Composite transparent conductive film, preparation method and application thereof, and composite transparent conductive film production equipment

Abstract

The invention belongs to the technical field of transparent conductive thin film preparation, and relates to a composite transparent conductive thin film, a preparation method and application thereof, and composite transparent conductive thin film production equipment, the preparation method comprises the following steps: providing a carrier transport layer; carrying out first deposition on the surface of one side of the carrier transport layer under 0.2-0.6 Pa; performing second deposition on the surface of one side, far away from the carrier transport layer, of the formed first transparent conductive film under 0.7-1.1 Pa to obtain a composite transparent conductive film; the thickness of the first transparent conductive film is smaller than that of the second transparent conductive film. According to the invention, the thin first transparent conductive film is formed by low-pressure deposition, the crystal structure of the obtained film is more compact and ordered, good electrical properties are provided, and moderate internal stress is taken into account at the same time; and the thick second transparent conductive film is formed through high-pressure deposition, the obtained film is small in internal stress and not prone to falling off, and the overall film stress of the composite transparent conductive film is reduced.

Description

Technical Field

[0001] This invention relates to the field of transparent conductive film preparation technology, and in particular to a composite transparent conductive film, its preparation method and application, and composite transparent conductive film production equipment. Background Technology

[0002] Against the backdrop of the rapid development of display technology and the photovoltaic industry, transparent conductive films are a special type of functional film that simultaneously possesses high visible light transmittance (typically required to be >80%) and low surface resistance (typically required to be <100Ω / sq, and in some scenarios, <10Ω / sq). Their core function is to achieve both light transmission and conductivity, making them widely used in energy, display, and sensing fields, especially playing a crucial role in perovskite solar cells. Currently, the preparation of transparent conductive films (such as ITO films) has become a research hotspot, with physical vapor deposition (PVD) or solution methods commonly employed. PVD is the most widely used and mainstream process for its preparation.

[0003] For the fabrication of transparent conductive films using physical vapor deposition (PVD), deposition under a single gas pressure is often relied upon. However, this method can exhibit several fabrication defects on certain inorganic / organic substrates. For instance, if the process gas pressure is a single, fixed low pressure, the gas molecules are sparse, and the mean free path of the particles is long. This means that ions, accelerated by an electric field, have a lower probability of colliding with other particles, thus carrying higher kinetic energy to reach the substrate surface. This bombardment effect of high-energy particles provides additional surface migration energy for film growth, helping atoms to rearrange on the substrate and form a denser, more ordered crystal structure, providing better electrical properties for the film. However, the rapid formation of a dense film generates greater internal stress, which can significantly reduce the film's electrical properties. Deposition at a single, fixed high pressure increases the likelihood of cracking and detachment. A smaller mean free path of the target ions results in lower energy deposition onto the substrate surface, leading to poorer film density and increased interfacial problems with the inorganic / organic substrate. This negatively impacts electron transport and electrical performance, but the advantage lies in lower internal stress. While sacrificing some electrical properties, it ensures film stability and reduces the likelihood of detachment. Furthermore, deposition at a single pressure cannot be adjusted based on the type of inorganic / organic substrate or the required film quality. It cannot accommodate multiple process optimization directions and requires weighing various influencing factors, resulting in a very limited process adjustment window. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a composite transparent conductive film, its preparation method and application, and a production equipment for the composite transparent conductive film. This invention employs a dual-pressure deposition process. First, deposition is performed at a low pressure of 0.2 Pa to 0.6 Pa to form a thinner first transparent conductive film. The resulting first transparent conductive film has a denser, more ordered crystal structure with fewer defects, providing good electrical properties for the composite transparent conductive film while maintaining moderate internal stress. Then, deposition is performed at a high pressure of 0.7 Pa to 1.1 Pa to form a relatively thicker second transparent conductive film. The resulting second transparent conductive film has lower internal stress and is less prone to detachment, thereby reducing the overall film stress of the composite transparent conductive film. Therefore, by combining the low-pressure and high-pressure deposition processes, and with the synergistic effect of the first and second transparent conductive films, the composite transparent conductive film achieves both good electrical properties and good adhesion to the carrier transport layer. The dual-pressure deposition process of this invention requires no heating, making the preparation process simpler. In addition, it can increase the process adjustment window, making the process flow adjustment more flexible and better adaptable to the preparation of various transparent conductive films on the surface of charge carrier transport layers of various materials.

[0005] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a composite transparent conductive film, the method comprising the following steps: S1 provides a carrier transport layer; S2. Under a first process gas pressure of 0.2Pa to 0.6Pa, for example, 0.2Pa, 0.25Pa, 0.3Pa, 0.35Pa, 0.4Pa, 0.45Pa, 0.5Pa, 0.55Pa or 0.6Pa, a first deposition is performed on one side surface of the charge carrier transport layer to form a first transparent conductive film. S3. Under a second process gas pressure of 0.7Pa~1.1Pa, such as 0.7Pa, 0.75Pa, 0.8Pa, 0.85Pa, 0.9Pa, 0.95Pa, 1Pa, 1.05Pa or 1.1Pa, a second deposition is performed on the surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film, thereby obtaining a composite transparent conductive film. The thickness of the first transparent conductive film is less than the thickness of the second transparent conductive film.

[0006] It should be noted that the present invention does not impose specific requirements or limitations on the specific material types of the first transparent conductive film and the second transparent conductive film. The preparation methods provided by the present invention are applicable to the preparation of transparent conductive films commonly used in the art. Those skilled in the art can make adaptive selections and adjustments according to actual preparation needs. For example, it can be a variety of transparent conductive films such as IWO transparent conductive film, ITO transparent conductive film, IZO transparent conductive film or AZO transparent conductive film.

[0007] It should be noted that the first transparent conductive film and the second transparent conductive film in this invention can be films of the same material or films of different materials. Those skilled in the art can make adaptive selections and adjustments according to actual preparation requirements. For example, the first transparent conductive film can be an ITO transparent conductive film, the second transparent conductive film can be an ITO transparent conductive film, and the composite transparent conductive film can be a stacked ITO transparent conductive film-ITO transparent conductive film composite film. Alternatively, the first transparent conductive film can be an ITO transparent conductive film, the second transparent conductive film can be an IZO transparent conductive film, and the composite transparent conductive film can be a stacked ITO transparent conductive film-IZO transparent conductive film composite film.

[0008] This invention employs a dual-pressure deposition process. First, a thinner first transparent conductive film is formed using a low pressure (0.2 Pa to 0.6 Pa). This first transparent conductive film has a denser, more ordered crystal structure with fewer defects, providing excellent electrical properties for the composite transparent conductive film while maintaining moderate internal stress. Then, a thicker second transparent conductive film is formed using a high pressure (0.7 Pa to 1.1 Pa). This second transparent conductive film has lower internal stress, is less prone to detachment, and reduces the overall film stress of the composite transparent conductive film. Therefore, by combining low-pressure and high-pressure deposition processes, and with the synergistic effect of the first and second transparent conductive films, the composite transparent conductive film achieves both good film performance and low internal stress.

[0009] The dual-pressure deposition process of this invention requires no heating, making the preparation process simpler. In addition, it can increase the process adjustment window, making the process flow adjustment more flexible and better adaptable to the preparation of various transparent conductive films on the surface of charge carrier transport layers of various materials.

[0010] In this invention, the first process gas pressure is controlled to be 0.2 Pa to 0.6 Pa. If the first process gas pressure is too low, it will cause the internal stress of the first transparent conductive film to increase and the film to warp. If the first process gas pressure is too high, it will cause the electrical properties of the composite transparent conductive film to deteriorate.

[0011] In this invention, the second process gas pressure is controlled to be 0.7 Pa to 1.1 Pa. If the second process gas pressure is too low, it will cause the internal stress of the second transparent conductive film to increase, making it easy to fall off. If the second process gas pressure is too high, it will cause the electrical properties of the composite transparent conductive film to deteriorate.

[0012] In this invention, the thickness of the first transparent conductive film is controlled to be less than the thickness of the second transparent conductive film. If the thickness of the first transparent conductive film is greater than or equal to the thickness of the second transparent conductive film, the composite transparent conductive film will warp due to increased stress, reducing the bonding force with the charge carrier transport layer.

[0013] As a preferred technical solution of the present invention, the thickness of the first transparent conductive film in step S2 is 10nm~100nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm, etc.

[0014] In this invention, the thickness of the first transparent conductive film is controlled to be between 10 nm and 100 nm. If the first transparent conductive film is too thick, it will lead to increased stress and warping of the film; if the first transparent conductive film is too thin, it will lead to a deterioration in the electrical properties of the composite transparent conductive film.

[0015] As a preferred technical solution of the present invention, the thickness of the second transparent conductive film in step S3 is 100nm~500nm, such as 100nm, 120nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm, 480nm or 500nm, etc.

[0016] In this invention, the thickness of the second transparent conductive film is controlled to be 100nm~500nm. If the second transparent conductive film is too thick, the light transmittance of the composite transparent conductive film will be reduced and the laser scribing performance will be reduced. If the second transparent conductive film is too thin, the electrical performance of the composite transparent conductive film will be reduced.

[0017] As a preferred technical solution of the present invention, the first reaction gas of the first deposition in step S2 includes oxygen, and the flow rate of the oxygen is 18 sccm to 26 sccm, such as 18 sccm, 19 sccm, 20 sccm, 21 sccm, 22 sccm, 23 sccm, 24 sccm, 25 sccm or 26 sccm, etc.

[0018] As a preferred technical solution of the present invention, the second reaction gas for the second deposition in step S3 includes oxygen, and the flow rate of the oxygen is 6 sccm to 13 sccm, such as 6 sccm, 7 sccm, 8 sccm, 9 sccm, 10 sccm, 11 sccm, 12 sccm or 13 sccm, etc.

[0019] As a preferred embodiment of the present invention, the carrier transport layer in step S1 includes a hole transport layer, or the carrier transport layer includes an electron transport layer.

[0020] It should be noted that the present invention does not impose specific requirements or limitations on the selection of materials for the hole transport layer and the electron transport layer. Common hole transport layer and electron transport layer materials in the art are all suitable for the present invention, and those skilled in the art can make adaptive selections and adjustments according to actual conditions.

[0021] As a preferred technical solution of the present invention, the carrier transport layer in step S1 is disposed on the top layer of the underlying structure.

[0022] It should be noted that the top layer set in the bottom structure refers to the carrier transport layer, which is located at the top of the overall structure of the bottom structure, and the first transparent conductive film and the second transparent conductive film are prepared sequentially on its surface.

[0023] It should be noted that the present invention does not impose specific requirements or limitations on the other specific layer structures in the underlying structure besides the carrier transport layer. Those skilled in the art can make adaptive selections and adjustments according to actual applications. For example, when used in a perovskite solar cell module, if the carrier transport layer includes a hole transport layer, the underlying structure may include a substrate, an electron transport layer, a perovskite light-absorbing layer, and a hole transport layer stacked sequentially; or, if the carrier transport layer includes an electron transport layer, the underlying structure may include a substrate, a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer stacked sequentially.

[0024] In this invention, neither the first deposition in step S2 nor the second deposition in step S3 requires the initiation of a heating program. However, as the first and second deposition processes proceed, the temperature in the reaction chamber will accumulate with the increase of deposition time. Therefore, the specific temperature in the reaction chamber is between 20°C and 70°C.

[0025] As a preferred technical solution of the present invention, the first deposition in step S2 and the second deposition in step S3 are performed in different reaction chambers, or the first deposition in step S2 and the second deposition in step S3 are performed in the same reaction chamber.

[0026] In this invention, the first deposition in step S2 and the second deposition in step S3 are carried out in different reaction chambers, which can further improve the production cycle and increase the production capacity.

[0027] As a preferred technical solution of the present invention, the first deposition in step S2 and the second deposition in step S3 are performed in different reaction chambers. The process of the first deposition in step S2 and the second deposition in step S3 includes: continuously introducing an inert gas into the first reaction chamber and controlling it at a first process gas pressure, then introducing a first reaction gas to perform the first deposition; continuously introducing the inert gas into the second reaction chamber and controlling it at a second process gas pressure, then introducing a second reaction gas to perform the second deposition; turning on the ion source to start the reaction target, introducing the underlying structure into the first reaction chamber, passing through the first reaction chamber at a first speed, and performing a first deposition on one side surface of the charge carrier transport layer to form a first transparent conductive film; continuing to introduce the underlying structure with the first transparent conductive film deposited into the second reaction chamber, passing through the second reaction chamber at a second speed, and performing a second deposition on the side surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film, thus obtaining a composite transparent conductive film.

[0028] As a preferred technical solution of the present invention, before the inert gas is introduced, the background vacuum of the first reaction chamber and the second reaction chamber is <5E-4Pa, such as 4.9E-4Pa, 4.5E-4Pa, 4E-4Pa, 3E-4Pa, 2E-4Pa or 1E-4Pa.

[0029] As a preferred embodiment of the present invention, the ion source includes a cathode ion gun.

[0030] As a preferred technical solution of the present invention, the current of the cathode ion gun is 100A~160A, such as 100A, 110A, 120A, 130A, 140A, 150A or 160A.

[0031] As a preferred technical solution of the present invention, the first deposition in step S2 and the second deposition in step S3 are performed in the same reaction chamber. The process of the first deposition in step S2 and the second deposition in step S3 includes: continuously introducing an inert gas into the reaction chamber and controlling it at a first process gas pressure, then introducing a first reaction gas, turning on the ion source to start the reaction target, introducing the underlying structure into the reaction chamber, and performing a first deposition on one side surface of the charge carrier transport layer at a first speed from one end of the reaction chamber to the other to form a first transparent conductive film; adjusting the flow rate of the inert gas and controlling it at a second process gas pressure, then introducing a second reaction gas, and performing a second deposition on the side surface of the first transparent conductive film away from the charge carrier transport layer at a second speed from one end of the reaction chamber to the other to form a second transparent conductive film, thereby obtaining a composite transparent conductive film.

[0032] As a preferred technical solution of the present invention, before the inert gas is introduced, the background vacuum of the reaction chamber is <5E-4Pa, such as 4.9E-4Pa, 4.5E-4Pa, 4E-4Pa, 3E-4Pa, 2E-4Pa or 1E-4Pa.

[0033] As a preferred embodiment of the present invention, the ion source includes a cathode ion gun.

[0034] As a preferred technical solution of the present invention, the current of the cathode ion gun is 100A~160A, such as 100A, 110A, 120A, 130A, 140A, 150A or 160A.

[0035] It should be noted that in this invention, no specific requirements or special limitations are imposed on the reaction target material for the first deposition in step S2 and the second deposition in step S3. As long as the target material can be used to prepare the corresponding transparent conductive film, it is acceptable. Those skilled in the art can make adaptive selections and adjustments according to actual preparation needs. For example, it can be a variety of oxide targets such as IWO target, ITO target, IZO target or AZO target.

[0036] It should be noted that in this invention, the first deposition rate and the second deposition rate in step S2 and step S3 are not subject to specific requirements or special limitations, as long as they can be used to prepare a first transparent conductive film and a second transparent conductive film of the corresponding thickness. Those skilled in the art can make adaptive selections and adjustments according to actual preparation needs.

[0037] As a preferred embodiment of the present invention, the inert gas includes argon.

[0038] It should be noted that in this invention, inert gas is introduced into each reaction chamber to achieve the first process gas pressure and the second process gas pressure. Since the reaction chamber volumes of different reaction equipment are different in actual processes, there are no specific requirements or special limitations on the flow rate of the inert gas. As long as the corresponding first process gas pressure is 0.2 Pa to 0.6 Pa and the second process gas pressure is 0.7 Pa to 1.1 Pa, it is sufficient. Those skilled in the art can adaptively select and adjust the flow rate of the inert gas in each step according to the actual situation.

[0039] It should be noted that the entire preparation process of this invention is carried out in a vacuum coating equipment. No specific requirements or special limitations are imposed on the vacuum coating equipment. Commonly used vacuum coating equipment in the field are applicable to this invention. For example, it can be a reactive plasma deposition (RPD) device, a physical vapor deposition (PVD) device, etc. The PVD power supply type includes, but is not limited to, DC, MF, and RF. Different types of power supplies require different types of target materials. For example, DC and MF can use a rotating target, RF can use a planar target, and RPD can use a round ingot target. The size of the round ingot target includes, but is not limited to, 40×Φ30mm, 40×Φ27mm, or 40×Φ25mm.

[0040] In a second aspect, the present invention also provides a composite transparent conductive film, which is prepared according to the preparation method described in the first aspect. The composite transparent conductive film includes a first transparent conductive film and a second transparent conductive film from bottom to top, and the first transparent conductive film is bonded to the carrier transport layer.

[0041] As a preferred technical solution of the present invention, the thickness of the first transparent conductive film is 10nm~100nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm.

[0042] As a preferred embodiment of the present invention, the thickness of the second transparent conductive film is 100nm~500nm, for example, 100nm, 120nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm, 480nm or 500nm, etc.

[0043] Thirdly, the present invention also provides a perovskite solar cell module, the perovskite solar cell module comprising the composite transparent conductive film as described in the second aspect.

[0044] As a preferred embodiment of the present invention, the perovskite solar cell module includes: Base; A first carrier transport layer is stacked on one side of the substrate; A perovskite light-absorbing layer is stacked on the side of the first carrier transport layer away from the substrate; The second carrier transport layer is stacked on the side of the perovskite light-absorbing layer away from the first carrier transport layer; A composite transparent conductive film is stacked on the side of the second carrier transport layer away from the perovskite light-absorbing layer.

[0045] As a preferred embodiment of the present invention, the first carrier transport layer includes a hole transport layer and the second carrier transport layer includes an electron transport layer; or, the first carrier transport layer includes an electron transport layer and the second carrier transport layer includes a hole transport layer.

[0046] As a preferred technical solution of the present invention, the substrate includes a rigid transparent conductive glass substrate or an organic flexible conductive substrate.

[0047] As a preferred technical solution of the present invention, the rigid transparent conductive glass substrate includes an FTO conductive glass substrate and / or an ITO conductive glass substrate, and the organic flexible conductive substrate includes a PET conductive substrate and / or a PI conductive substrate.

[0048] As a preferred embodiment of the present invention, the substrate is a pretreated substrate, and the pretreatment process includes cleaning.

[0049] As a preferred technical solution of the present invention, the cleaning includes sequentially performing pure water cleaning, cleaning fluid cleaning, pure water + ultrasonic cleaning, and air knife drying.

[0050] In this invention, a multi-step cleaning process is employed to ensure the surface cleanliness of the substrate, free from glass powder, cleaning agents, and organic residues. If the substrate is an organic flexible conductive substrate, attention must be paid to the cleaning method and the drying temperature must be adjusted accordingly to avoid substrate deformation that could affect the deposition effect.

[0051] Fourthly, the present invention also provides a photovoltaic cell module, the photovoltaic cell module comprising the perovskite solar cell module as described in the third aspect.

[0052] Fifthly, the present invention also provides a composite transparent conductive film production equipment, which is used to produce the composite transparent conductive film described in the second aspect.

[0053] As a preferred technical solution of the present invention, the composite transparent conductive film production equipment includes a feeding chamber, a feeding buffer chamber, a process chamber, a discharging buffer chamber and a discharging chamber connected in sequence. The process chamber includes a first coating chamber and a second coating chamber, each of which is independent. A molecular pump is provided between the first coating chamber and the second coating chamber.

[0054] Compared with the prior art, the present invention has at least the following beneficial effects: 1) This invention employs a dual-pressure deposition process. First, a low pressure of 0.2 Pa to 0.6 Pa is used for deposition to form a thinner first transparent conductive film. The resulting first transparent conductive film has a denser, more ordered crystal structure with fewer defects, providing good electrical properties for the composite transparent conductive film while also taking into account moderate internal stress. Then, a high pressure of 0.7 Pa to 1.1 Pa is used for deposition to form a relatively thicker second transparent conductive film. The resulting second transparent conductive film has lower internal stress and is less prone to detachment, thus reducing the overall film stress of the composite transparent conductive film.

[0055] 2) This invention combines low-pressure deposition and high-pressure deposition processes, and the first transparent conductive film and the second transparent conductive film work together to make the composite transparent conductive film have both good electrical properties and low internal stress.

[0056] 3) The dual-pressure deposition process of this invention has a simpler preparation process and can also increase the process adjustment window, making the process adjustment more flexible. Attached Figure Description

[0057] Figure 1 This is a flowchart illustrating the preparation process of the composite transparent conductive film of this invention.

[0058] Figure 2 This is a flowchart illustrating the process steps for preparing the composite transparent conductive film of the present invention in different reaction chambers.

[0059] Figure 3 This is a cross-sectional SEM image of the composite transparent conductive film provided in Embodiment 1 of the present invention.

[0060] Figure 4 This is a structural diagram of the RPD (Recombinant Transparent Conductive Film) device used in the production of the composite transparent conductive film of Example 1 of this invention.

[0061] Among them, 1-feed chamber; 2-feed buffer chamber; 3-process chamber; 31-first coating chamber; 32-second coating chamber; 33-molecular pump; 4-discharge buffer chamber; 5-discharge chamber.

[0062] Figure 5 This is a cross-sectional SEM image of the composite transparent conductive film provided in Embodiment 13 of the present invention. Detailed Implementation

[0063] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0064] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0065] Figure 1 A flowchart illustrating the preparation process of the composite transparent conductive film of the present invention is shown. The preparation method includes the following steps: S1, providing a carrier transport layer; S2, performing a first deposition on one side surface of the carrier transport layer under a first process pressure of 0.2 Pa to 0.6 Pa to form a first transparent conductive film; S3, performing a second deposition on the side surface of the first transparent conductive film away from the carrier transport layer under a second process pressure of 0.7 Pa to 1.1 Pa to form a second transparent conductive film, thereby obtaining a composite transparent conductive film; the thickness of the first transparent conductive film is less than the thickness of the second transparent conductive film.

[0066] This invention employs a dual-pressure deposition process. First, a thin first transparent conductive film is deposited using a low pressure of 0.2 Pa to 0.6 Pa. This first transparent conductive film has a denser, more ordered crystal structure with fewer defects, providing excellent electrical properties for the composite transparent conductive film while maintaining moderate internal stress. Then, a thicker second transparent conductive film is deposited using a high pressure of 0.7 Pa to 1.1 Pa. This second transparent conductive film has lower internal stress, is less prone to detachment, and reduces the overall film stress of the composite transparent conductive film. Therefore, by combining low-pressure and high-pressure deposition processes, and with the synergistic effect of the first and second transparent conductive films, the composite transparent conductive film achieves both excellent electrical properties and good adhesion to the charge carrier transport layer.

[0067] Figure 2The diagram illustrates the process steps for preparing the composite transparent conductive film of the present invention in different reaction chambers. The preparation method includes the following steps: providing a carrier transport layer, which is disposed on the top layer of the underlying structure; controlling the background vacuum of the first reaction chamber to be <5E-4Pa, continuously introducing argon gas into the first reaction chamber and controlling it at a first process gas pressure of 0.2Pa~0.6Pa, followed by introducing oxygen at 18sccm~26sccm for the first deposition; controlling the background vacuum of the second reaction chamber to be <5E-4Pa, continuously introducing argon gas into the second reaction chamber and controlling it at a second process gas pressure of 0.7Pa~1.1Pa, followed by introducing oxygen at 6sccm~13sccm for the second deposition; turning on the cathode ion gun and setting the current parameters to 100A~16A. 0A, argon gas is introduced for target ignition. After successful ignition, the flow rate is changed to maintain the argon flow rate at the first process pressure. An empty carrier is first introduced into the first reaction chamber, and the heat engine is continuously run to maintain a stable atmosphere inside the chamber while removing impurities and moisture adsorbed on the carrier surface. Then, the bottom layer structure is loaded into the carrier and introduced into the first reaction chamber to begin deposition. Through the first reaction chamber, a first deposition is performed on one side surface of the charge carrier transport layer to form a first transparent conductive film with a thickness of 10nm~100nm. The bottom layer structure with the first transparent conductive film deposited is then introduced into the second reaction chamber. Through the second reaction chamber, a second deposition is performed on the side surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film with a thickness of 100nm~500nm, resulting in a composite transparent conductive film.

[0068] Example 1 This embodiment provides a composite transparent conductive film and its preparation method, the preparation method including the following steps: A NiO hole transport layer is provided, which is disposed on the top layer of the underlying structure. The underlying structure includes, from bottom to top, an FTO conductive glass substrate, a SnO2 electron transport layer, a perovskite light-absorbing layer (in the perovskite solution, the molar ratio of lead iodide:formamidinium hydroiodate:methylammonium iodide:cesium iodide is 1:0.9:0.05:0.05, the mixed solvent DMF:DMSO is 4:1, and the concentration is 1.5 mol / L) and the NiO hole transport layer. The FTO conductive glass substrate is pretreated. The pretreatment process includes cleaning the FTO conductive glass substrate to be deposited in the following order: pure water, cleaning solution, pure water + ultrasonication, and air knife drying.

[0069] The deposition process takes place in different reaction chambers. The base vacuum of the first reaction chamber is controlled to be below 5E-4 Pa. Argon gas at 40 sccm is continuously introduced into the first reaction chamber, maintaining a first process gas pressure of 0.45 Pa. Then, oxygen at 26 sccm is introduced for the first deposition. The base vacuum of the second reaction chamber is controlled to be below 5E-4 Pa. Argon gas at 500 sccm is continuously introduced into the second reaction chamber, maintaining a second process gas pressure of 1.1 Pa. Then, oxygen at 9.5 sccm is introduced for the second deposition. The cathode ion gun is turned on with a current parameter of 150 A, and 70 sccm of argon gas is introduced for target ignition. After successful target ignition, the flow rate is changed to 40 sccm, and the unloaded state is maintained. The substrate is first introduced into the first reaction chamber and continuously heated for 30 minutes to maintain a stable atmosphere within the chamber and remove impurities and moisture adsorbed on the surface of the substrate. Then, the underlying structure is loaded into the substrate and introduced into the first reaction chamber to begin deposition. It passes through the first reaction chamber at a speed of 28 mm / s to perform a first deposition on the surface of the NiO hole transport layer, forming a first transparent conductive film with a thickness of 15 nm. The underlying structure with the first transparent conductive film deposited is then introduced into the second reaction chamber and passes through the second reaction chamber at a speed of 5 mm / s to perform a second deposition on the side of the first transparent conductive film away from the NiO hole transport layer, forming a second transparent conductive film with a thickness of 285 nm, thus obtaining a composite transparent conductive film.

[0070] Figure 3 A cross-sectional SEM image of the composite transparent conductive film provided in Embodiment 1 of the present invention is shown. As can be seen from the figure, the composite transparent conductive film provided in this embodiment has good contact with the underlying structure (the SnO2 electron transport layer is relatively thin, so it is not clearly shown in the SEM image).

[0071] The composite transparent conductive film is used in perovskite solar cell modules, which are used in photovoltaic cell modules.

[0072] The composite transparent conductive film is produced in a composite transparent conductive film production equipment. Figure 4 The diagram shows the structure of the composite transparent conductive film production equipment RPD of the production embodiment 1 of the present invention. The composite transparent conductive film production equipment includes a feeding chamber 1, a feeding buffer chamber 2, a process chamber 3, a discharge buffer chamber 4, and a discharge chamber 5 connected in sequence. The process chamber 3 includes a first coating chamber 31 and a second coating chamber 32, each of which is independent. A molecular pump 33 is disposed between the first coating chamber 31 and the second coating chamber 32.

[0073] Example 2 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 14 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 30 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 5.3 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 270 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0074] Example 3 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 8.4 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 50 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 5.7 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 250 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0075] Example 4 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 28 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 15 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 7.7 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 185 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0076] Example 5 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 14 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 30 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 8.38 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 170 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0077] Example 6 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 8.4 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 50 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 9.5 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 150 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0078] Example 7 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 6 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 70 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 6.19 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 230 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0079] Example 8 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 6 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 70 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 10.96 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 130 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0080] Example 9 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 14 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 30 nm, and a second deposition is performed on the side of the first transparent conductive film away from the NiO hole transport layer at a speed of 2.74 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 520 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0081] Example 10 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 52.5 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 8 nm, and a second deposition is performed on the surface of the first transparent conductive film away from the NiO hole transport layer at a speed of 4.88 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 292 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0082] Example 11 This embodiment provides a composite transparent conductive film and its preparation method, the preparation method including the following steps: A SnO2 electron transport layer is provided, which is disposed on the top layer of the underlying structure. The underlying structure includes, from bottom to top, a PI conductive substrate (a PI substrate with an ITO layer on the surface), a NiO hole transport layer, a perovskite light-absorbing layer (in the perovskite solution, the molar ratio of lead iodide:formamidinium hydroiodate:methylammonium iodide:cesium iodide is 1:0.9:0.05:0.05, the mixed solvent DMF:DMSO is 4:1, and the concentration is 1.5mol / L) and the SnO2 electron transport layer. The PI conductive substrate is pretreated. The pretreatment process includes cleaning the PI conductive substrate to be deposited in the following order: pure water, cleaning solution, pure water + ultrasonication, and air knife drying (to avoid curling the substrate).

[0083] The deposition process takes place in different reaction chambers. The background vacuum in the first reaction chamber is controlled to be below 5E-4 Pa. Argon gas at 18 sccm is continuously introduced into the first reaction chamber, maintaining a first process gas pressure of 0.2 Pa. Then, oxygen at 20 sccm is introduced to initiate the first deposition reaction. The background vacuum in the second reaction chamber is controlled to be below 5E-4 Pa. Argon gas at 300 sccm is continuously introduced into the second reaction chamber, maintaining a second process gas pressure of 0.7 Pa. Then, oxygen at 11 sccm is introduced to initiate the second deposition reaction. The cathode ion gun is turned on with a current parameter of 150 A, and 70 sccm of argon gas is introduced for target ignition. After successful target ignition, the flow rate is changed to 40 sccm. The empty carrier is first... The material is introduced into the first reaction chamber and continuously heated for 30 minutes to maintain a stable atmosphere within the chamber and remove impurities and moisture adsorbed on the carrier surface. Subsequently, the underlying structure is loaded into the carrier and introduced into the first reaction chamber to begin deposition. It passes through the first reaction chamber at a speed of 42 mm / s to perform a first deposition on the surface of the SnO2 electron transport layer, forming a first transparent conductive film with a thickness of 10 nm. The underlying structure with the deposited first transparent conductive film is then introduced into the second reaction chamber and passes through the second reaction chamber at a speed of 14.25 mm / s to perform a second deposition on the side of the first transparent conductive film away from the SnO2 electron transport layer, forming a second transparent conductive film with a thickness of 100 nm, thus obtaining a composite transparent conductive film.

[0084] Example 12 This embodiment provides a composite transparent conductive film and its preparation method, the preparation method including the following steps: A NiO hole transport layer is provided, which is disposed on the top layer of the underlying structure. The underlying structure includes, from bottom to top, an FTO conductive glass substrate, a SnO2 electron transport layer, a perovskite light-absorbing layer (in the perovskite solution, the molar ratio of lead iodide:formamidinium hydroiodate:methylammonium iodide:cesium iodide is 1:0.9:0.05:0.05, the mixed solvent DMF:DMSO is 4:1, and the concentration is 1.5 mol / L) and the NiO hole transport layer. The FTO conductive glass substrate is pretreated. The pretreatment process includes cleaning the FTO conductive glass substrate to be deposited in the following order: pure water, cleaning solution, pure water + ultrasonication, and air knife drying.

[0085] The deposition process takes place in the same reaction chamber. The background vacuum in the reaction chamber is controlled to be below 5E-4 Pa. Argon gas at 53 sccm is continuously introduced into the reaction chamber, and the first process gas pressure is controlled at 0.6 Pa. Then, oxygen at 23 sccm is introduced. The cathode ion gun is turned on and the current parameter is set to 150 A. Argon gas at 70 sccm is introduced for target ignition. After successful target ignition, the flow rate is changed to 40 sccm. An empty carrier is first introduced into the first reaction chamber and the warm-up engine is continuously run for 30 minutes to maintain a stable atmosphere in the chamber and remove impurities and moisture adsorbed on the carrier surface. Then, the underlying structure is loaded into the carrier and introduced into the above-mentioned reaction chamber to begin deposition. Argon gas is continuously introduced into the reaction chamber at a flow rate of 4.2 mm / s to form a first transparent conductive film with a thickness of 100 nm on the surface of the NiO hole transport layer. The flow rate of argon gas is controlled at 400 sccm and maintained at a second process gas pressure of 0.9 Pa. Then, oxygen gas is introduced at 10 sccm to continue introducing the underlying structure of the deposited first transparent conductive film into the reaction chamber. The second transparent conductive film is deposited on the side of the first transparent conductive film away from the NiO hole transport layer at a flow rate of 2.85 mm / s, forming a second transparent conductive film with a thickness of 500 nm, thus obtaining a composite transparent conductive film.

[0086] Example 13 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 3.5 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 120 nm, and a second deposition is performed on the side of the first transparent conductive film away from the NiO hole transport layer at a speed of 7.92 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 180 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0087] Figure 5 The figure shows a cross-sectional SEM image of the composite transparent conductive film provided in Embodiment 13 of the present invention. As can be seen from the figure, when the thickness of the first transparent conductive film is too high, the physical properties will be affected, resulting in voids and island structures, and the contact with the NiO hole transport layer will show a hollow phenomenon. The black area outlined by the solid line in the figure (the SnO2 electron transport layer is thinner, so it is not clearly shown in the SEM image) is not clearly shown.

[0088] Example 14 This embodiment provides a composite transparent conductive film and its preparation method. The difference between the preparation method and that of Embodiment 1 is that a first deposition is performed on the surface of the NiO hole transport layer at a speed of 4.2 mm / s through the first reaction chamber to form a first transparent conductive film with a thickness of 100 nm, and a second deposition is performed on the side of the first transparent conductive film away from the NiO hole transport layer at a speed of 17.81 mm / s through the second reaction chamber to form a second transparent conductive film with a thickness of 80 nm. The remaining preparation methods and parameters are consistent with those of Embodiment 1.

[0089] The cross-sectional SEM image of the composite transparent conductive film in this embodiment is similar to... Figure 5 Similarly, this still leads to voids and island-like structures, resulting in bulging at the contact with the NiO hole transport layer.

[0090] Comparative Example 1 This comparative example provides a transparent conductive thin film and its preparation method, the preparation method comprising the following steps: A NiO hole transport layer is provided, which is disposed on the top layer of the underlying structure. The underlying structure includes, from bottom to top, an FTO conductive glass substrate, a SnO2 electron transport layer, a perovskite light-absorbing layer (in the perovskite solution, the molar ratio of lead iodide:formamidinium hydroiodate:methylammonium iodide:cesium iodide is 1:0.9:0.05:0.05, the mixed solvent DMF:DMSO is 4:1, and the concentration is 1.5 mol / L) and the NiO hole transport layer. The FTO conductive glass substrate is pretreated. The pretreatment process includes cleaning the FTO conductive glass substrate to be deposited in the following order: pure water, cleaning solution, pure water + ultrasonication, and air knife drying.

[0091] The deposition process takes place in the first reaction chamber. The base vacuum of the first reaction chamber is controlled to be below 5E-4Pa. Argon gas at 40 sccm is continuously introduced into the first reaction chamber, and the first reaction chamber is controlled at the first process gas pressure of 0.45Pa. Then, oxygen at 26 sccm is introduced simultaneously for the first deposition. The cathode ion gun is turned on and the current parameter is set to 150A. Argon gas at 70 sccm is introduced for target ignition. After successful target ignition, the flow rate is changed to 40 sccm, and an empty carrier is introduced into the first reaction chamber. The warm-up engine is run continuously for 30 minutes to maintain a stable atmosphere in the chamber and remove impurities and moisture adsorbed on the carrier surface. Then, the bottom layer structure is loaded into the carrier and introduced into the first reaction chamber to begin deposition. It passes through the first reaction chamber at a speed of 1.4 mm / s to deposit a transparent conductive film with a thickness of 300 nm on the surface of the NiO hole transport layer.

[0092] Comparative Example 2 This comparative example provides a transparent conductive film and its preparation method. The difference between the preparation method and that of Comparative Example 1 is that the film is deposited on the surface of the NiO hole transport layer at a speed of 2.1 mm / s through the first reaction chamber to form a transparent conductive film with a thickness of 200 nm. The rest of the preparation method and parameters are the same as those of Comparative Example 1.

[0093] Comparative Example 3 This comparative example provides a transparent conductive film and its preparation method. The difference between the preparation method and that of Comparative Example 1 is that the film is deposited on the surface of the NiO hole transport layer at a speed of 4.2 mm / s through the first reaction chamber to form a transparent conductive film with a thickness of 100 nm. The rest of the preparation method and parameters are the same as those of Comparative Example 1.

[0094] Comparative Example 4 This comparative example provides a transparent conductive thin film and its preparation method, the preparation method comprising the following steps: A NiO hole transport layer is provided, which is disposed on the top layer of the underlying structure. The underlying structure includes, from bottom to top, an FTO conductive glass substrate, a SnO2 electron transport layer, a perovskite light-absorbing layer (in the perovskite solution, the molar ratio of lead iodide:formamidinium hydroiodate:methylammonium iodide:cesium iodide is 1:0.9:0.05:0.05, the mixed solvent DMF:DMSO is 4:1, and the concentration is 1.5 mol / L) and the NiO hole transport layer. The FTO conductive glass substrate is pretreated. The pretreatment process includes cleaning the FTO conductive glass substrate to be deposited in the following order: pure water, cleaning solution, pure water + ultrasonication, and air knife drying.

[0095] The deposition process takes place in the second reaction chamber. The background vacuum of the second reaction chamber is controlled to be below 5E-4Pa. Argon gas at 500 sccm is continuously introduced into the second reaction chamber, and the second reaction chamber is controlled at the second process gas pressure of 1.1Pa. Then, oxygen at 9.5 sccm is introduced simultaneously to prepare for the second deposition reaction. The cathode ion gun is turned on and the current parameter is set to 150A. Argon gas at 70 sccm is introduced for target ignition. After successful target ignition, the flow rate is changed to 40 sccm, and an empty carrier is introduced into the second reaction chamber. The warm-up engine is run continuously for 30 minutes to maintain a stable atmosphere in the chamber and remove impurities and moisture adsorbed on the carrier surface. Then, the bottom layer structure is loaded into the carrier and introduced into the second reaction chamber to begin deposition. It passes through the second reaction chamber at a speed of 4.75 mm / s to deposit a transparent conductive film with a thickness of 300 nm on the surface of the NiO hole transport layer.

[0096] Comparative Example 5 This comparative example provides a transparent conductive film and its preparation method. The difference between the preparation method and that of Comparative Example 4 is that the film is deposited on the surface of the NiO hole transport layer at a speed of 7.12 mm / s through the second reaction chamber to form a transparent conductive film with a thickness of 200 nm. The rest of the preparation method and parameters are the same as those of Comparative Example 4.

[0097] Comparative Example 6 This comparative example provides a transparent conductive film and its preparation method. The difference between the preparation method and that of Comparative Example 4 is that the film is deposited on the surface of the NiO hole transport layer at a speed of 14.25 mm / s through the second reaction chamber to form a transparent conductive film with a thickness of 100 nm. The rest of the preparation method and parameters are the same as those of Comparative Example 4.

[0098] Comparative Example 7 This comparative example provides a composite transparent conductive film and its preparation method. The difference between the preparation method and Example 1 is that the first process gas pressure is controlled at 0.65 Pa, and the rate at which the underlying structure passes through the first reaction chamber is adaptively adjusted to obtain a first transparent conductive film with a thickness of 15 nm. The remaining preparation methods and parameters are consistent with those of Example 1.

[0099] Comparative Example 8 This comparative example provides a composite transparent conductive film and its preparation method. The difference between the preparation method and Example 1 is that the second process gas pressure is controlled at 0.65 Pa, and the rate at which the bottom layer structure of the first transparent conductive film is deposited passes through the second reaction chamber is adaptively adjusted to obtain a second transparent conductive film with a thickness of 285 nm. The remaining preparation methods and parameters are consistent with those of Example 1.

[0100] Comparative Example 9 This comparative example provides a composite transparent conductive film and its preparation method. The difference between the preparation method and Example 1 is that the second process gas pressure is controlled at 1.15 Pa, and the rate at which the bottom layer structure of the first transparent conductive film is deposited passes through the second reaction chamber is adaptively adjusted to obtain a second transparent conductive film with a thickness of 285 nm. The remaining preparation methods and parameters are consistent with those of Example 1.

[0101] Comparative Example 10 This comparative example provides a composite transparent conductive film and its preparation method. The difference between the preparation method and Example 1 is that the first process gas pressure is controlled at 1.1 Pa, the second process gas pressure is controlled at 0.45 Pa, the rate at which the underlying structure passes through the first reaction chamber is adaptively adjusted to obtain a first transparent conductive film with a thickness of 15 nm, and the rate at which the underlying structure deposited with the first transparent conductive film passes through the second reaction chamber is adaptively adjusted to obtain a second transparent conductive film with a thickness of 285 nm. The remaining preparation methods and parameters are consistent with those of Example 1.

[0102] The resistivity of the composite transparent conductive films and transparent conductive films provided in Examples 1-14 and Comparative Examples 1-10 was tested, and their contact with the carrier transport layer was observed. Specific data are shown in Table 1. To ensure data accuracy, the resistivity of all samples was measured at 23 points. The following data are average resistivity values.

[0103] Table 1 Note: " / " indicates that the corresponding process was not carried out and the corresponding transparent conductive film was not prepared.

[0104] The test results show that: (1) As can be seen from Examples 1-8, 11 and 12, the present invention adopts a dual-pressure deposition process. First, a thinner first transparent conductive film is formed by deposition at a low pressure of 0.2 Pa to 0.6 Pa. The resulting first transparent conductive film has a denser, more ordered crystal structure with fewer defects, providing good electrical performance for the composite transparent conductive film while taking into account moderate internal stress. Then, a thicker second transparent conductive film is formed by deposition at a high pressure of 0.7 Pa to 1.1 Pa. The resulting second transparent conductive film has lower internal stress and is less prone to falling off, reducing the overall film stress of the composite transparent conductive film. This makes the composite transparent conductive film in close contact with the carrier transport layer and also has good electrical performance, with resistivity ≤9.00E-04Ω·cm.

[0105] (2) As can be seen from Examples 9-10 and 13-14, the present invention further controls the thickness of the first transparent conductive film to 10nm-100nm and the thickness of the second transparent conductive film to 100nm-500nm. The optimal electrical and physical properties can be achieved by matching the thicknesses of the two films. If the first transparent conductive film is too thick (Example 13), the stress of the first transparent conductive film will increase, the film will warp, and there will be bulging when it contacts the charge carrier transport layer. If the first transparent conductive film is too thin (Example 10), the electrical properties of the first transparent conductive film will deteriorate. If the second transparent conductive film is too thick (Example 9), although the overall performance can be maintained, the transmittance of the composite transparent conductive film will deteriorate and the laser scribing performance will deteriorate. If the second transparent conductive film is too thin (Example 14), the electrical properties of the composite transparent conductive film will also deteriorate.

[0106] (3) As can be seen from Comparative Examples 1 to 6, if deposition is carried out only under low pressure, the thicker the first transparent conductive film, the better the electrical performance and the lower the resistivity of the film. However, it will also lead to poor contact with the carrier transport layer, increased stress, film warping, and voids in the contact with the carrier transport layer. If deposition is carried out only under high pressure, the second transparent conductive film will satisfy the requirement of close contact with the carrier transport layer. However, the thicker the film, the worse the electrical performance and the higher the resistivity. Therefore, only by combining deposition under low pressure and deposition under high pressure, and controlling the process pressure and film thickness of each film, can we achieve both close contact (physical performance) between the film and the carrier transport layer and good electrical performance.

[0107] (4) As can be seen from Comparative Examples 7-10, by further adjusting the first process gas pressure to 0.2 Pa to 0.6 Pa and the second process gas pressure to 0.7 Pa to 1.1 Pa, the optimal electrical and physical properties can be achieved by combining the two process gas pressures. If the first process gas pressure is too low, the stress of the first transparent conductive film will increase; if the first process gas pressure is too high, the electrical properties of the first transparent conductive film will deteriorate. If the second process gas pressure is too low, the stress of the composite transparent conductive film will increase, making it easy to fall off; if the second process gas pressure is too high, the electrical properties of the composite transparent conductive film will deteriorate.

[0108] In summary, this invention employs a dual-pressure deposition process. First, a thinner first transparent conductive film is deposited using a low pressure of 0.2 Pa to 0.6 Pa. This results in a denser, more ordered crystal structure with fewer defects, providing excellent electrical properties for the composite transparent conductive film. Then, a thicker second transparent conductive film is deposited using a high pressure of 0.7 Pa to 1.1 Pa. This second film has lower internal stress, is less prone to detachment, and reduces the overall film stress of the composite transparent conductive film. Therefore, by combining low-pressure and high-pressure deposition processes, and with the synergistic effect of the first and second transparent conductive films, the composite transparent conductive film achieves both excellent electrical properties and good adhesion to the charge carrier transport layer. This dual-pressure deposition process eliminates the need for heating, simplifying the preparation process. Furthermore, it increases the process adjustment window, allowing for more flexible adjustments and better adaptability for preparing various transparent conductive films on the surface of charge carrier transport layers of different materials.

[0109] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a composite transparent conductive film, characterized in that, The preparation method includes the following steps: S1 provides a carrier transport layer; S2. Under a first process pressure of 0.2Pa~0.6Pa, a first deposition is performed on one side surface of the charge carrier transport layer to form a first transparent conductive film; S3. Under the second process pressure of 0.7Pa~1.1Pa, a second deposition is performed on the surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film, thereby obtaining a composite transparent conductive film. The thickness of the first transparent conductive film is less than the thickness of the second transparent conductive film.

2. The preparation method according to claim 1, characterized in that, In step S2, the thickness of the first transparent conductive film is 10nm~100nm.

3. The preparation method according to claim 1, characterized in that, In step S3, the thickness of the second transparent conductive film is 100nm~500nm.

4. The preparation method according to claim 1, characterized in that, In step S2, the first reaction gas for the first deposition includes oxygen, and the flow rate of the oxygen is 18 sccm to 26 sccm.

5. The preparation method according to claim 1, characterized in that, In step S3, the second reaction gas for the second deposition includes oxygen, and the flow rate of the oxygen is 6 sccm to 13 sccm.

6. The preparation method according to claim 1, characterized in that, The carrier transport layer in step S1 includes a hole transport layer, or the carrier transport layer includes an electron transport layer.

7. The preparation method according to claim 6, characterized in that, The carrier transport layer described in step S1 is located at the top layer of the underlying structure.

8. The preparation method according to claim 7, characterized in that, Step S2, the first deposition, and step S3, the second deposition, are performed in different reaction chambers, or step S2, the first deposition, and step S3, the second deposition, are performed in the same reaction chamber.

9. The preparation method according to claim 8, characterized in that, Step S2, the first deposition, and step S3, the second deposition, are performed in different reaction chambers. The processes of step S2, the first deposition, and step S3, the second deposition include: An inert gas is continuously introduced into the first reaction chamber and controlled at the first process gas pressure. Then, a first reaction gas is introduced to prepare for the first deposition. The inert gas is continuously introduced into the second reaction chamber and controlled at the second process gas pressure. Then, a second reaction gas is introduced to prepare for the second deposition. The ion source is turned on to start the reaction target, and the underlying structure is introduced into the first reaction chamber. It passes through the first reaction chamber at a first speed and performs a first deposition on one side surface of the charge carrier transport layer to form a first transparent conductive film. The underlying structure with the first transparent conductive film deposited thereon is further introduced into the second reaction chamber and passes through the second reaction chamber at a second speed. A second deposition is performed on the surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film, thus obtaining a composite transparent conductive film.

10. The preparation method according to claim 8, characterized in that, Step S2, the first deposition, and step S3, the second deposition, are performed in the same reaction chamber. The process of step S2, the first deposition, and step S3, the second deposition includes: An inert gas is continuously introduced into the reaction chamber and controlled at the first process gas pressure. Then, the first reaction gas is introduced, the ion source is turned on to start the reaction target, and the underlying structure is introduced into the reaction chamber. The material is deposited on one side surface of the charge carrier transport layer at a first speed from one end of the reaction chamber to the other end to form a first transparent conductive film. The flow rate of the inert gas is adjusted to control the second process gas pressure, and then the second reaction gas is introduced. The underlying structure on which the first transparent conductive film is deposited is moved from one end of the reaction chamber to the other end at a second speed. A second deposition is performed on the surface of the first transparent conductive film away from the charge carrier transport layer to form a second transparent conductive film, thus obtaining a composite transparent conductive film.

11. A composite transparent conductive film, characterized in that, The composite transparent conductive film is prepared by the preparation method according to any one of claims 1 to 10. The composite transparent conductive film includes a first transparent conductive film and a second transparent conductive film from bottom to top. The first transparent conductive film is bonded to the carrier transport layer.

12. The composite transparent conductive film according to claim 11, characterized in that, The thickness of the first transparent conductive film is 10nm~100nm.

13. The composite transparent conductive film according to claim 11, characterized in that, The thickness of the second transparent conductive film is 100nm~500nm.

14. A perovskite solar cell module, characterized in that, The perovskite solar cell module includes the composite transparent conductive film as described in any one of claims 11 to 13.

15. A photovoltaic cell module, characterized in that, The photovoltaic cell module includes the perovskite solar cell module as described in claim 14.

16. A composite transparent conductive film production equipment, characterized in that, The composite transparent conductive film production equipment is used to produce the composite transparent conductive film according to any one of claims 11 to 13.

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