A film layer of a perovskite solar cell, a preparation method thereof, and a preparation device

Abstract

The present invention provides a film layer for a perovskite solar cell, a preparation method thereof, and a preparation device. The film layer preparation device includes a reaction chamber and a vacuum pumping device communicated with the reaction chamber. A rotating device is arranged at the bottom of the inner cavity of the reaction chamber, and the space above the rotating device is divided into at least two working areas in the counterclockwise or clockwise direction; among the at least two working areas, at least one working area is communicated with a first gas source through a pipeline, and at least one working area is communicated with a second gas source through a pipeline. The present invention can obtain a high-quality film layer while greatly shortening the preparation time, meeting the requirements of industrialization.

Description

Technical Field

[0001] The present invention belongs to the field of photovoltaics, and in particular relates to a film layer of a perovskite solar cell and a preparation method and preparation equipment thereof. Background Art

[0002] Over the past few years, there has been a significant amount of research and development in perovskite solar cells. The surge in interest in perovskite solar cells stems from the achievement of power conversion efficiencies (PCEs) exceeding 25% using low-cost solution-processing methods to fabricate perovskite solar cells.

[0003] However, perovskite materials are prone to decomposition in environments such as water, light, heat and oxygen, which makes the stability of the prepared perovskite solar cell devices poor, which has become a huge obstacle to their industrial application. In recent years, significant progress has been made in solving the instability of metal halide perovskite solar cells, which are caused by external pressures (such as moisture, heat, oxygen or light). Studies have found that by using atomic layer deposition, the effects of external factors such as moisture and oxygen on the stability of perovskite solar cells can be better solved. This is because the thickness and composition of the film can be precisely controlled during its preparation process, so the resulting film has excellent barrier properties, effectively improving the stability of the film and the device.

[0004] Currently, there are two main methods for preparing thin films using atomic layer deposition (ALD). One is time-based ALD. The long preparation cycle of time-based ALD equipment limits its application in industrial production. The other is space-based ALD. For example, CN112239861A discloses a method for producing a coating, which includes determining the surface defect area and the location of the surface defect in a coating on a substrate, and further includes applying a correction coating area to the surface defect area using a space-based ALD reactor, thereby selectively and locally correcting the surface defect. The advantage of space-based ALD is that it can significantly shorten the preparation time of thin films, which is difficult to achieve with time-based ALD. In perovskite solar cells, space-based ALD must be used to meet the needs of industrialization. However, if space-based ALD uses a faster deposition rate, more chemical vapor reactions will occur during the film deposition process, which will lead to poor film performance. If the deposition rate is reduced to ensure sufficient ALD reactions, the preparation time will be greatly increased, which conflicts with industrialization requirements.

[0005] Therefore, using atomic layer deposition to shorten the film preparation cycle of perovskite batteries and at the same time prepare high-quality films to meet the requirements of industrialization is a technical problem that needs to be solved urgently. Summary of the Invention

[0006] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a film layer for a perovskite solar cell, a preparation method thereof, and a preparation device. The present invention divides the space above the rotating tray in the reaction chamber into at least two working areas. Among the at least two working areas, at least one working area is connected to a first gas source, and at least one working area is connected to a second gas source. With the aid of this device, a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition can be completed in a relatively short time, realizing the preparation of a high-quality film layer and meeting the industrial requirements of industrialization.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted by the present invention:

[0008] In the first aspect, the present invention provides a film layer preparation device for a perovskite solar cell. The film layer preparation device includes a reaction chamber and a vacuum pumping device connected to the reaction chamber. A rotating device is provided at the bottom of the inner cavity of the reaction chamber, and the space above the rotating device is divided into at least two working areas in the counterclockwise or clockwise direction;

[0009] Among the at least two working areas, at least one working area is connected to a first gas source through a pipeline, and at least one working area is connected to a second gas source through a pipeline.

[0010] The present invention divides the space above the rotating device in the reaction chamber into at least two working areas. Among the at least two working areas, at least one working area is connected to a first gas source, and at least one working area is connected to a second gas source. With the aid of this device, a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition can be completed in a relatively short time, realizing the preparation of a high-quality film layer and meeting the industrial requirements of industrialization. The present invention divides the space above the rotating tray in the reaction chamber into four independent chambers, and connects a first precursor gas source, a first inert gas source, a second precursor gas source, and a second inert gas source to the first chamber, the second chamber, the third chamber, and the fourth chamber respectively, thereby completing a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition in a relatively short time, realizing the preparation of a high-quality film layer, and meeting the industrial requirements of industrialization.

[0011] In the present invention, the type of the gas source is not limited. Exemplarily, for example, it can be a source bottle or the like.

[0012] In the present invention, the rotating device is not limited. Exemplarily, for example, it can be a rotating tray or a guide rail or the like.

[0013] In the present invention, the rotating tray is rotated in the reaction chamber under the control of a motor.

[0014] Preferably, a chamber cover plate is provided at the top opening of the reaction chamber.

[0015] Preferably, the chamber cover plate includes a ventilation panel corresponding to the working area arranged in a counterclockwise or clockwise direction, and ventilation openings are formed in the ventilation panel.

[0016] Preferably, the number of ventilation openings on each ventilation panel includes at least one.

[0017] Preferably, the ventilation openings are selected from slits or holes.

[0018] In the present invention, using a slit or a hole as the ventilation opening can make the introduced gas deposit more uniformly on the substrate.

[0019] Preferably, the number of ventilation openings on each ventilation panel includes at least two, and the at least two ventilation openings are evenly distributed on each ventilation panel.

[0020] In the present invention, the type of the vacuum pumping device is not limited. Exemplarily, for example, it can be a mechanical pump or a Roots pump, etc.

[0021] Preferably, the upper space of the rotating device is divided into four working areas in a counterclockwise or clockwise direction, including a first working area, a second working area, a third working area, and a fourth working area;

[0022] Among the four working areas, the first working area is connected to the first gas source through a pipeline, the second working area is connected to the first inert gas source through a pipeline, the third working area is connected to the second gas source through a pipeline, and the fourth working area is connected to the second inert gas source through a pipeline.

[0023] Preferably, a partition is arranged in the reaction chamber, and the upper space of the rotating device is divided into a first chamber, a second chamber, a third chamber, and a fourth chamber in a counterclockwise or clockwise direction;

[0024] The first gas source is connected to the first chamber through a pipeline, the second gas source and the third chamber are connected through a pipeline, the first inert gas source is connected to the second chamber through a pipeline, and the second inert gas source is connected to the fourth chamber through a pipeline.

[0025] In a second aspect, the present invention provides a method for preparing a film layer of a perovskite solar cell. The preparation method uses the film layer preparation device described in the first aspect, and the preparation method includes the following steps:

[0026] (1) Place a substrate on the rotating device in the reaction chamber and evacuate it through the vacuum pumping device;

[0027] (2) Introduce the source gases in the first gas source and the second gas source into the corresponding working areas in the reaction chamber;

[0028] (3) Rotate the rotating device so that the substrate passes through the working area communicated with the first gas source and the working area communicated with the second gas source clockwise or counterclockwise, and perform a reaction to prepare the film layer.

[0029] The reaction in step (3) includes a first-order reaction, a second-order reaction, and a third-order reaction that are carried out in sequence. The first-order reaction and the third-order reaction are ALD reactions, and the second-order reaction is a CVD reaction.

[0030] The present invention has completed a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition. On the premise of obtaining a high-quality film layer, the preparation time is greatly shortened, meeting the requirements of industrialization.

[0031] It should be noted that in the present invention, the combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition, also known as the combined reaction of ALD reaction - CVD reaction - ALD reaction. In the ALD reaction, after the first precursor (i.e., the substance transported by the first gas source) undergoes an adsorption reaction, it is purged with an inert gas, leaving only a single layer of the first precursor adsorbed on the surface of the substrate. This reacts fully with the subsequently adsorbed second precursor (i.e., the substance transported by the second gas source), and then the excess second precursor is purged with an inert gas. At this time, only the reaction product remains. The CVD reaction means that after the first precursor undergoes an adsorption reaction and is purged with an inert gas, a relatively thick layer of the first precursor remains adsorbed on the surface of the substrate, which is not purged into a single layer of atoms. After reacting with the subsequently adsorbed second precursor, at this time, a part of the first precursor that has not participated in the reaction, the reaction product, and the excess second precursor remain. Then, the excess second precursor is purged with an inert gas, but a certain thickness of the second precursor still remains, which is not purged into a single layer of atoms. At this time, the product includes the first precursor, the reaction product, and the second precursor in sequence.

[0032] Preferably, the rate of the second-order reaction is greater than the rate of the first-order reaction, and the rate of the second-order reaction is greater than the rate of the third-order reaction.

[0033] In the present invention, if the rates of the first-order reaction, the second-order reaction, and the third-order reaction are equal, then only the same type of reaction is carried out, and it is difficult to simultaneously achieve short preparation time and high-quality film layer preparation. If the rates of the first-order reaction and the third-order reaction are both greater than the second-order reaction, then a combined reaction of chemical vapor deposition - atomic layer deposition - chemical vapor deposition will occur, reducing the film layer quality.

[0034] Preferably, the rotation rate of the first-order reaction is 20 - 60 rpm, for example, it can be 20 rpm, 30 rpm, 40 rpm, 50 rpm, or 60 rpm, etc.

[0035] Preferably, the rotation rate of the second-order reaction is 60 to 100 rpm, for example, it can be 60 rpm, 70 rpm, 80 rpm, 90 rpm, or 100 rpm, etc.

[0036] Preferably, the rotation rate of the third-order reaction is 20 to 60 rpm, for example, it can be 20 rpm, 30 rpm, 40 rpm, 50 rpm, or 60 rpm, etc.

[0037] Preferably, the reaction time of step (3) is 50 to 200 s, for example, it can be 50 s, 70 s, 90 s, 110 s, 130 s, 150 s, 170 s, 180 s, 190 s, or 200 s, etc.

[0038] Preferably, the specific steps of introducing the source gases in the first gas source and the second gas source into the corresponding working areas in the reaction chamber in step (2) include:

[0039] Introduce the source gas in the first gas source, the gas in the first inert gas source, the source gas in the second gas source, and the gas in the second inert gas source into the first working area, the second working area, the third working area, and the fourth working area in a clockwise or counterclockwise order;

[0040] In the second working area, the flow rate of the gas in the first inert gas source during the ALD reaction is greater than that during the CVD reaction;

[0041] In the fourth working area, the flow rate of the gas in the second inert gas source during the ALD reaction is greater than that during the CVD reaction.

[0042] In the present invention, when the gas flow rates in the first inert gas source and the second inert gas source are fast, the purging effect is strong, and the reactants can deposit only a single atomic layer without residue, so that the ALD reaction can be achieved. When the gas flow rates in the first inert gas source and the second inert gas source are slow, the purging effect is weak, and there is residue of the reactants, so that the CVD reaction can be achieved. For the specific gas flow rate design, those skilled in the art can select according to the specific types of chemical reactions, subject to meeting the requirements of the actual effect, and this application does not make any restrictions.

[0043] Preferably, the rotation rates of the first-order reaction, the second-order reaction, and the third-order reaction are the same.

[0044] Preferably, the preparation method includes the following steps:

[0045] (a) Place the substrate on the rotating device in the reaction chamber and evacuate it through a vacuum pumping device;

[0046] (b) Feed the source gas in the first gas source into the first working area in the reaction chamber through a pipeline, feed the source gas in the second gas source into the third working area in the reaction chamber through a pipeline, feed the gas in the first inert gas source into the second working area in the reaction chamber through a pipeline, and feed the gas in the second inert gas source into the fourth working area in the reaction chamber through a pipeline;

[0047] (c) Rotate the rotating tray device so that the substrate sequentially passes through the first working area, the second working area, the third working area, and the fourth working area in a clockwise or counterclockwise direction to carry out reactions and prepare the film layer.

[0048] Preferably, the temperature of the substrate in step (a) is 80 - 150 °C, for example, it can be 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, or 150 °C, etc.

[0049] Preferably, the degree of vacuum in the reaction chamber evacuated in step (a) is less than or equal to 10 Pa, for example, it can be 10 Pa, 8 Pa, 6 Pa, 4 Pa, 2 Pa, or 1 Pa, etc.

[0050] In the present invention, the reaction chamber only needs to maintain a low vacuum and does not require a high vacuum.

[0051] Preferably, the source gas in the first gas source in step (b) includes a first carrier gas and a substance transported by the first carrier gas, and the substance transported by the first carrier gas includes tin(IV) bis(dimethylamino) or trimethylaluminum.

[0052] In the present invention, the first carrier gas can refer to a gas that does not chemically react with the substances it contacts during transportation and is used to carry the substances that need to be transported. The carrier gas can be an inert gas, for example, it can be any one or a combination of at least two of nitrogen, helium, neon, argon, krypton, xenon, and radon. The same applies to the "second carrier gas" below.

[0053] In the present invention, if multiple substances transported by the first carrier gas are mixed, they will contaminate each other, resulting in problems such as pipeline blockage and source pollution.

[0054] Preferably, the flow rate of the substance transported by the first carrier gas is 500 - 2000 sccm, for example, it can be 500 sccm, 1000 sccm, 1500 sccm, or 2000 sccm, etc.

[0055] In the present invention, the flow rate of the substance transported by the first carrier gas refers to the flow rate of the substance transported by the first carrier gas in the gaseous state, and the gaseous state includes the mist state.

[0056] Preferably, the source gas in the second gas source in step (b) includes a second carrier gas and a substance transported by the second carrier gas, and the substance transported by the second carrier gas includes any one of O2, O3, H2O, or H2O2.

[0057] Preferably, the flow rate of the substance transported by the second carrier gas is 500 - 2000 sccm, and for example, it can be 500 sccm, 1000 sccm, 1500 sccm, or 2000 sccm, etc.

[0058] In the present invention, the flow rate of the substance transported by the second carrier gas refers to the flow rate of the substance transported by the second carrier gas in the gaseous state, and the gaseous state includes the fog state.

[0059] Preferably, the temperature of the first gas source in step (b) is 50 - 80 °C, and for example, it can be 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, or 80 °C, etc.

[0060] Preferably, the temperature of the second gas source in step (2) is 20 - 50 °C, and for example, it can be 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, or 50 °C, etc.

[0061] Preferably, the temperature of the pipeline in step (2) is 50 - 120 °C, and for example, it can be 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, or 120 °C, etc.

[0062] Preferably, the gas in the first inert gas source and the gas in the second inert gas source independently include any one of nitrogen, helium, neon, argon, krypton, xenon, or radon.

[0063] It should be noted that in the present invention, "independently" means that the gas in the first inert gas source can select any one of helium, neon, argon, krypton, xenon, or radon, and the gas in the second inert gas source can select any one of helium, neon, argon, krypton, xenon, or radon. The two can select the same type or different types, without interfering with each other. The following "independently" is the same in principle.

[0064] Preferably, the flow rate of the gas in the second working area and the fourth working area is greater than or equal to the flow rate of the source gas in the first working area, and the flow rate of the gas in the second working area and the fourth working area is greater than or equal to the flow rate of the source gas in the third working area.

[0065] In the present invention, in the working area where the first inert gas source and the second inert gas source are connected, the flow rate of the corresponding gas is greater than or equal to the flow rate of the source gas in the first working area or the flow rate of the source gas in the third working area, which can play a separating role. Therefore, the gases in the first inert gas source and the second inert gas source are also called separating gases.

[0066] Preferably, the flow rates of the gases in the first inert gas source and the second inert gas source are independently 5000 - 8000 sccm, for example, they can be 5000 sccm, 5500 sccm, 6000 sccm, 6500 sccm, 7000 sccm, 7500 sccm or 8000 sccm, etc.

[0067] Preferably, the temperatures of the first inert gas source and the second inert gas source are independently room temperature.

[0068] In the present invention, room temperature refers to 25 ± 5 °C, for example, it can be 20 °C, 22 °C, 24 °C, 26 °C, 28 °C or 30 °C, etc.

[0069] As a preferred technical solution, the preparation method includes the following steps:

[0070] (Ⅰ) Place the substrate on the rotating device in the reaction chamber, and at the same time control the temperature of the substrate to be 80 - 150 °C. Evacuate to a vacuum degree less than or equal to 10 Pa in the reaction chamber through the vacuum device, introduce the source gas in the first gas source into the first working area, the source gas in the second gas source into the third working area, the gas in the first inert gas source into the second working area, and the gas in the second inert gas source into the fourth working area;

[0071] Among them, the source gas in the first gas source includes the first carrier gas and the substance transported by the first carrier gas. The temperature of the first gas source is 50 - 80 °C, and the flow rate of the substance transported by the first carrier gas is 500 - 2000 sccm; the source gas in the second gas source includes the second carrier gas and the substance transported by the second carrier gas. The temperature of the second gas source is 20 - 50 °C, and the flow rate of the substance transported by the second carrier gas is 500 - 2000 sccm; the temperatures of the first inert gas source and the second inert gas source are independently room temperature, and the gas flow rates are independently 5000 - 8000 sccm; the temperature of the pipeline is 50 - 120 °C;

[0072] (Ⅱ) Rotate the rotating device at a rotation rate of 20 - 100 rpm, so that the substrate sequentially passes through the first working area, the second working area, the third working area and the fourth working area in a clockwise or counterclockwise direction, and perform the first-order reaction, the second-order reaction and the third-order reaction in sequence. After 50 - 200 s, the film layer is prepared;

[0073] Among them, the rate of the second-order reaction is greater than that of the first-order reaction, the rate of the second-order reaction is greater than that of the third-order reaction, the time of the second-order reaction is less than that of the first-order reaction, and the time of the second-order reaction is less than that of the third-order reaction.

[0074] In a third aspect, the present invention provides a film layer of a perovskite solar cell, and the film layer is prepared by using the preparation method described in the second aspect.

[0075] In the present invention, the prepared film layer has high quality and good compactness.

[0076] Preferably, the thickness of the film layer is 5-30 nm, and for example, it can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm or 30 nm, etc.

[0077] Preferably, the film layer includes any one of a perovskite layer, an electron transport layer, a hole transport layer or a packaging layer.

[0078] The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above numerical ranges not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the ranges.

[0079] Compared with the prior art, the present invention has the following beneficial effects:

[0080] The present invention divides the space above the rotating tray in the reaction chamber into at least two working areas. Among the at least two working areas, at least one working area is connected to a first gas source, and at least one working area is connected to a second gas source. With the aid of this device, a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition is completed in a short time, realizing the preparation of a high-quality film layer and meeting the industrial requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 It is a schematic diagram of the mechanism of the first-order reaction and the third-order reaction in Example 1 of the present invention.

[0082] Figure 2 It is a schematic diagram of the mechanism of the second-order reaction in Example 1 of the present invention.

[0083] Figure 3 It is a schematic diagram of the preparation equipment adopted in Example 1 of the present invention.

[0084] Figure 4 It is a schematic diagram of the preparation equipment provided by a specific embodiment in the present invention.

[0085] Figure 5 It is a schematic diagram of the chamber cover plate of the preparation equipment adopted in Example 1 of the present invention.

[0086] Figure 6 Schematic diagram of the rotating tray in the preparation equipment adopted in Embodiment 1 of the present invention.

[0087] Wherein, 1 - reaction chamber, 2 - rotating device, 3 - chamber cover plate, 4 - ventilation panel, 5 - ventilation port, 6 - substrate, 7 - partition board. Detailed implementation manners

[0088] It should be understood that in the description of the present invention, the orientation or positional relationships indicated by the terms "center", "longitudinal", "transverse", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientation or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first", "second", etc. may explicitly or implicitly include one or more of such features. In the description of the present invention, unless otherwise specified, the meaning of "a plurality" is two or more.

[0089] It should be noted that in the description of the present invention, unless otherwise clearly defined and limited, the terms "arranged", "connected", "coupled" should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; it may be directly connected or indirectly connected through an intermediate medium, and it may be the internal communication of two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0090] The technical solution of the present invention will be further described below with reference to the drawings and through specific implementation manners.

[0091] In a specific implementation manner, the present invention provides a film layer preparation device for a perovskite solar cell, as Figure 3 shown. The film layer preparation device includes a reaction chamber 1 and a vacuum pumping device communicated with the reaction chamber 1. A rotating device 2 is arranged at the bottom of the inner cavity of the reaction chamber 1. The rotating device 2 is as Figure 6 shown. The space above the rotating device 2 is divided into at least two working areas in the counterclockwise or clockwise direction;

[0092] Among the at least two working areas, at least one working area is communicated with a first gas source through a pipeline, and at least one working area is communicated with a second gas source through a pipeline.

[0093] In the present invention, the space above the rotating device 2 in the reaction chamber 1 is divided into at least two working areas. Among the at least two working areas, at least one working area is in communication with a first gas source, and at least one working area is in communication with a second gas source. With the aid of this device, a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition can be completed in a relatively short time, realizing the preparation of a high-quality film layer and meeting the industrial requirements of industrialization. In the present invention, the type of the gas source is not limited. Exemplarily, for example, it can be a source bottle or the like.

[0094] In the present invention, the rotating device 2 is not limited. Exemplarily, for example, it can be a rotating tray or a guide rail or the like.

[0095] In the present invention, the rotating device 2 is rotated in the reaction chamber 1 under the control of a motor.

[0096] Further, a chamber cover plate 3 is provided at the top opening of the reaction chamber 1.

[0097] Further, as Figure 5 shown, the chamber cover plate 3 includes a ventilation panel 4 corresponding to the working area and arranged along the counterclockwise or clockwise direction. The ventilation panel 4 is provided with ventilation openings 5.

[0098] Further, the number of ventilation openings 5 on each ventilation panel 4 includes at least one.

[0099] Further, the ventilation openings 5 are selected from slits or holes.

[0100] In the present invention, using a slit or a hole as the ventilation opening 5 can make the introduced gas deposit more uniformly on the substrate 6.

[0101] Further, the number of ventilation openings 5 on each ventilation panel 4 includes at least two, and the at least two ventilation openings are uniformly distributed on each ventilation panel 4.

[0102] In the present invention, the type of the vacuum pumping device is not limited. Exemplarily, for example, it can be a mechanical pump or a Roots pump or the like.

[0103] Preferably, the space above the rotating device 2 is divided into four working areas along the counterclockwise or clockwise direction, including a first working area, a second working area, a third working area, and a fourth working area;

[0104] Among the four working areas, the first working area is in communication with the first gas source through a pipeline, the second working area is in communication with the first inert gas source through a pipeline, the third working area is in communication with the second gas source through a pipeline, and the fourth working area is in communication with the second inert gas source through a pipeline.

[0105] In another specific embodiment, the schematic diagram of the preparation device is as shown in Figure 4 As shown, a partition 7 is arranged in the reaction chamber 1, and the partition 7 divides the space above the rotating device 2 into a first chamber, a second chamber, a third chamber, and a fourth chamber in the counterclockwise or clockwise direction.

[0106] The first gas source is communicated with the first chamber through a pipeline, the second gas source and the third chamber are communicated through a pipeline, the first inert gas source is communicated with the second chamber through a pipeline, and the second inert gas source is communicated with the fourth chamber through a pipeline.

[0107] In another specific embodiment, the present invention provides a method for preparing a film layer of a perovskite solar cell. The preparation method uses the above-mentioned film layer preparation device, and the preparation method includes the following steps:

[0108] (1) Place the substrate 6 on the rotating device 2 in the reaction chamber 1, and at the same time control the temperature of the substrate 6 to be 80-150 °C. Evacuate to a vacuum degree in the reaction chamber 1 less than or equal to 10 Pa through a vacuum device, and introduce the source gas in the first gas source into the first working area, the source gas in the second gas source into the third working area, the gas in the first inert gas source into the second working area, and the gas in the second inert gas source into the fourth working area;

[0109] Among them, the source gas in the first gas source includes a first carrier gas and a substance transported by the first carrier gas. The temperature of the first gas source is 50-80 °C, and the flow rate of the substance transported by the first carrier gas is 500-2000 sccm; the source gas in the second gas source includes a second carrier gas and a substance transported by the second carrier gas. The temperature of the second gas source is 20-50 °C, and the flow rate of the substance transported by the second carrier gas is 500-2000 sccm; the temperatures of the first inert gas source and the second inert gas source are independently room temperature, and the gas flow rates are independently 5000-8000 sccm; the temperature of the pipeline is 50-120 °C;

[0110] (2) Rotate the rotating device 2 at a rotation rate of 20-100 rpm, so that the substrate 6 sequentially passes through the first working area, the second working area, the third working area, and the fourth working area in the clockwise or counterclockwise direction, and perform a first-order reaction, a second-order reaction, and a third-order reaction in sequence. After 50-200 s, the film layer is prepared;

[0111] Among them, the rate of the second-order reaction is greater than the rate of the first-order reaction, the rate of the second-order reaction is greater than the rate of the third-order reaction, the time of the second-order reaction is less than the time of the first-order reaction, and the time of the second-order reaction is less than the time of the third-order reaction.

[0112] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0113] Example 1

[0114] This example provides a method for preparing a film layer of a perovskite solar cell. The preparation method uses the film layer preparation equipment provided in the above embodiments. The preparation method includes the following steps:

[0115] (1) On a cleaned fluorine-doped tin oxide (FTO) conductive glass with a size of 2.5×2.5 cm, nickel oxide with a thickness of 20 nm is prepared as a hole transport layer by magnetron sputtering. Subsequently, a perovskite layer is prepared on the hole transport layer by solution spin coating, and an electron transport layer C is prepared by thermal evaporation. 60 to obtain a substrate.

[0116] (2) Place the substrate 6 on the rotating device 2 (i.e., the rotating tray) in the reaction chamber 1, and at the same time control the temperature of the substrate 6 to be 120°C. The reaction chamber 1 is evacuated to a vacuum degree of 10 Pa by a mechanical pump;

[0117] Among them, the number of ventilation ports 5 (i.e., slits) on each ventilation panel 4 in the chamber cover 3 is 2;

[0118] (3) The substance conveyed by the first carrier gas with a flow rate of 1000 sccm and the first carrier gas are introduced into the first working area through a pipeline to form a source gas with a flow rate of 7000 sccm in the first working area; the substance conveyed by the second carrier gas with a flow rate of 2000 sccm and the second carrier gas are introduced into the third working area through a pipeline to form a source gas with a flow rate of 7000 sccm in the third working area; the gas in the first inert gas source with a flow rate of 7000 sccm is introduced into the second working area through a pipeline, and the gas in the second inert gas source with a flow rate of 7000 sccm is introduced into the fourth working area;

[0119] Among them, the first carrier gas is nitrogen, the substance conveyed by the first carrier gas is tetra(dimethylamino)tin (TDMASn), the temperature of the first gas source is 65°C, the second carrier gas is nitrogen, the substance conveyed by the second carrier gas is H2O, the temperature of the second gas source is 35°C, the gases in the first inert gas source and the second inert gas source are both nitrogen, the temperatures of the first inert gas source and the second inert gas source are both 25°C, and the temperature of the pipeline is 90°C;

[0120] (4) Rotate the rotating device 2 step by step so that the substrate 6 passes through the first working area, the second working area, the third working area, and the fourth working area in sequence, and rotate at 20 rpm for 100 s, 60 rpm for 30 s, and 20 rpm for 100 s in sequence to complete the first-order reaction, the second-order reaction, and the third-order reaction, and obtain the film layer, that is, SnO2, with a thickness of 20 nm.

[0121] Figure 1 This is a schematic diagram of the mechanism of the first-order reaction and the third-order reaction in this embodiment. It can be seen from the figure that during the first-order reaction or the third-order reaction, after the first precursor undergoes an adsorption reaction, an inert gas is purged, and only a layer of the first precursor adsorbed on the substrate surface remains, which reacts fully with the subsequently adsorbed second precursor, and then the excess second precursor is purged by the inert gas. At this time, only the reaction product remains.

[0122] Figure 2 This is a schematic diagram of the mechanism of the second-order reaction in this embodiment. It can be seen from the figure that during the second-order reaction, after the first precursor undergoes an adsorption reaction, an inert gas is purged, but a relatively thick layer of the first precursor adsorbed on the substrate surface remains, which is not purged into a single layer of atoms; after reacting with the subsequently adsorbed second precursor, at this time, a part of the first precursor that has not participated in the reaction, the reaction product, and the excess second precursor remain; then the excess second precursor is purged by the inert gas, but a certain thickness of the second precursor still remains, which is not purged into a single layer of atoms. At this time, the products include the first precursor, the reaction product, and the second precursor in sequence.

[0123] Example 2

[0124] This embodiment provides a method for preparing a film layer of a perovskite solar cell. The preparation method uses the film layer preparation equipment provided in the above embodiment. The preparation method includes the following steps:

[0125] (1) On a cleaned FTO conductive glass with a specification of 2.5×2.5 cm, use the solution spin-coating method to prepare 20 nm of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) as the hole transport layer. Subsequently, use the solution spin-coating method to prepare a perovskite layer on the hole transport layer, and use thermal evaporation to prepare the electron transport layer C 60 , and obtain the substrate 6.

[0126] (2) Place the substrate 6 on the rotating device 2 (i.e., the rotating tray) in the reaction chamber 1, and at the same time control the temperature of the substrate 6 to be 80 °C, and pump the vacuum in the reaction chamber 1 to 10 Pa through a mechanical pump;

[0127] Among them, the number of ventilation openings 5 (i.e., slits) on each ventilation panel 4 in the chamber cover 3 is 2;

[0128] (3) The substances conveyed by the first carrier gas with a flow rate of 2000 sccm and the first carrier gas with a flow rate of 5000 sccm are introduced into the first working area through a pipeline, and a source gas with a flow rate of 7000 sccm is formed in the first working area; the substances conveyed by the second carrier gas with a flow rate of 1000 sccm and the second carrier gas with a flow rate of 6000 sccm are introduced into the third working area through a pipeline, and a source gas with a flow rate of 7000 sccm is formed in the third working area; the gas in the first inert gas source with a flow rate of 8000 sccm is introduced into the second working area through a pipeline, and the gas in the second inert gas source with a flow rate of 8000 sccm is introduced into the fourth working area through a pipeline;

[0129] Among them, the first carrier gas is nitrogen, the substance conveyed by the first carrier gas is trimethylaluminum (TMA), the temperature of the first gas source is 50 °C, the second carrier gas is nitrogen, the substance conveyed by the second carrier gas is O2, the temperature of the second gas source is 20 °C, the gases in the first inert gas source and the second inert gas source are both nitrogen, the temperatures of the first inert gas source and the second inert gas source are both 25 °C, and the temperature of the pipeline is 50 °C;

[0130] (4) Rotate the rotating device 2 step by step, so that the substrate 6 passes through the first working area, the second working area, the third working area and the fourth working area in sequence, and at the same time rotate at 40 rpm for 40 s, rotate at 80 rpm for 10 s, and rotate at 40 rpm for 40 s in sequence to complete the first-order reaction, the second-order reaction and the third-order reaction, and obtain the film layer, that is, Al2O3, with a thickness of 20 nm.

[0131] Example 3

[0132] This example provides a method for preparing a film layer of a perovskite solar cell. The preparation method uses the film layer preparation equipment provided by the above-mentioned embodiment. The preparation method includes the following steps:

[0133] (1) On a cleaned FTO conductive glass with a specification of 2.5×2.5 cm, 20 nm of poly(trihexylthiophene) (P3HT) is prepared as a hole transport layer by solution spin coating method. Subsequently, a perovskite layer is prepared on the hole transport layer by solution spin coating method, and an electron transport layer C 60 is obtained to get the substrate 66.

[0134] (2) Place the substrate 6 on the rotating device 2 (i.e., rotating tray) in the reaction chamber 1, and at the same time control the temperature of the substrate 6 to be 150 °C, and pump the vacuum in the reaction chamber 1 to a vacuum degree of 10 Pa through a mechanical pump;

[0135] Among them, the number of ventilation ports 5 (i.e., slits) on each ventilation panel 4 in the chamber cover 3 is 3;

[0136] (3) Transfer the substance conveyed by the first carrier gas with a flow rate of 500 sccm and the first carrier gas with a flow rate of 5000 sccm into the first working area through a pipeline, and form a source gas with a flow rate of 5500 sccm in the first working area; transfer the substance conveyed by the second carrier gas with a flow rate of 500 sccm and the first carrier gas with a flow rate of 5000 sccm into the third working area through a pipeline, and form a source gas with a flow rate of 5500 sccm in the third working area; transfer the gas in the first inert gas source with a flow rate of 6000 sccm into the second working area through a pipeline, and transfer the gas in the second inert gas source with a flow rate of 6000 sccm into the fourth working area through a pipeline;

[0137] Among them, the first carrier gas is helium, the substance conveyed by the first carrier gas is TDMASn, the temperature of the first gas source is 80 °C, the second carrier gas is helium, the substance conveyed by the second carrier gas is O2, the temperature of the second gas source is 50 °C, the gases in the first inert gas source and the second inert gas source are both helium, the temperatures of the first inert gas source and the second inert gas source are both 25 °C, and the temperature of the pipeline is 120 °C;

[0138] (4) Rotate the rotating device 2 step by step, so that the substrate 6 sequentially passes through the first working area, the second working area, the third working area and the fourth working area, and at the same time rotates at 60 rpm for 60 s, rotates at 100 rpm for 10 s, and rotates at 60 rpm for 60 s in sequence, to complete the first-order reaction, the second-order reaction and the third-order reaction, and obtain the film layer, that is, SnO2, with a thickness of 10 nm.

[0139] Example 4

[0140] The difference between this example and Example 1 is that the step-by-step rotation in step (4) is adjusted to one-step rotation, that is, rotate at 20 rpm for 500 s.

[0141] The remaining preparation methods and parameters are the same as those in Example 1.

[0142] Example 5

[0143] The difference between this example and Example 1 is that the rotation speeds of the first-order reaction and the third-order reaction in step (4) are both adjusted to 60 rpm, and the rotation speed of the second-order reaction is adjusted to 20 rpm.

[0144] The remaining preparation methods and parameters are the same as those in Example 1.

[0145] Example 6

[0146] The difference between this example and Example 1 is that the step-by-step rotation in step (4) is adjusted to one-step rotation, that is, rotate at 60 rpm for 230 s.

[0147] The remaining preparation methods and parameters are the same as those in Example 1.

[0148] Example 7

[0149] The difference between this example and Example 1 is that the time of the first-order reaction described in step (4) is adjusted to 30 s, the time of the third-order reaction is 30 s, and the time of the second-order reaction is 100 s.

[0150] The remaining preparation methods and parameters are the same as those in Example 1.

[0151] Comparative Example 1

[0152] The difference between this comparative example and Example 1 is that the space above the rotating device 2 is not divided into regions, that is, the space above the rotating device 2 is an entire reaction chamber 1, and the chamber cover plate 3 is also a whole chamber cover plate 3.

[0153] The remaining preparation methods and parameters are the same as those in Example 1.

[0154] Comparative Example 2

[0155] The difference between this comparative example and Example 1 is that the space above the rotating tray 2 is not split, and the first gas source, the first inert gas source, the second gas source, and the second inert gas source are sequentially introduced into the reaction chamber.

[0156] The remaining preparation methods and parameters are the same as those in Example 1.

[0157] Performance Test

[0158] Take out the samples prepared in Examples 1-7 and Comparative Example 1, and then use the vacuum deposition method to prepare a metal electrode Cu on the surface of the samples to obtain a perovskite solar cell with an effective area of 1 cm 2 ².

[0159] Perform optoelectronic performance tests on the obtained perovskite solar cells.

[0160] The test conditions are: AM1.5, 1000 W / m 2 ², 25 ± 2 °C.

[0161] The test results are shown in Table 1.

[0162] Table 1

[0163]

[0164]

[0165] Analysis:

[0166] As can be seen from the above table, the present invention has completed a combined reaction of atomic layer deposition - chemical vapor deposition - atomic layer deposition. On the premise of obtaining a high-quality film layer, the preparation time is greatly shortened, meeting the requirements of industrialization. Meanwhile, a perovskite solar cell with excellent performance is prepared.

[0167] From the comparison of the data results of Example 1 and Example 4, it can be seen that if one-step rotation is carried out at a low speed, the film quality cannot be further improved, and the performance of the prepared battery will be slightly lower.

[0168] From the comparison of the data results of Example 1 and Example 5, it can be seen that if the rotation speed of the first-order reaction and the rotation speed of the third-order reaction are both greater than the rotation speed of the second-order reaction, it will become a CVD + ALD + CVD reaction, which will greatly reduce the film quality.

[0169] From the comparison of the data results of Example 1 and Example 6, it can be seen that if one-step rotation is carried out at a high speed, only CVD reaction will occur, and too many unreacted precursors will remain in the SnO2 film, reducing the battery performance.

[0170] From the comparison of the data results of Example 1 and Example 7, it can be seen that if the time of the first-order reaction and the third-order reaction are both shorter than the time of the second-order reaction, the battery performance will be severely reduced.

[0171] From the comparison of the data results of Example 1 and Comparative Example 1, it can be seen that if the space above the rotating device is not divided into regions, that is, the space above the rotating device is an entire reaction chamber and the chamber cover is also an entire chamber cover, SnO2 will be generated in the chamber before the precursor is deposited on the film surface, so that it cannot be deposited on the film surface, and further may block the pipeline, affecting the service life of the equipment.

[0172] From the comparison of the data results of Example 1 and Comparative Example 2, it can be seen that if the space above the rotating device is not divided into regions and the first gas source, the first inert gas source, the second gas source and the second inert gas source are sequentially introduced into the reaction chamber, the preparation time of the film layer and the battery will be greatly prolonged, and the industrialization requirements cannot be met.

[0173] The applicant declares that the present invention uses the above examples to illustrate the process method of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the raw materials selected by the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for preparing a film layer of a perovskite solar cell, characterized in that, The preparation method uses the following film layer preparation equipment; The film layer preparation equipment includes a reaction chamber and a vacuum pumping device communicated with the reaction chamber. A rotating device is arranged at the bottom of the inner cavity of the reaction chamber. The space above the rotating device is divided into at least two working areas in the counterclockwise or clockwise direction; among the at least two working areas, at least one working area is communicated with a first gas source through a pipeline, and at least one working area is communicated with a second gas source through a pipeline; The preparation method includes the following steps: (1) Place the substrate on the rotating device in the reaction chamber and evacuate it through the vacuum pumping device; (2) Introduce the source gases in the first gas source and the second gas source into the corresponding working areas in the reaction chamber; (3) Rotate the rotating device to make the substrate circulate clockwise or counterclockwise through the working area communicated with the first gas source and the working area communicated with the second gas source to carry out the reaction and prepare the film layer; The reaction in step (3) includes a first-order reaction, a second-order reaction, and a third-order reaction carried out in sequence. The first-order reaction and the third-order reaction are ALD reactions, and the second-order reaction is a CVD reaction; The time of the second-order reaction is less than the time of the first-order reaction, and the time of the second-order reaction is less than the time of the third-order reaction; The substance conveyed by the first gas source is a first precursor, and the substance conveyed by the second gas source is a second precursor. The CVD reaction means that after the first precursor undergoes an adsorption reaction, it is purged with an inert gas, but there is still the first precursor adsorbed on the surface of the substrate, which is not purged into a single layer of atoms; after reacting with the subsequently adsorbed second precursor, at this time, there is a part of the first precursor that has not participated in the reaction, reaction products, and excess second precursor; then the excess second precursor is purged with an inert gas, but a certain thickness of the second precursor is still retained, which is not purged into a single layer of atoms. At this time, the products include the first precursor, reaction products, and the second precursor in sequence.

2. The preparation method according to claim 1, characterized in that, The space above the rotating device is divided into four working areas in the counterclockwise or clockwise direction, including a first working area, a second working area, a third working area, and a fourth working area; Among the four working areas, the first working area is communicated with the first gas source through a pipeline, the second working area is communicated with a first inert gas source through a pipeline, the third working area is communicated with the second gas source through a pipeline, and the fourth working area is communicated with a second inert gas source through a pipeline.

3. The preparation method according to claim 1 or 2, characterized in that, A partition is arranged in the reaction chamber, and the partition divides the space above the rotating tray into a first chamber, a second chamber, a third chamber, and a fourth chamber in the counterclockwise or clockwise direction The first gas source is communicated with the first chamber through a pipeline, the second gas source and the third chamber are communicated through a pipeline, the first inert gas source is communicated with the second chamber through a pipeline, and the second inert gas source is communicated with the fourth chamber through a pipeline.

4. The preparation method according to claim 1, wherein The rotation rate of the second-order reaction is greater than the rotation rate of the first-order reaction, and the rotation rate of the second-order reaction is greater than the rotation rate of the third-order reaction.

5. The preparation method according to claim 4, characterized in that, The rotation rate of the first-order reaction is 20-60 rpm.

6. The preparation method according to claim 4, characterized in that, The rotation rate of the second-order reaction is 60-100 rpm.

7. The preparation method according to claim 4, characterized in that, The rotation rate of the third-order reaction is 20 - 60 rpm.

8. The preparation method according to claim 4, wherein The reaction time in step (3) is 50 - 200 s.

9. The preparation method according to claim 1, characterized in that, The specific steps of introducing the source gases in the first gas source and the second gas source into the corresponding working areas in the reaction chamber in step (2) include: Sequentially introducing the source gas in the first gas source, the gas in the first inert gas source, the source gas in the second gas source, and the gas in the second inert gas source into the first working area, the second working area, the third working area, and the fourth working area in a clockwise or counterclockwise direction; In the second working area, the flow rate of the gas in the first inert gas source during the ALD reaction is greater than that during the CVD reaction; In the fourth working area, the flow rate of the gas in the second inert gas source during the ALD reaction is greater than that during the CVD reaction.

10. The preparation method according to claim 9, characterized in that, The rotation rates of the first-order reaction, the second-order reaction, and the third-order reaction are the same.

11. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: (a) Place the substrate on the rotating device in the reaction chamber and evacuate it through a vacuum device; (b) Introduce the source gas in the first gas source into the first working area in the reaction chamber through a pipeline, introduce the source gas in the second gas source into the third working area in the reaction chamber through a pipeline, introduce the gas in the first inert gas source into the second working area in the reaction chamber through a pipeline, and introduce the gas in the second inert gas source into the fourth working area in the reaction chamber through a pipeline; (c) Rotate the rotating device to make the substrate sequentially pass through the first working area, the second working area, the third working area, and the fourth working area in a clockwise or counterclockwise direction to carry out the reaction and prepare the film layer.

12. The preparation method according to claim 11, wherein, The temperature of the substrate in step (a) is 80 - 150 °C.

13. The preparation method according to claim 11, characterized in that, In step (a), evacuate to a vacuum degree in the reaction chamber less than or equal to 10 Pa.

14. The preparation method according to claim 11, wherein The source gas in the first gas source in step (b) includes a first carrier gas and a substance transported by the first carrier gas, and the substance transported by the first carrier gas includes tin(IV) bis(dimethylamino) or trimethylaluminum.

15. The preparation method according to claim 14, characterized in that, The flow rate of the substance transported by the first carrier gas is 500 - 2000 sccm.

16. The preparation method according to claim 11, characterized in that, The source gas in the second gas source in step (b) includes a second carrier gas and a substance transported by the second carrier gas, and the substance transported by the second carrier gas includes any one of O2, O3, H2O, or H2O2.

17. The preparation method according to claim 16, characterized in that, The flow rate of the substance transported by the second carrier gas is 500 - 2000 sccm.

18. The preparation method according to claim 11, wherein The temperature of the first gas source in step (b) is 50 - 80 °C.

19. The preparation method according to claim 11, characterized in that, The temperature of the second gas source in step (b) is 20 - 50 °C.

20. The preparation method according to claim 11, wherein The temperature of the pipeline in step (b) is 50 - 120 °C.

21. The preparation method according to claim 11, wherein The gas in the first inert gas source and the gas in the second inert gas source independently include any one of nitrogen, helium, neon, argon, krypton, xenon, or radon.

22. The preparation method according to claim 11, wherein, The flow rate of the gas in the second working area and the fourth working area is greater than or equal to the flow rate of the source gas in the first working area, and the flow rate of the gas in the second working area and the fourth working area is greater than or equal to the flow rate of the source gas in the third working area.

23. The preparation method according to claim 11, characterized in that, The flow rates of the gases in the first inert gas source and the second inert gas source are independently 5000 - 8000 sccm.

24. A film layer of a perovskite solar cell, characterized in that, The film layer is prepared by the preparation method described in any one of claims 1 - 23.

25. The film layer according to claim 24, characterized in that, The thickness of the film layer is 5 - 30 nm.

26. The film layer according to claim 24, wherein The film layer includes any one of a perovskite layer, an electron transport layer, a hole transport layer, or a packaging layer.

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