A method for preparing an atomic layer deposition thin film

Abstract

The present invention discloses a method for preparing an atomic layer deposition thin film. The preparation method comprises the following steps: A1 placing a substrate in an atomic layer deposition system and injecting a first insulating gas; A2 introducing a first precursor and a first reactant; A3 pushing the substrate to move back and forth in the system; A4 obtaining a substrate / ALD-buffer layer, stopping the back-and-forth movement and evacuating, and introducing a second insulating gas; A5 introducing a second precursor and a second reactant; A6 pushing the ALD-buffer layer / substrate to move back and forth in the system; A7 obtaining a substrate / ALD-buffer layer / ALD-SnO2 film layer. In the present invention, the two film layers can be prepared in the same production process using the same ALD equipment, which greatly reduces production costs, simplifies the production process, and improves production efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to a method for preparing an atomic layer deposition thin film. Background Art

[0002] Inverted structure (pin type) perovskite solar cells have attracted much attention in recent years due to their excellent operational stability, low hysteresis, low temperature processing, and low processing cost. However, the photoelectric conversion efficiency of inverted perovskite solar cells is still lower than that of traditional normal structure perovskite solar cells, among which the electron transport layer has an important influence on the photoelectric conversion efficiency of the cell. The tin oxide (ALD-SnO2) film prepared by atomic layer deposition (ALD) technology can be used as an electrode material in inverted structure perovskite solar cells, such as as an electron transport layer or back electrode. ALD technology can ensure the uniformity of the tin oxide film layer and precisely control the thickness, thereby optimizing the battery performance. This film layer helps to provide efficient electron transport and power collection functions in solar cells, while providing good light transmittance and reducing light absorption losses.

[0003] The preparation process of ALD-SnO2 film generally requires water (H2O), hydrogen peroxide (H2O2), ozone (O3) or plasma oxygen (O2-Plasma) as reactants. However, these reactants will cause the hydrolysis or oxidation of the perovskite solar cell absorption layer, thereby affecting the photoelectric conversion efficiency of the perovskite solar cell and even causing failure. Therefore, the ALD-SnO2 film cannot be used directly as an electron transport layer. It is necessary to insert a layer of fullerene (carbon 60) or fullerene derivatives (such as [6,6]-phenyl-C 61 The electron transport layer composed of an ALD-SnO2 film and fullerene (or fullerene derivative) is called a double electron transport layer. The double electron transport layer perovskite solar cell structure is: glass / transparent conductive layer / hole transport layer / perovskite light absorbing layer / fullerene (or fullerene derivative) / ALD-SnO2 / electrode.

[0004] However, the production of the buffer layer / ALD-SnO2 double electron transport layer faces the following problems: fullerenes are generally formed by evaporation (the evaporation method takes a long time to form films, generally more than 15 minutes), fullerene derivatives are generally formed by coating, and ALD-SnO2 requires the use of ALD technology. Therefore, the preparation of the double electron transport layer requires at least two different types of coating equipment, which will lead to increased production costs, complicated production processes, and low production efficiency.

[0005] Based on this, it is urgent to develop a new method for preparing atomic layer deposition thin films to reduce production costs, simplify production processes, and improve production efficiency. Summary of the Invention

[0006] The technical problems to be solved by the present invention are:

[0007] Provided is a method for preparing an atomic layer deposition thin film.

[0008] In order to solve the technical problem, the technical solution adopted by the present invention is:

[0009] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0010] A1 places a substrate in an atomic layer deposition system and injects a first isolation gas;

[0011] A2 forms a non-contact first precursor region and a first reactant region separated by a first isolation gas region in the system reaction chamber by introducing a first precursor and a first reactant region;

[0012] A3 pushes the substrate to move back and forth, passing through the first precursor area, the first isolation gas area, and the first reactant area in sequence;

[0013] After A4 reaches the required coating thickness, the substrate / ALD-buffer layer is obtained, the reciprocating motion is stopped, the vacuum is evacuated, and the second isolation gas is introduced;

[0014] A5 forms a non-contact second precursor region and a second reactant region separated by a second isolation gas region in the system reaction chamber by introducing a second precursor and a second reactant region;

[0015] A6 pushes the substrate / ALD-buffer layer to move back and forth, passing through the second precursor area, the second isolation gas area, and the second reactant area in sequence;

[0016] After A7 reaches the required coating thickness, the substrate / ALD-buffer layer / ALD-SnO2 film layer is obtained.

[0017] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0018] This paper proposes using ALD technology to simultaneously prepare an ALD-buffer layer and an ALD-SnO2 film, integrating the electron transport layer of perovskite solar cells into a single process to simplify the production process and improve production efficiency. Benefiting from the excellent film properties of ALD technology, the ALD-coated buffer layer has a higher density than that of evaporation or coating technologies, effectively preventing the reactants in the ALD preparation process of the second electron transport layer from damaging the perovskite absorber layer.

[0019] This paper uses a non-aqueous, non-oxidative ALD technique to deposit a buffer layer (ALD-buffer layer), replacing the traditional fullerene or fullerene derivative buffer layer, for the preparation of the electron transport layer (ETL) of inverse (pin) perovskite solar cells. Furthermore, combined with conventional ALD-SnO2 deposition technology, this enables the full ALD process for preparing the ETL (ALD-buffer layer / ALD-SnO2).

[0020] Furthermore, the ALD-buffer layer and the ALD-SnO2 film layer described in the present invention can be prepared by the same ALD equipment in the same production process, which greatly reduces the production cost, simplifies the production process, and improves the production efficiency.

[0021] According to one embodiment of the present invention, in step A2, the first precursor and the first reactant introduced to prepare the ALD-buffer layer are both non-aqueous and non-oxidizing substances, and the selected precursors and reactants do not cause hydrolysis or oxidation of the perovskite absorption layer.

[0022] According to one embodiment of the present invention, the film type of the ALD-buffer layer is a metal oxide or a metal-based organic-inorganic hybrid film layer.

[0023] According to one embodiment of the present invention, the metal oxide includes at least one of tin oxide, titanium oxide, aluminum oxide, hafnium oxide, zirconium oxide, and nickel oxide prepared by ALD technology.

[0024] According to one embodiment of the present invention, the metal-based organic-inorganic hybrid film layer includes at least one of an aluminum-based organic-inorganic hybrid material, a gallium-based organic-inorganic hybrid material, an indium-based organic-inorganic hybrid material, an antimony-based organic-inorganic hybrid material, a beryllium-based organic-inorganic hybrid material, and a tellurium-based organic-inorganic hybrid material prepared by ALD technology.

[0025] According to one embodiment of the present invention, the first precursor includes at least one of a metal alkoxide complex and a metal alkyl compound.

[0026] According to one embodiment of the present invention, the metal alkoxide complex includes at least one of tin tert-butoxide, titanium tert-butoxide, aluminum tert-butoxide, hafnium tert-butoxide, zirconium tert-butoxide, nickel tert-butoxide, tin isopropoxide, titanium isopropoxide, aluminum isopropoxide, hafnium isopropoxide, zirconium isopropoxide, nickel isopropoxide, tin sec-butoxide, titanium sec-butoxide, aluminum sec-butoxide, hafnium sec-butoxide, zirconium sec-butoxide, nickel sec-butoxide, tin isobutoxide, titanium isobutoxide, aluminum isobutoxide, hafnium isobutoxide, zirconium isobutoxide, and nickel isobutoxide.

[0027] According to one embodiment of the present invention, the metal alkyl compound includes at least one of trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc, trimethylgallium, triethylgallium, trimethylindium, triethylindium, trimethylantimony, diethylberyllium, and diethyltellurium.

[0028] According to one embodiment of the present invention, when the first precursor is a metal alkoxide complex, the first reactant is a carboxylic acid substance, and the carboxylic acid substance includes at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.

[0029] According to one embodiment of the present invention, when the first precursor is a metal alkoxide complex, it should be recognized that the first reactant can be any carboxyl-containing alkyl acid reactant that does not damage the perovskite absorber layer.

[0030] According to one embodiment of the present invention, when the first precursor is a metal alkyl compound, the first reactant is a polycarboxylic acid or a polyol compound.

[0031] According to one embodiment of the present invention, the polycarboxylic acid includes at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.

[0032] According to one embodiment of the present invention, the polyol compound includes at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0033] According to one embodiment of the present invention, when the first precursor is a metal alkyl compound, it should be recognized that the first reactant can be any polycarboxylic acid or alcohol compound that does not damage the perovskite absorption layer.

[0034] According to one embodiment of the present invention, the second precursor includes tetrakis(dimethylamino)tin.

[0035] According to one embodiment of the present invention, the second reactant includes at least one of water, hydrogen peroxide, ozone, and plasma oxygen.

[0036] According to one embodiment of the present invention, the thickness of the ALD buffer layer is 0.2-1 nm.

[0037] The buffer layer prepared by ALD technology is thin enough to be 0.2-1nm, ensuring full coverage while achieving electron tunneling.

[0038] According to one embodiment of the present invention, before the coating process begins, the substrate coated with the perovskite absorption layer is transferred to the ALD chamber by a robot.

[0039] According to one embodiment of the present invention, before the coating process begins, the film transfer between the front-end process and the ALD process is carried out through a vacuum transition chamber.

[0040] According to one embodiment of the present invention, the substrate is a glass substrate.

[0041] According to one embodiment of the present invention, step A1 further includes the step of heating the substrate so that the substrate is heated to 50°C-150°C. After the temperature is constant, the substrate needs to maintain this temperature throughout the entire process.

[0042] According to one embodiment of the present invention, the pressure of the reaction chamber during the ALD process is maintained at 10-30 Torr, preferably 13 Torr.

[0043] According to one embodiment of the present invention, the first isolation gas and the second isolation gas are inert gases, such as high-purity nitrogen or high-purity argon.

[0044] According to one embodiment of the present invention, in step A4, after vacuuming, the pressure in the reaction chamber is about 0.005 Torr.

[0045] According to one embodiment of the present invention, the speed of the reciprocating motion of the substrate in step A3 and the reciprocating motion of the substrate / ALD-buffer layer in step A6 are both 0.01-10 m / s.

[0046] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0048] Figure 1 Flowchart of the method for preparing a thin film by atomic layer deposition in Example 1. DETAILED DESCRIPTION

[0049] In the description of the present invention, if there is a description of first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0050] The terms "preferably," "more preferably," and the like, used herein refer to embodiments of the present invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present invention.

[0051] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are understood to include any and all subranges subsumed therein.

[0052] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts are within the scope of the present invention.

[0053] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0054] Example 1

[0055] Example 1: An electron transport layer for an inverse perovskite solar cell having an ALD-TiO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0056] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0057] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0058] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0059] A2. The sample was heated to 80°C, and 10 SLM of titanium isopropoxide (a titanium precursor) and 10 SLM of acetic acid (a reactant) were simultaneously introduced into the ALD chamber.

[0060] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with one cycle five times to obtain a TiO2 film with a thickness of 0.6 nm.

[0061] A4. After the sample stops moving, turn off the titanium precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0062] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0063] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0064] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0065] Example 2

[0066] Example 2: An electron transport layer for an inverse perovskite solar cell is prepared, wherein the film system is ALD-aluminum-based organic-inorganic hybrid film / ALD-SnO2. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0067] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0068] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0069] A1. Place a 2m wide and 2m long sample in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen isolation gas at a flow rate of 40 SLM into the ALD chamber.

[0070] A2. The sample was heated to 80°C, and 10 SLM of trimethylaluminum (aluminum precursor) and 10 SLM of ethylene glycol (ethylene glycol) were introduced into the ALD chamber simultaneously.

[0071] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with a cycle three times to obtain an aluminum-based organic-inorganic hybrid film with a thickness of 0.6 nm;

[0072] A4. After the sample stops moving, turn off the aluminum precursor, ethylene glycol, and nitrogen barrier gas, pump down the chamber pressure to 0.005 Torr, and introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0073] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0074] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0075] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0076] Example 3

[0077] The difference between Example 3 and Example 1 is that the titanium precursor in Example 3 is titanium sec-butoxide.

[0078] Example 3: An electron transport layer for an inverse perovskite solar cell having an ALD-TiO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer having a structural formula of methylamine lead iodide (CH3NH3PbI3).

[0079] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0080] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0081] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0082] A2. The sample was heated to 80°C, and 10 SLM of titanium precursor titanium sec-butoxide gas and 10 SLM of reactant acetic acid gas were simultaneously introduced into the atomic layer deposition chamber.

[0083] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with one cycle five times to obtain a TiO2 film with a thickness of 0.6 nm.

[0084] A4. After the sample stops moving, turn off the titanium precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0085] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0086] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0087] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0088] Example 4

[0089] The difference between Example 4 and Example 1 is that the titanium precursor in Example 4 is titanium tert-butoxide.

[0090] Example 4: An electron transport layer for an inverse perovskite solar cell having an ALD-TiO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer having a structural formula of methylamine lead iodide (CH3NH3PbI3).

[0091] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0092] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0093] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0094] A2. The sample was heated to 80°C, and 10 SLM of titanium precursor tert-butoxide gas and 10 SLM of reactant acetic acid gas were simultaneously introduced into the ALD chamber.

[0095] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with one cycle five times to obtain a TiO2 film with a thickness of 0.6 nm.

[0096] A4. After the sample stops moving, turn off the titanium precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0097] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0098] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0099] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0100] Example 5

[0101] The difference between Example 5 and Example 1 is that the first precursor of Example 5 is aluminum precursor aluminum tert-butoxide.

[0102] Example 5: An electron transport layer for an inverse perovskite solar cell having an ALD-Al2O3 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0103] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0104] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0105] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0106] A2. The sample was heated to 80°C, and 10 SLM of aluminum precursor (aluminum tert-butoxide) and 10 SLM of acetic acid were introduced simultaneously into the ALD chamber.

[0107] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction zone with one cycle five times to obtain an Al2O3 film with a thickness of 0.6 nm.

[0108] A4. After the sample stops moving, turn off the aluminum precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0109] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0110] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0111] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0112] Example 6

[0113] The difference between Example 6 and Example 1 is that the first precursor of Example 6 is aluminum isopropoxide, which is an aluminum precursor.

[0114] Example 6: An electron transport layer for an inverse perovskite solar cell having an ALD-Al2O3 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0115] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0116] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0117] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0118] A2. The sample was heated to 80°C, and 10 SLM of aluminum isopropoxide (aluminum precursor) and 10 SLM of acetic acid (a reactant) were introduced into the ALD chamber simultaneously.

[0119] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction zone with one cycle five times to obtain an Al2O3 film with a thickness of 0.6 nm.

[0120] A4. After the sample stops moving, turn off the aluminum precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0121] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0122] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0123] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0124] Example 7

[0125] The difference between Example 7 and Example 1 is that the first precursor of Example 7 is nickel isopropoxide, which is a nickel precursor.

[0126] Example 7: An electron transport layer for an inverse perovskite solar cell having an ALD-NiO / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0127] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0128] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0129] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0130] A2. The sample was heated to 80°C, and 10 SLM of nickel isopropoxide (nickel precursor) and 10 SLM of acetic acid (reactant) were introduced into the ALD chamber simultaneously.

[0131] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with one cycle five times to obtain a NiO film with a thickness of 0.6 nm.

[0132] A4. After the sample stops moving, turn off the nickel precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0133] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0134] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0135] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0136] Example 8

[0137] The difference between Example 8 and Example 1 is that the first precursor in Example 8 is a hafnium precursor, hafnium isobutoxide.

[0138] Example 8: An electron transport layer for an inverse perovskite solar cell having an ALD-HfO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0139] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0140] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0141] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0142] A2. The sample was heated to 80°C, and 10 SLM of hafnium isobutoxide (the hafnium precursor) and 10 SLM of acetic acid (the reactant) were introduced into the ALD chamber simultaneously.

[0143] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with a cycle five times to obtain a HfO2 film with a thickness of 0.6 nm;

[0144] A4. After the sample stops moving, turn off the hafnium precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0145] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0146] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0147] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0148] Example 9

[0149] The difference between Example 9 and Example 1 is that the first precursor of Example 9 is the zirconium precursor hafnium isobutoxide, and the first reactant is propionic acid.

[0150] Example 9: An electron transport layer for an inverse perovskite solar cell having an ALD-HfO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0151] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0152] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0153] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0154] A2. The sample was heated to 80°C, and 10 SLM of hafnium isobutoxide (the hafnium precursor) and 10 SLM of propionic acid (the reactant) were simultaneously introduced into the ALD chamber.

[0155] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with a cycle five times to obtain a HfO2 film with a thickness of 0.6 nm;

[0156] A4. After the sample stops moving, turn off the hafnium precursor, propionic acid reactant, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0157] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0158] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0159] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0160] Example 10

[0161] The difference between Example 10 and Example 2 is that the film system of Example 10 is an ALD-zinc-based organic-inorganic hybrid film / ALD-SnO2, and the first precursor is dimethyl zinc.

[0162] Example 10: An electron transport layer for an inverse perovskite solar cell having an ALD-zinc-based organic-inorganic hybrid film / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0163] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0164] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0165] A1. Place a 2m wide and 2m long sample in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen isolation gas at a flow rate of 40 SLM into the ALD chamber.

[0166] A2. The sample was heated to 80°C, and 10 SLM of dimethylzinc (Zn) gas (a zinc precursor) and 10 SLM of ethylene glycol (EG) gas (a reactant) were simultaneously introduced into the ALD chamber.

[0167] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with a cycle three times to obtain a zinc-based organic-inorganic hybrid film with a thickness of 0.6 nm;

[0168] A4. After the sample stops moving, turn off the zinc precursor, ethylene glycol, and nitrogen barrier gas, pump down the chamber pressure to 0.005 Torr, and introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0169] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20 SLMS and a reactant water gas at a flow rate of 20 SLM are simultaneously introduced into the atomic layer deposition chamber;

[0170] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0171] A7. After the sample stops moving, turn off the tin precursor, reactant water, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0172] Example 11

[0173] The difference between Example 11 and Example 1 is that the second reactant in Example 11 is hydrogen peroxide.

[0174] Example 11: An electron transport layer for an inverse perovskite solar cell having an ALD-TiO2 / ALD-SnO2 film system is prepared. The electron transport layer is directly attached to a commercial perovskite absorption layer, and the structural formula of the perovskite absorption layer is methylamine lead iodide (CH3NH3PbI3).

[0175] The sample used to prepare the electron transport layer is a sheet substrate with a glass substrate, a thickness of 3 mm and an area of ​​4 m 2 The specific structure of the sample is: glass / ITO / NiO / CH3NH3PbI3.

[0176] A method for preparing an atomic layer deposition thin film comprises the following steps:

[0177] A1. Place a 2m wide and 2m long substrate in the ALD chamber. Use a dry pump to reduce the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 40 SLM into the ALD chamber.

[0178] A2. The sample was heated to 80°C, and 10 SLM of titanium isopropoxide (a titanium precursor) and 10 SLM of acetic acid (a reactant) were simultaneously introduced into the ALD chamber.

[0179] A3. Start the sample moving device and move the deposited sample back and forth in both directions at a speed of 5 m / s through the reaction area with one cycle five times to obtain a TiO2 film with a thickness of 0.6 nm.

[0180] A4. After the sample stops moving, turn off the titanium precursor, reactant acetic acid, and nitrogen barrier gas, and pump down the chamber pressure to 0.005 Torr. Then, introduce high-purity nitrogen barrier gas at a flow rate of 50 SLM into the ALD chamber.

[0181] A5. A tin precursor tetradimethylamine tin gas at a flow rate of 20SLMS and a reactant hydrogen peroxide gas at a flow rate of 20SLM are simultaneously introduced into the atomic layer deposition chamber;

[0182] A6. Start the sample moving device and move the deposited sample back and forth through the reaction zone with one cycle in both directions at a speed of 6 m / s 150 times to obtain a SnO2 film with a thickness of 20 nm;

[0183] A7. After the sample stops moving, turn off the tin precursor, reactant hydrogen peroxide, and nitrogen barrier gas, evacuate to 0.005 Torr, turn off sample heating, backfill with nitrogen, open the atomic layer deposition system chamber door, and remove the processed sample.

[0184] The above are merely embodiments of the present invention and are not intended to limit the scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the scope of protection of the present invention.

Claims

1. A method for preparing an atomic layer deposition thin film for an inverted perovskite solar cell, characterized by: The following steps are involved: A1 places a substrate in an atomic layer deposition system and injects a first isolation gas; A2 forms a non-contact first precursor region and a first reactant region separated by a first isolation gas region in the system reaction chamber by introducing the first precursor and the first reactant; A3 pushes the substrate to move back and forth, passing through the first precursor area, the first isolation gas area, and the first reactant area in sequence; A4 After the required coating thickness is reached, the substrate / ALD-buffer layer is obtained, the reciprocating motion is stopped, the vacuum is evacuated, and the second isolation gas is introduced; A5 forms a non-contact second precursor region and a second reactant region separated by a second isolation gas region in the system reaction chamber by introducing a second precursor and a second reactant region; A6 pushes the ALD-buffer layer / substrate to move back and forth, passing through the second precursor area, the second isolation gas area, and the second reactant area in sequence; A7 After the required coating thickness is reached, the substrate / ALD-buffer layer / ALD-SnO2 film layer is obtained; The first precursor is a metal alkoxy complex or a metal alkyl compound; When the first precursor is a metal alkoxy complex, the first reactant is a carboxylic acid substance; when the first precursor is a metal alkyl compound, the first reactant is a polycarboxylic acid or a polyol compound.

2. The method according to claim 1, wherein: The metal alkoxide complex includes at least one of tin tert-butoxide, titanium tert-butoxide, aluminum tert-butoxide, hafnium tert-butoxide, zirconium tert-butoxide, nickel tert-butoxide, tin isopropoxide, titanium isopropoxide, aluminum isopropoxide, hafnium isopropoxide, zirconium isopropoxide, nickel isopropoxide, tin sec-butoxide, titanium sec-butoxide, aluminum sec-butoxide, hafnium sec-butoxide, zirconium sec-butoxide, nickel sec-butoxide, tin isobutoxide, titanium isobutoxide, aluminum isobutoxide, hafnium isobutoxide, zirconium isobutoxide, and nickel isobutoxide.

3. The method according to claim 1, wherein: The metal alkyl compound includes at least one of trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc, trimethylgallium, triethylgallium, trimethylindium, triethylindium, trimethylantimony, diethylberyllium, and diethyltellurium.

4. The method according to claim 1, wherein: The carboxylic acid substance includes at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.

5. The method according to claim 1, wherein: The second precursor includes tetrakis dimethylaminotin.

6. The method according to claim 1, wherein: The second reactant includes at least one of water, hydrogen peroxide, ozone, and plasma oxygen.

7. The method according to claim 1, wherein: The thickness of the ALD buffer layer is 0.2-1 nm.

8. The method according to claim 1, wherein: The speed of the substrate reciprocating motion in step A3 and the substrate / ALD-buffer layer reciprocating motion in step A6 are both 0.01-10 m / s.

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