，因原子层沉积工艺是一种在气相中使用连续化学反应的薄膜形成工艺，其可以将物质以单原子膜形式一层一层的镀在基底表面，故采用原子层沉积工艺制造电子传输层可以使得所形成的电子传输层的厚度均匀。另外，原子层沉积工艺具有自限制机制，可以在提高电子传输层的厚度精度的同时，便于控制电子传输层内氧化锡和锡氧化物的化学计量比，确保电子传输层具有较高电子传输能力。基于此，本申请实施例提供的钙钛矿太阳能电池的制造方法优选采用原子层沉积工艺制造电子传输层。在此情况下，在实际制造时，需要向原子层沉积设备的反应腔室内交替通入锡源和氧源，直至形成目标厚度的电子传输层。
可以理解的是，在上述锡源内锡的化合价不同、以及氧源的氧化性强弱的不同，所形成的含锡的氧化物中锡元素和氧元素的化学计量比也不相同。基于此，可以将采用原子层沉积工艺形成电子传输层时，反应原材料包括的锡源和氧源至少分为以下三种情况进行说明：
第一种：锡源内锡的化合价为+2价。氧源包括第一氧源和第二氧源。 第一氧源包括水和醇中的至少一种。第二氧源包括氧气、臭氧和双氧水中的至少一种。在此情况下，上述水和醇的氧化性较弱，而氧气、臭氧和双氧水的氧化性较强。基于此，在锡源内锡的化合价为+2价时，第一氧源与+2价锡源反应可以形成氧化亚锡。第二氧源可以将+2价锡氧化为更高的+4价锡等，从而可以制造出材料包括锡混合价态的电子传输层。
具体的，在锡源内锡的化合价为+2价的情况下，该锡源可以为二甲基氨基-2-甲基-2-丙氧基锡(II)、双(N-乙氧基-2,2-二甲基丙酰胺基)锡(II)或双(叔戊氧基)-锡(II)等。
另外，上述第一氧源可以仅为水，也可以仅为醇，还可以是水和醇的混合溶液。其中，当第一氧源为水和醇的混合溶液时，混合溶液中水和醇的比例可以根据实际需求进行设置，此处不做具体限定。上述醇可以是乙醇、丙醇等。
上述第二氧源可以仅包括氧气、臭氧和双氧水中的任一种。或者，第二氧源可以包括氧气、臭氧和双氧水中的任意两种。又或者，第二氧源可以包括氧气、臭氧和双氧水。其中，当第二氧源包括氧气、臭氧和双氧水中的至少两种时，第二氧源中各成分的比例可以根据实际需求进行设置，此处不做具体限定。
在实际的应用过程中，当锡源和氧源为上述第一种情况限定的锡源、第一氧源和第二氧源时，可以根据电子传输层内氧化锡和锡氧化物的分布情况确定向反应腔室内通入锡源、第一氧源和第二氧源的方式。
在一种示例中，在第一种情况下，形成电子传输层包括以下步骤：首先，向反应腔室内X次交替通入锡源和第一氧源。X为大于或等于1的正整数。接着，向反应腔室内Y次交替通入锡源和第二氧源。Y为大于或等于1的正整数。然后循环Z次上述操作，直至形成具有目标厚度的电子传输层。Z为大于或等于1的正整数。
在此情况下，向反应腔室内X次交替通入上述锡源和第一氧源，可以形成一层具有一定厚度的含锡的氧化物层。另外，向反应腔室内Y次交替通入上述锡源和第二氧源，可以在其上形成另一层含锡的氧化物层。可以理解的是，因这两次操作中的锡源为+2价锡源、且第一氧源和第二氧源的氧化性 不同，同时第一氧源与+2价锡源反应可以形成氧化亚锡，第二氧源可以将+2价锡氧化为更高的+4价锡等，故上述两层含锡的氧化物层的材料不同。基于此，在循环Z此上述操作后，可以获得由上述两层含锡的氧化层交替层叠Z次设置的电子传输层。其中，该情况下具有的有益效果可以参考前文所述的电子传输层包括交替层叠设置的第一含锡氧化物层和第二含锡氧化物层的有益效果分析，此处不再赘述。
具体的，当进行上述第一步操作时，向反应腔室内通入一次锡源，并通入一次第一氧源为一次交替。其中，可以是先向反应腔室内通入一定时间的第一氧源，并在停止通第一氧源后，再向反应腔室内通入一定时间的锡源。或者，也可以是先向反应腔室内通入一定时间的锡源，并在停止通锡源后，再向反应腔室内通入一定时间的第一氧源。
当进行上述第二步操作时，锡源和第二氧源的通入顺序可以参考前文所述的第一步操作时锡源和第一氧源的通入顺序。此处不再赘述。
执行上述第一步操作时每次交替中锡源和第一氧源的通入时间、以及第二步操作时每次交替中锡源和第二氧源的通入时间可以根据实际应用场景设置。例如：第一步操作时每次交替中锡源的通入时间可以为10s至20s，第一氧源的通入时间可以为10s至20s。第二步操作时每次交替中锡源的通入时间可以为10s至20s，第二氧源的通入时间可以为10s至20s。
另外，上述X、Y的具体数值可以根据电子传输层内氧化锡和锡氧化物的化学计量比进行确定。示例性的，1≤X≤10，30≤Y≤50。在此情况下，如前文所述，在+2价锡源与第一氧源反应所形成的材料为氧化亚锡。而在+2价锡源与第二氧源反应所形成的材料中锡的化合价高于+2价、且小于等于+4价。并且，上述材料中锡的化合价大于等于+2价、且小于+4价的一者为锡氧化物。基于此，当第一氧源为氧化性较弱的氧源、且第二氧源为氧化性较强的氧源时，1≤X≤10、且30≤Y≤50时，电子传输层内氧化锡和锡氧化物的化学计量比的范围为5:1至50:1，该情况下具有的有益效果可以参考前文所述的电子传输层内氧化锡和氧化亚锡的化学计量比的范围为5:1至50:1具有的有益效果分析，此处不再赘述。
再者，Z的具体数值可以根据电子传输层的目标厚度进行确定。例如： 在电子传输层的目标厚度为30nm的情况下，Z可以等于230。
需要说明的是，该示例中，也可以是先向反应腔室内Y次交替通入锡源和第二氧源。接着再向反应腔室内X次交替通入锡源和第一氧源。然后循环Z次上述操作，直至形成具有目标厚度的电子传输层。换句话说，该示例中，向反应腔室内X次交替通入锡源和第一氧源的操作步骤，与向反应腔室内Y次交替通入锡源和第二氧源的操作步骤的执行先后顺序可以互换。
在另一种示例中，在上述第一种情况下，形成电子传输层包括步骤：向反应腔室内交替通入锡源、以及由第一氧源和第二氧源组成的混合物，直至形成具有目标厚度的电子传输层。其中，向反应腔室内通入一次锡源，并通入一次第一氧源和第二氧源组成的混合物为一次交替。另外，每次交替中，可以先通入锡源，再通入上述混合物。或者，每次交替中，可以先通入上述混合物，再通入锡源。再者，每次交替中，锡源和上述混合物的通入时间、以及混合物中第一氧源和第二氧源的比例可以根据锡氧化物中锡元素和氧元素的化学计量比、以及电子传输层内氧化锡和锡氧化物的化学计量比进行确定，此处不做具体限定。
采用上述技术方案的情况下，以先向反应腔室内通入锡源为例对电子传输层包括的其中一子层的形成过程进行说明：向反应腔室内通入+2价的锡源后，向该反应腔室内通入了第一氧源和第二氧源的混合物。此时，因第一氧源氧化性较弱、且第二氧源的氧化性较强，故如前文所述，+2价的锡源与氧化性不同的第一氧源和第二氧源所形成的每一子层的材料不仅包括氧化锡，还包括锡氧化物。基于此，通过该方式形成的电子传输层为氧化锡和锡氧化物混合而成的混合材料层。相应的，该情况下具有的有益效果可以参考前文所述的电子传输层为氧化锡和锡氧化物混合而成的混合材料层的有益效果分析，此处不再赘述。
第二种：上述锡源包括第一锡源和第二锡源。第一锡源内锡的化合价为+2价，第二锡源内锡的化合价为+4价。氧源包括水和醇中的至少一种。此时，可以制造出材料包括锡混合价态的电子传输层，为形成电子传输层提供了更多的实现方案，提高了本申请实施例提供的制造方法在不同应用场景下的适用性。
具体的，+2价的锡源的种类可以参考前文。+4价的锡源可以为四(二甲氨基)锡等。
在实际的应用过程中，当锡源和氧源为上述第二种情况限定的第一锡源、第二锡源和氧源时，同样也可以根据电子传输层内氧化锡和锡氧化物的分布情况确定向反应腔室内通入第一锡源、第二锡源和氧源的方式。
在一种示例中，在上述第二种情况下，形成电子传输层包括以下步骤：首先，向反应腔室内X次交替通入第一锡源和氧源。X为大于或等于1的正整数。接着，向反应腔室内Y次交替通入第二锡源和氧源。Y为大于或等于1的正整数。然后循环Z次上述操作，直至形成具有目标厚度的电子传输层。Z为大于或等于1的正整数。在此情况下，向反应腔室内X次交替通入上述第一锡源和氧源，可以形成一层具有一定厚度的含锡的氧化物层。另外，向反应腔室内Y次交替通入上述第二锡源和氧源，可以在其上形成另一层含锡的氧化物层。可以理解的是，因这两次操作中的氧源为氧化性较弱的氧源、且第一锡源和第二锡源内锡的化合价不同，同时在不采用等离子体等方式辅助反应的情况下第一锡源和第二锡源与氧化性较弱的氧源反应所获得的材料内锡的化合价基本不变，故上述两层含锡的氧化物层的材料不同。基于此，在循环Z此上述操作后，可以获得由上述两层含锡的氧化层交替层叠Z次设置的电子传输层。其中，该情况下具有的有益效果可以参考前文所述的电子传输层包括交替层叠设置的第一含锡氧化物层和第二含锡氧化物层的有益效果分析，此处不再赘述。
具体的，当进行上述第一步操作时，向反应腔室内通入一次第一锡源，并通入一次氧源为一次交替。其中，可以是先向反应腔室内通入一定时间的氧源，并在停止通氧源后，再向反应腔室内通入一定时间的第一锡源。或者，也可以是先向反应腔室内通入一定时间的第一锡源，并在停止通第一锡源后，再向反应腔室内通入一定时间的氧源。
当进行上述第二步操作时，第二锡源和氧源的通入顺序可以参考前文所述的第一步操作时第一锡源和氧源的通入顺序。此处不再赘述。
执行上述第一步操作时每次交替中第一锡源和氧源的通入时间、以及第二步操作时每次交替中第二锡源和氧源的通入时间可以根据实际应用场景 设置。例如：第一步操作时每次交替中第一锡源的通入时间可以为10s至20s，氧源的通入时间可以为10s至30s。第二步操作时每次交替中第二锡源的通入时间可以为10s至20s，氧源的通入时间可以为10s至30s。
另外，上述X、Y的具体数值可以根据电子传输层内氧化锡和锡氧化物的化学计量比进行确定。示例性的，1≤X≤10，30≤Y≤50。该情况下具有的有益效果可以参考前文，此处不再赘述。
再者，Z的具体数值可以根据电子传输层的目标厚度进行确定。例如：在电子传输层的目标厚度为50nm的情况下，Z可以等于380。
需要说明的是，该示例中，也可以是先向反应腔室内Y次交替通入第二锡源和氧源。接着再向反应腔室内X次交替通入第一锡源和氧源。然后循环Z次上述操作，直至形成具有目标厚度的电子传输层。换句话说，该示例中，向反应腔室内X次交替通入第一锡源和氧源的操作步骤，与向反应腔室内Y次交替通入第二锡源和氧源的操作步骤的执行先后顺序可以互换。
在另一种示例中，在上述第二种情况下，形成电子传输层包括步骤：向反应腔室内交替通入由第一锡源和第二锡源组成的混合物、以及氧源，直至形成具有目标厚度的电子传输层。
其中，向反应腔室内通入一次第一锡源和第二锡源组成的混合物，并通入一次氧源为一次交替。另外，每次交替中，可以先通入上述混合物，再通入氧源。或者，每次交替中，可以先通入氧源，再通入上述混合物。再者，每次交替中，上述混合物和氧源的通入时间、以及混合物中第一锡源和第二锡源的比例可以根据锡氧化物中锡元素和氧元素的化学计量比、以及电子传输层内氧化锡和锡氧化物的化学计量比进行确定，此处不做具体限定。
第三种：上述锡源中内锡的化合价为+2价。氧源包括水和醇中的至少一种。在上述情况下，形成电子传输层包括步骤：向反应腔室内Z次交替通入锡源和氧源，直至形成具有目标厚度的电子传输层。其中，在X次交替通入过程中，向反应腔室内通入锡源的同时进行等离子体放电。Z为大于1的正整数。X为小于Z、且大于等于1的正整数。
在实际的制造过程中，在向反应腔室内通入+2价锡源的同时进行等离子体放电，可以通过等离子体的引入，产生大量活性自由基，增强了+2价 锡源的反应活性。此时，即使再向反应腔室内通入氧化性较弱的氧源，也可以将+2价锡源中的锡氧化为具有更高价态的锡，从而可以使得一次交替后所形成的子层的材料包括氧化锡等锡的化合价大于+2价、且小于等于+4价的含锡的氧化物。而在反应腔室内通入锡源时不进行等离子放电的情况，再向反应腔室内通入氧化性较弱的氧源，可以形成氧化亚锡，从而制造出材料包括锡混合价态的电子传输层。在上述情况下，上述X和Z的大小可以根据电子传输层内氧化锡和锡氧化物的化学计量比、以及电子传输层的目标厚度进行确定。例如：在电子传输层内氧化锡和锡氧化物的化学计量比为50:1、且Z等于8250的情况下，X等于165。
另外，在X为大于等于2的正整数的情况下，具体是在哪一次通入锡源时进行等离子体放电辅助，可以根据电子传输层内氧化锡和锡氧化物的分布进行确定，此处不做具体限定。
作为一种可能的实现方式，向反应腔室内通入锡源前，钙钛矿太阳能电池的制造方法还包括：采用保护气体吹扫反应腔室。在此情况下，可以将反应腔室内多余的氧源吹扫至反应腔室外，确保一次交替反应中锡源和氧源的比例满足预设方案的要求，提高制造精度。同时，还可以在第一次交替后，将反应腔室内多余的反应副产物吹扫至反应腔室外，防止反应副产物影响所制造的电子传输层的成膜质量，进一步提高电子传输层具有的电子传输能力。
作为一种可能的实现方式，向反应腔室内通入氧源前，钙钛矿太阳能电池的制造方法还包括：采用保护气体吹扫反应腔室。在此情况下，可以将反应腔室内多余的锡源吹扫至反应腔室外，确保一次交替反应中锡源和氧源的比例满足预设方案的要求，提高制造精度。同时，还可以在第一次交替后，将反应腔室内多余的反应副产物吹扫至反应腔室外，防止反应副产物影响所制造的电子传输层的成膜质量，进一步提高电子传输层具有的电子传输能力。
具体的，上述向反应腔室内通入锡源前采用保护气体吹扫反应腔室的吹扫时间、以及上述向反应腔室内通入氧源前采用保护气体吹扫反应腔室的吹扫时间可以根据实际应用场景设置，此处不做具体限定。例如：吹扫时间可以为10s至30s。另外，上述保护气体可以为氮气、氦气和氩气等。
作为一种可能的实现方式，形成电子传输层的反应温度为50℃至250℃。 在此情况下，形成电子传输层的反应温度大小适中，防止因反应温度较小而导致锡源和氧源反应不完全影响电子传输层的形成质量，还可以防止因反应温度较低使得反应速率较小而导致电子传输层的制造效率较低，提高钙钛矿太阳能电池的良率和速率。此外，还可以防止因反应温度较大而导致电子传输层与光吸收层之间的兼容性变差，确保上述电子传输层在钙钛矿太阳能电池中具有较高的可应用性。
当然，也可以根据不同的实际应用场景将电子传输层的反应温度设置为其它合适数值，此处不做具体限定。
本申请还提供了以下具体实施例来进一步说明本申请所述钙钛矿太阳能电池的制造方法，具体操作步骤如下：
实施例1：
采用透明导电玻璃作为基底。将洁净后的基底放入原子层沉积设备的反应腔室中，真空抽至0.1Pa。并将反应腔室内的温度保持在100℃，通入50sccm N2作为锡源载气。采用二甲基氨基-2-甲基-2-丙氧基锡(Ⅱ)作为锡源，并使得锡源保持80℃。第一氧源和第二氧源分为H2O源和O3源，并且第一氧源和第二氧源保持室温。先向反应腔室内通入锡源12s，接着采用N2吹扫15s。再向反应腔室内通入O3源12s，接着采用N2吹扫15s，以此作为一个第一循环。并在执行40次上述第一循环后，改为先向反应腔室内通入锡源12s，接着采用N2吹扫15s。再向反应腔室内通入H2O源12s，接着采用N2吹扫15s，以此作为一个第二循环。并执行5次上述第二循环。通过交替执行上述第一循环和第二循环230次，可以形成目标厚度为30nm的电子传输层。
然后，在电子传输层上形成材料为(FAPbI3)0.87(MAPbI3)0.13、厚度为800nm的光吸收层。接着，在光吸收层上形成材料为spiro-MeOTAD、且厚度为150nm的空穴传输层。最后在空穴传输层上形成了材料为金、且厚度为100nm的第一电极，获得钙钛矿太阳能电池。
实施例2：
采用透明导电玻璃作为基底。将洁净后的基底放入原子层沉积设备的反应腔室中，真空抽至0.1Pa。并将反应腔室内的温度保持在120℃，通入50sccm N2作为锡源载气。采用温度均为80℃的四(二甲氨基)锡(Ⅳ)和二甲基氨基 -2-甲基-2-丙氧基锡(Ⅱ)分别作为第一锡源和第二锡源。采用温度为室温的H2O作为氧源。基于此，先向反应腔室内通入四(二甲氨基)锡(Ⅳ)源10s，接着采用N2吹扫12s。再向反应腔室内通入H2O源10s，接着采用N2吹扫12s，以此作为一个第一循环。并在执行30次上述第一循环后，改为先向反应腔室内通入二甲基氨基-2-甲基-2-丙氧基锡(Ⅱ)源10s，接着采用N2吹扫12s。再向反应腔室内通入H2O源10s，接着采用N2吹扫12s，以此作为一个第二循环。并执行3次上述第二循环。通过交替执行上述第一循环和第二循环380次，可以形成目标厚度为50nm的电子传输层。
然后，在电子传输层上形成材料为Cs0.05FA0.8MA0.15PbI3、且厚度为1000nm的光吸收层。接着，在光吸收层上形成材料为spiro-MeOTAD、且厚度为50nm的空穴传输层。最后在空穴传输层上形成了材料为金、且厚度为100nm的第一电极，获得钙钛矿太阳能电池。
实施例3：
采用透明导电玻璃作为基底。将洁净后的基底放入原子层沉积设备的反应腔室中，真空抽至0.1Pa。并将反应腔室内的温度保持在120℃，通入50sccm N2作为锡源载气。采用二甲基氨基-2-甲基-2-丙氧基锡(Ⅱ)作为锡源，并使得锡源保持80℃。采用温度为室温的H2O作为氧源。基于此，先向反应腔室内通入二甲基氨基-2-甲基-2-丙氧基锡(Ⅱ)源10s，接着采用N2吹扫12s，再向反应腔室内通入H2O源10s，接着采用N2吹扫12s。同时，设置好等离体子系统跟随锡源通入时间使脉冲调制射频放电，以此作为一个第一循环。并在执行50次上述第一循环后，改为先向反应腔室内通入二甲基氨基-2-甲基-2-丙氧基锡(Ⅱ)源10s，接着采用N2吹扫12s，再向反应腔室内通入H2O源10s，接着采用N2吹扫12s。同时设置脉冲调制射频不再放电，以此作为一个第二循环。并执行5次第二循环。通过交替执行上述第一循环和第二循环150次，可以形成目标厚度为20nm的电子传输层。
然后，在电子传输层上形成材料为Cs0.05FA0.8MA0.15PbI3、且厚度为1000nm的光吸收层。接着，在光吸收层上形成材料为spiro-MeOTAD、且厚度为50nm的空穴传输层。最后在空穴传输层上形成了材料为金、且厚度为100nm的第一电极，获得钙钛矿太阳能电池。
进一步地，本申请还提供了如下对比例制造钙钛矿太阳能电池，具体操作步骤如下：
对比例1：
采用透明导电玻璃作为基底。将洁净后的基底放入原子层沉积设备的反应腔室中，真空抽至0.1Pa。并将反应腔室内的温度保持在120℃，通入50sccm N2作为锡源载气。采用原子层沉积工艺，以四(二甲氨基)锡(Ⅳ)为锡源，并以H2O或O3为氧源。在80℃至150℃的反应温度下，先向反应腔室内通入锡源10s至20s，接着采用N2吹扫10s至50s。再向反应腔室内通入氧源10s至20s，并采用N2吹扫时间10s至50s。如此循环160次，可以形成目标厚度为20nm的电子传输层。
然后，在电子传输层上形成材料为Cs0.05FA0.8MA0.15PbI3、且厚度为1000nm的光吸收层。接着，在光吸收层上形成材料为spiro-MeOTAD、且厚度为50nm的空穴传输层。最后在空穴传输层上形成了材料为金、且厚度为100nm的第一电极，获得钙钛矿太阳能电池。
其中，表1对通过上述实施例1、实施例2、实施例3和对比例所制造的钙钛矿太阳能电池进行测试，并对上述四种钙钛矿太阳能电池的参数进行比较。
表1：实施例1、实施例2、实施例3和对比例所制造的钙钛矿太阳能电池各项参数比较
由表1中示出的各项数据可以看出，实施例1、实施例2和实施例3制造的钙钛矿太阳能电池的效率、开路电压、短路电流密度和填充因子的平均值均分别高于通过对比例制造的钙钛矿太阳能电池对应的效率、开路电压、 短路电流密度和填充因子的平均值，即实施例1至3制造的钙钛矿太阳能电池的钝化品质优于对比例制造的钙钛矿太阳能电池。
在以上的描述中，对于各层的构图、刻蚀等技术细节并没有做出详细的说明。但是本领域技术人员应当理解，可以通过各种技术手段，来形成所需形状的层、区域等。另外，为了形成同一结构，本领域技术人员还可以设计出与以上描述的方法并不完全相同的方法。另外，尽管在以上分别描述了各实施例，但是这并不意味着各个实施例中的措施不能有利地结合使用。
以上对本申请的实施例进行了描述。但是，这些实施例仅仅是为了说明的目的，而并非为了限制本申请的范围。本申请的范围由所附权利要求及其等价物限定。不脱离本申请的范围，本领域技术人员可以做出多种替代和修改，这些替代和修改都应落在本申请的范围之内。

Claims (14)

  1. 一种钙钛矿太阳能电池，其中，包括：光吸收层；
    空穴传输层，形成在所述光吸收层的一侧；
    电子传输层，形成在所述光吸收层背离所述空穴传输层的一侧；所述电子传输层的材料包括氧化锡和锡氧化物；所述锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，所述锡氧化物包括氧化亚锡。
  3. 根据权利要求2所述的钙钛矿太阳能电池，其中，所述电子传输层内所述氧化锡和所述氧化亚锡的化学计量比的范围为：5:1至50:1。
  4. 根据权利要求1所述的钙钛矿太阳能电池，其中，沿着所述光吸收层的厚度方向，所述电子传输层包括交替层叠的第一含锡氧化物层和第二含锡氧化物层；所述第一含锡氧化物层的材料为所述氧化锡；所述第二含锡氧化物层的材料为所述锡氧化物；或，
    所述电子传输层为所述氧化锡和所述锡氧化物混合而成的混合材料层。
  5. 根据权利要求1～4任一项所述的钙钛矿太阳能电池，其中，所述电子传输层的厚度为10nm至200nm。
  6. 一种叠层太阳能电池，其中，所述叠层太阳能电池包括底电池、以及位于所述底电池上的顶电池；
    所述顶电池为权利要求1～5任一项所述的钙钛矿太阳能电池。
  7. 一种钙钛矿太阳能电池的制造方法，其中，
    提供一基底；
    在所述基底上依次形成空穴传输层、光吸收层和电子传输层；或，在所述基底上依次形成电子传输层、光吸收层和空穴传输层；其中，
    所述电子传输层的材料包括氧化锡和锡氧化物；所述锡氧化物内锡元素和氧元素的化学计量比大于1:2，且小于等于1:1。
  8. 根据权利要求7所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层包括：
    向反应腔室内X次交替通入锡源和第一氧源；其中，X为大于或等于1的正整数，所述锡源内锡的化合价为+2价，所述第一氧源包括水和醇中的 至少一种；
    向所述反应腔室内Y次交替通入所述锡源和第二氧源；其中，Y为大于或等于1的正整数，所述第二氧源包括氧气、臭氧和双氧水中的至少一种；
    循环Z次上述操作，直至形成具有目标厚度的所述电子传输层；Z为大于或等于1的正整数。
  9. 根据权利要求7所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层包括：
    向反应腔室内交替通入锡源、以及由第一氧源和第二氧源组成的混合物，直至形成具有目标厚度的所述电子传输层；
    其中，所述锡源内锡的化合价为+2价，所述第一氧源包括水和醇中的至少一种，上述第二氧源包括氧气、臭氧和双氧水中的至少一种。
  10. 根据权利要求7所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层包括：
    向反应腔室内X次交替通入第一锡源和氧源；其中，Y为大于或等于1的正整数，所述第一锡源内锡的化合价为+2价，所述氧源包括水和醇中的至少一种；
    向所述反应腔室内Y次交替通入第二锡源和所述氧源；其中，X为大于或等于1的正整数，所述第二锡源内锡的化合价为+4价；
    循环Z次上述操作，直至形成具有目标厚度的所述电子传输层；Z为大于或等于1的正整数。
  11. 根据权利要求8或10所述的钙钛矿太阳能电池的制造方法，其中，1≤X≤10，30≤Y≤50。
  12. 根据权利要求7所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层包括：
    向反应腔室内交替通入由第一锡源和第二锡源组成的混合物、以及氧源，直至形成具有目标厚度的所述电子传输层；
    其中，所述第一锡源内锡的化合价为+2价，所述第二锡源内锡的化合价为+4价，所述氧源包括水和醇中的至少一种。
  13. 根据权利要求7所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层包括：
    向反应腔室内Z次交替通入锡源和氧源，直至形成具有目标厚度的所述电子传输层；其中，在X次交替通入过程中，向所述反应腔室内通入所述锡源的同时进行等离子体放电；Z为大于1的正整数；X为小于Z、且大于等于1的正整数；所述锡源中内锡的化合价为+2价；所述氧源包括水和醇中的至少一种。
  14. 根据权利要求7～10、12、13任一项所述的钙钛矿太阳能电池的制造方法，其中，形成所述电子传输层的反应温度为50℃至250℃。
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