High-performance transparent conductive film and preparation method and application thereof

Abstract

The invention discloses a high-performance transparent conductive film and a preparation method and application thereof, and relates to the technical field of photoelectric materials. The preparation method of the high-performance transparent conductive film comprises the following steps: introducing mixed gas of Ar and O2 into a vacuum cavity, and depositing a first TCO layer on a substrate; pure Ar gas is introduced into the vacuum cavity, and a metal layer is deposited on the first TCO layer; pure Ar gas is introduced into the vacuum cavity, and a second TCO layer is deposited on the metal layer; after deposition is finished, the sample is subjected to first-time annealing treatment at the first preset temperature in the aerobic atmosphere, then the sample is subjected to second-time annealing treatment at the second preset temperature in the vacuum or inert gas atmosphere, and the first preset temperature is lower than the second preset temperature. According to the technical scheme, the overall performance of the transparent conductive film is improved, and the transparent conductive film has great application potential in the field of transparent low-power-consumption electronic devices.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and particularly to a high-performance transparent conductive thin film, a preparation method thereof, and an application thereof. Background Art

[0002] Transparent conductive oxide (TCO) materials have many applications in fields such as flat panel displays, solar cells, photodetectors, FETs, and transparent electrodes due to their unique light transmittance and conductivity; most TCO thin films have a high transmittance in the visible light band, but the sheet resistance is large, and there is a large power loss during application; at the same time, in fields such as solar cells, a high carrier concentration is beneficial to improving the efficiency and stability of the battery structure. However, the carrier concentration of common TCO thin films is low; for example, the most common ITO thin film, the sheet resistance of the ITO thin film prepared by magnetron sputtering is usually greater than 25 Ω after annealing treatment, and the carrier concentration is lower than 1×10 21 / cm 3 , which greatly limits its application potential in transparent low-power electronic devices.

[0003] At present, there are studies on preparing transparent conductive thin films with a TCO-metal layer-TCO laminated structure through physical vapor deposition processes. The metal layer is used as the intermediate layer between the two transparent conductive oxides to reduce the sheet resistance of the transparent conductive thin film and increase its carrier concentration; however, the high light transmittance and low resistance of the transparent conductive thin film have always been a difficult-to-reconcile contradiction. When traditional TCO thin films reduce the sheet resistance and increase the carrier concentration, the light transmittance often decreases significantly due to the enhanced free carrier absorption; most studies use pure argon as the working gas when preparing the two-layer TCO, and the prepared TCO film layer has more crystal defects, which has an adverse effect on the uniformity, stability, and light transmittance of the thin film; there are also studies that pass a small amount of oxygen when preparing the two-layer TCO, but the presence of oxygen inevitably oxidizes the metal layer (such as metal layers of Cu, Ag, Ni, Al, Ti, Zn, Cr, etc. that are susceptible to the oxygen atmosphere) when preparing the top layer TCO, thereby increasing the sheet resistance of the thin film; in addition, there are studies that use special nanostructure designs or graphene and carbon nanomaterials to simultaneously improve the electrical and optical properties of the thin film, but these designs are often more complex and costly; in addition, the post-annealing process also has a significant impact on the overall performance of the laminated structure transparent conductive thin film. However, most studies only use vacuum annealing or air annealing at a fixed temperature, lacking consideration of the differences between the film layers and the diffusion of atoms between the film layers; therefore, the existing studies still have limited improvement in the overall performance of the TCO-metal layer-TCO laminated structure transparent conductive thin film. Summary of the Invention

[0004] The present invention provides a method for preparing a high-performance transparent conductive film, aiming to improve the overall performance of the transparent conductive film through the optimized design of the physical vapor deposition atmosphere and the overall annealing process of the film.

[0005] The preparation of the high-performance transparent conductive film includes the following steps:

[0006] S1, placing the cleaned substrate in a vacuum chamber and pumping to the base vacuum degree;

[0007] S2, introducing a mixed gas of Ar and O2 into the vacuum chamber, adjusting to a preset pressure, using a first transparent conductive oxide as the coating material, and depositing a first TCO layer on the substrate;

[0008] S3, pumping the vacuum chamber to the base vacuum degree, introducing pure Ar gas, adjusting to a preset pressure, using a metal as the coating material, and depositing a metal layer on the first TCO layer;

[0009] The metal is at least one of Cu, Ag, Ni, Al, Ti, Zn, Cr; the deposited metal layer can be a single metal of Cu, Ag, Ni, Al, Ti, Zn, Cr, or an alloy material formed by two or more metals, or a laminated structure formed by two or more metals; these metal materials mentioned in the present invention are easily oxidized by oxygen during physical vapor deposition, and other metal materials that are easily oxidized by oxygen not mentioned are also applicable to the present invention.

[0010] S4, after completing the deposition of the metal layer, pumping the vacuum chamber to the base vacuum degree again, introducing pure Ar gas, adjusting to a preset pressure, using a second transparent conductive oxide as the coating material, and depositing a second TCO layer on the metal layer;

[0011] S5, taking out the sample after deposition, performing a first annealing treatment on the sample at a first preset temperature in an oxygen-containing atmosphere, and then performing a second annealing treatment on the sample at a second preset temperature in a vacuum or inert gas atmosphere, where the first preset temperature is lower than the second preset temperature.

[0012] The processes of depositing the first TCO layer, the metal layer, and the second TCO layer are physical vapor deposition.

[0013] Optionally, the process of depositing the first TCO layer, the metal layer, and the second TCO layer is at least one of magnetron sputtering, electron beam evaporation, and vacuum evaporation; for example, the first TCO layer, the metal layer, and the second TCO layer can all be prepared by magnetron sputtering, or all by electron beam evaporation, or all by vacuum evaporation, or the first TCO layer and the second TCO layer can be prepared by electron beam evaporation, and the metal layer can be prepared by magnetron sputtering. It can be understood that the technical effects of the present invention can be achieved by using different physical vapor deposition processes to prepare the TCO-metal layer-TCO laminated structure transparent conductive film; preferably, the first TCO layer, the metal layer, and the second TCO layer are all prepared by magnetron sputtering, which not only ensures the coherence of the process but also fully exerts the advantages of high film-forming quality, strong process adaptability, high deposition efficiency, and controllable deposition process of magnetron sputtering.

[0014] Optionally, the substrate is a transparent material, such as glass (doped Sn glass, soda-lime glass, etc.), quartz, alumina, transparent polymer film materials, etc.

[0015] Optionally, the first transparent conductive oxide or the second transparent conductive oxide is at least one of indium oxide (In2O3), tin oxide (SnO x ), zinc oxide (ZnO), indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), tin zinc oxide (ZTO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO); the first TCO layer and the second TCO layer can choose the same material, such as both choosing ITO; the first TCO layer and the second TCO layer can also choose different materials, such as the first TCO layer choosing ITO and the second TCO layer choosing AZO.

[0016] Optionally, the aerobic atmosphere is one of air, pure oxygen, and a mixture of oxygen and inert gas.

[0017] Based on the above preparation method, the present invention proposes a high-performance transparent conductive film with an ITO / Cu / ITO structure, that is, the first TCO layer is ITO, the metal layer is Cu, and the second TCO layer is ITO.

[0018] Optionally, in the step S2, the flow ratio of Ar and O2 in the mixed gas is (99:1) to (97:3); for example, the flow ratio of Ar and O2 can be 99:1, 98.5:1.5, 98:2, 97.5:2.5, 97:3, and other specific ratios within the numerical range are also applicable to the present invention.

[0019] Optionally, in the step S2, the first TCO layer is deposited by magnetron sputtering; the magnetron sputtering parameters are: working pressure 0.1~1 Pa, sputtering power 100 W, pre-sputtering duration 5~15 min, sputtering rate 5~10 nm / min.

[0020] Optionally, in the step S3, the metal layer is deposited by magnetron sputtering; the magnetron sputtering parameters are: working pressure 0.1~1 Pa, sputtering power 100 W, sputtering rate 3~10 nm / min.

[0021] Optionally, in the step S4, the second TCO layer is deposited by magnetron sputtering; the magnetron sputtering parameters are: working pressure 0.1~1 Pa, sputtering power 100 W, pre-sputtering duration 5~15 min, sputtering rate 5~10 nm / min.

[0022] Optionally, in the step S5, the first preset temperature is 150°C~230°C, and the duration of the first annealing treatment is 0.5~1 h; the second preset temperature is 280°C~400°C, and the duration of the second annealing treatment is 0.5~1 h.

[0023] The present invention also provides a transparent low-power electronic device, including the high-performance transparent conductive film prepared by the above preparation method.

[0024] The transparent low-power electronic device can be an organic light-emitting diode (OLED) transparent display, a Micro LED transparent display, a microelectromechanical system (MEMS) transparent display, an electrochromic device, a transparent electrophoretic electronic paper, a transparent solar cell, a transparent supercapacitor, a transparent sensor, a transparent storage device, a transparent antenna, a transparent radio frequency identification tag, a VR / AR / XR head-mounted display device, etc.

[0025] Among these transparent low-power electronic devices, the transparent conductive film is the core basic material and is widely used as electrodes and conductive lines. It not only requires good uniformity and stability, but also needs to simultaneously have excellent light transmittance and conductivity to meet the requirements of transparency and low power consumption. In some applications (such as solar cells), the transparent conductive film also needs to have a high carrier concentration; the high-performance transparent conductive film prepared by the present invention meets the high requirements of these transparent low-power electronic devices for the overall performance of the transparent conductive film.

[0026] The present invention has the following beneficial effects:

[0027] The present invention prepares a transparent conductive film with a TCO-metal layer-TCO laminated structure by physical vapor deposition. The first TCO layer is prepared under the condition of introducing oxygen to ensure the integrity of the crystal structure of the first TCO layer. The second TCO layer is deposited in a pure argon atmosphere to prevent the oxidation of the easily oxidized intermediate metal layer by oxygen. After depositing the laminated structure, the crystal structure of the second TCO layer is improved by the first annealing in an aerobic atmosphere, reducing crystal defects and oxygen vacancies, increasing the overall light transmittance of the film. At the same time, the oxidation drive can accelerate the diffusion of intermediate layer metal atoms into the two TCO layers, effectively reducing the sheet resistance of the film and increasing the carrier concentration. Finally, the second annealing at a higher temperature is carried out in a vacuum or protective atmosphere to further enhance the crystallinity and densification of the film, improving the light transmittance, stability and uniformity of the film. The technical solution of the present invention improves both the electrical and optical properties of the transparent conductive film, realizing the improvement of the overall performance of the transparent conductive film. The prepared high-performance transparent conductive film has great application potential in the field of transparent low-power electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or in the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0029] Figure 1 It is a flowchart of some embodiments of the method for preparing a high-performance transparent conductive film of the present invention;

[0030] Figure 2 It is a schematic diagram of the film layer structure of the high-performance transparent conductive film prepared in some embodiments of the present invention;

[0031] Figure 3 It is a schematic process flow diagram of some embodiments of the method for preparing a high-performance transparent conductive film of the present invention;

[0032] Figure 4 It is a graph of the sheet resistance test results of the high-performance transparent conductive film prepared in some embodiments of the present invention;

[0033] Figure 5 It is a graph of the carrier concentration test results of the high-performance transparent conductive film prepared in some embodiments of the present invention;

[0034] Figure 6 It is a transmittance spectrum diagram of the high-performance transparent conductive film prepared in some embodiments of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0035] To make the objectives, features, and advantages of the present invention more apparent and understandable, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the embodiments described below are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0036] The terms "first" and "second" in the specification and drawings of the present invention are only used to distinguish similar objects and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products, or devices.

[0037] Refer to Figure 1 , the high-performance transparent conductive film provided by the embodiments of the present invention is prepared through the following steps S1 to S5:

[0038] S1, Place the cleaned substrate in a vacuum chamber and evacuate to the base vacuum.

[0039] In some preferred embodiments, the substrate is a transparent material, such as glass (doped Sn glass, soda-lime glass, etc.), quartz, alumina, transparent polymer film, etc.

[0040] S2, Introduce a mixed gas of Ar and O2 into the vacuum chamber, adjust to the preset pressure, use the first transparent conductive oxide as the coating material, and deposit the first TCO layer on the substrate by physical vapor deposition.

[0041] The first transparent conductive oxide includes but is not limited to one or more of In2O3, SnO x , ZnO, ITO, IZO, AZO, GZO, ZTO, FTO, ATO; the processes available for depositing the first TCO layer include but are not limited to magnetron sputtering, electron beam evaporation, and vacuum evaporation.

[0042] Preparing the first TCO layer under the condition of introducing oxygen can ensure the integrity of the crystal structure of the first TCO layer, reduce crystal defects and oxygen vacancies, and improve the light transmittance, uniformity, and stability of the film.

[0043] S3. Evacuate the vacuum chamber to the background vacuum degree, introduce pure Ar gas, adjust it to the preset pressure, use a metal as the coating material, and deposit a metal layer on the first TCO layer. The metal is at least one of Cu, Ag, Ni, Al, Ti, Zn, and Cr; the processes available for depositing the metal layer include but are not limited to magnetron sputtering, electron beam evaporation, and vacuum evaporation.

[0044] S4. After completing the deposition of the metal layer, evacuate the vacuum chamber to the background vacuum degree again, introduce pure Ar gas, adjust it to the preset pressure, use a second transparent conductive oxide as the coating material, and deposit a second TCO layer on the metal layer.

[0045] The second transparent conductive oxide includes but is not limited to one or more of In2O3, SnO x , ZnO, ITO, IZO, AZO, GZO, ZTO, FTO, and ATO; the processes available for depositing the second TCO layer include but are not limited to magnetron sputtering, electron beam evaporation, and vacuum evaporation.

[0046] Metals such as Cu, Ag, Ni, Al, Ti, Zn, and Cr are easily oxidized in a physical vapor deposition environment with oxygen, thereby increasing the sheet resistance of the film. Depositing the second TCO layer in a pure argon atmosphere can prevent the oxidation of the easily oxidized intermediate metal layer by oxygen.

[0047] S5. Take out the sample after deposition, perform a first annealing treatment on the sample at a first preset temperature in an oxygen-containing atmosphere (air, pure oxygen, or a mixture of oxygen and inert gas), and then perform a second annealing treatment on the sample at a second preset temperature in a vacuum or inert gas atmosphere (such as nitrogen). The first preset temperature is lower than the second preset temperature.

[0048] In the embodiment of the present invention, physical vapor deposition is used to prepare a transparent conductive film with a TCO-metal layer-TCO laminated structure (for the film layer structure, refer to Figure 2), the first TCO layer is prepared under the condition of introducing oxygen to ensure the integrity of the crystal structure of the first TCO layer. The second TCO layer is deposited in a pure argon atmosphere to prevent the oxidation of the easily oxidized intermediate metal layer by oxygen. After depositing the stacked structure, the crystal structure of the second TCO layer is improved by the first annealing in an aerobic atmosphere, reducing crystal defects and oxygen vacancies, increasing the overall light transmittance of the thin film. At the same time, oxidation driving can accelerate the diffusion of intermediate layer metal atoms into the two TCO layers (wherein, due to more defects in the second TCO layer, the diffusion rate of intermediate layer metal atoms into the second TCO layer is higher than that into the first TCO layer), effectively reducing the sheet resistance of the thin film and increasing the carrier concentration. Finally, the second annealing at a higher temperature is carried out in a vacuum or protective atmosphere to further enhance the crystallinity of the thin film, improving the light transmittance, stability and uniformity of the thin film. The embodiment of the present invention realizes the improvement of the overall performance of the transparent conductive thin film, and the prepared high-performance transparent conductive thin film has great application potential in the field of transparent low-power electronic devices.

[0049] Based on the above method embodiments, the present invention proposes a high-performance transparent conductive thin film with an ITO / Cu / ITO stacked structure.

[0050] ITO is the most common TCO thin film material. In the ITO thin film usually prepared by magnetron sputtering, the sheet resistance of the thin film is greater than 25 Ω after annealing treatment, and the carrier concentration is lower than 1×10 21 / cm 3 ; ITO has many advantages and is favored in fields such as photovoltaics and displays. However, its high sheet resistance and low carrier concentration limit its application potential. Therefore, it is of great significance to optimize its overall performance.

[0051] Refer to Figure 3 , in some embodiments, the high-performance transparent conductive thin film with an ITO / Cu / ITO stacked structure provided by the present invention is prepared by the following steps:

[0052] Prepare a cleaned and dried substrate.

[0053] Load the substrate into the vacuum coating chamber. When the equipment vacuum degree is better than 5×10 -4 Pa, introduce a mixed gas of Ar and O2 (a certain ratio within the range of the flow ratio of Ar and O2 being (99:1) to (97:3)), adjust the working pressure to 0.1 - 1 Pa, use an ITO target (In2O3:SnO2 = 9:1) as the sputtering source, with a power of 100 W, and perform pre-sputtering for 15 min. After stabilization, prepare the first layer of ITO thin film at a sputtering rate of 5 - 10 nm / min.

[0054] Adjust the equipment to a vacuum degree better than 5×10 -4Introduce Ar gas, adjust the pressure to 0.1 - 1 Pa. Use a Cu target (purity 99.999%) as the sputtering source, with a power of 100 W, and prepare the Cu film at a sputtering rate of 3 - 10 nm / min.

[0055] Adjust the equipment vacuum, introduce Ar gas, adjust the pressure to 0.1 - 1 Pa. Use an ITO target (the same as the target used for the first - layer ITO film) as the sputtering source, with a power of 100 W, and perform pre - sputtering for 5 - 15 min. After stabilization, prepare the second - layer ITO film at a sputtering rate of 5 - 10 nm / min.

[0056] After the coating is completed, take out the sample. In an oxygen - containing atmosphere, anneal the sample at a relatively low temperature (150°C - 230°C) for 0.5 - 1 h. After the sample cools to room temperature, perform a second annealing at a higher temperature (280°C - 400°C) in a vacuum or protective atmosphere for 0.5 - 1 h.

[0057] It should be noted that the preparation of the ITO / Cu / ITO stacked structure can not only adopt the magnetron sputtering process, but also adopt the electron beam evaporation or vacuum evaporation process. For example, when preparing ITO by electron beam evaporation or vacuum evaporation, place the substrate in the coating fixture, pre - evaporate the ITO film material for a certain time first, and then deposit the ITO film on the substrate at a certain rate. During the evaporation coating process, a mixed gas of argon and oxygen can be introduced to prepare the first - layer ITO film.

[0058] Based on the above embodiments of the ITO / Cu / ITO stacked - structure transparent conductive film, the present application also proposes the following specific embodiments. It should be noted that the following specific embodiments are only for illustrative purposes and do not limit the protection scope of the present application in any form.

[0059] Example 1

[0060] Ultrasonically clean the glass substrate with dishwashing liquid for 10 min, clean it with ultrapure water for 10 min, ultrasonically clean it with acetone for 10 min, ultrasonically clean it with absolute ethanol for 10 min, ultrasonically clean it with ultrapure water for 15 min, and finally heat - dry the substrate.

[0061] Prepare an ITO target (In2O3:SnO2 = 9:1) and a Cu target (purity 99.999%).

[0062] When the equipment vacuum is better than 5×10 -4At a pressure of [[Pa]], a mixed gas of Ar and O2 is introduced, and the pressure is adjusted to 0.1 - 1 [[Pa]]. Using an ITO target as the sputtering source with a power of 100 W, pre-sputtering is carried out for 15 min. After stabilization, the first layer of ITO thin film is prepared at a sputtering rate of 10 nm / min, and the thickness of the first layer of ITO thin film is 50 nm.

[0063] The equipment is adjusted to the process vacuum again, Ar is introduced, the pressure is adjusted to 0.1 - 1 [[Pa]], using a Cu target as the sputtering source with a power of 100 W, a Cu layer is prepared at a sputtering rate of 5 nm / min, and the thickness of the Cu layer is 5 nm.

[0064] The vacuum degree of the equipment is adjusted, Ar is introduced, the pressure is adjusted to 0.1 - 1 [[Pa]], using an ITO target as the sputtering source with a power of 100 W, pre-sputtering is carried out for 5 - 15 min. After stabilization, the second layer of ITO thin film is prepared at a sputtering rate of 10 nm / min, and the thickness of the second layer of ITO thin film is 50 nm.

[0065] After the coating is completed, the sample is taken out and annealed; first, in an oxygen-containing atmosphere, the sample is annealed at a lower temperature (150 °C - 230 °C) for 0.5 - 1 h; after the sample is cooled to room temperature, it is annealed again at a higher temperature (280 °C - 400 °C) in a vacuum or protective atmosphere for a treatment duration of 0.5 - 1 h.

[0066] Example 2

[0067] The preparation steps of the transparent conductive thin film provided in this example refer to Example 1, and the difference from Example 1 is that the thickness of the middle Cu layer is 10 nm.

[0068] Example 3

[0069] The preparation steps of the transparent conductive thin film provided in this example refer to Example 1, and the difference from Example 1 is that the thickness of the middle Cu layer is 15 nm.

[0070] Comparative Example 1

[0071] The preparation steps of the transparent conductive thin film provided in this comparative example refer to Example 1, and the difference from Example 1 is that the thin film is not annealed.

[0072] Comparative Example 2

[0073] The preparation steps of the transparent conductive thin film provided in this comparative example refer to Example 2, and the difference from Example 2 is that the thin film is not annealed.

[0074] Comparative Example 3

[0075] The preparation steps of the transparent conductive thin film provided in this comparative example refer to Example 3, and the difference from Example 3 is that the thin film is not annealed.

[0076] Measurement of Electrical and Optical Properties:

[0077] The sheet resistance of the samples of Examples 1 to 3 and Comparative Examples 1 to 3 was measured by a sheet resistance meter respectively, and the results are as Figure 4 shown. The data points marked as "RT" represent the samples (Comparative Examples) without annealing treatment at room temperature, and the data points marked as "Annealing" represent the samples (Examples) with annealing treatment; it can be Figure 4 seen that the sheet resistance of the thin film samples after annealing treatment decreased significantly. Among them, the sheet resistance of the sample of Example 1 was 2.84 Ω, the sheet resistance of the sample of Example 2 was 0.41 Ω, and the sheet resistance of the sample of Example 3 was 0.36 Ω. Each example had an extremely low sheet resistance, meeting the requirements for the conductivity of transparent conductive films in most application scenarios.

[0078] The carrier concentration of the samples of Examples 1 to 3 and Comparative Examples 1 to 3 was measured by a Hall tester respectively, and the results are as Figure 5 shown. The carrier concentration of the thin film samples increased significantly after annealing treatment. Among them, the carrier concentration of the sample of Example 1 was 3.18×10 22 / cm 3 , the carrier concentration of the sample of Example 2 was 7.28×10 22 / cm 3 , and the carrier concentration of the sample of Example 3 was 1.03×10 23 / cm 3 . Compared with the carrier concentration of the ITO thin film prepared by traditional magnetron sputtering, which is less than 1×10 21 / cm 3 , and the carrier concentration of the order of 10 21 / cm 3 of the ITO / Ag / ITO laminate structure in the prior art, the carrier concentration of the ITO / Cu / ITO laminate structure transparent conductive film prepared in the examples of the present invention has been significantly improved.

[0079] The transmittance spectra of the samples of Examples 1 to 3 were measured, and the results are as Figure 6 shown. The samples of Examples 1 to 3 had excellent transmittance (greater than 80%) in the long wavelength band (greater than 600 nm).

[0080] As can be seen from the above, the ITO / Cu / ITO laminated transparent conductive film prepared in the embodiment of the present invention has significant advantages of low sheet resistance, high carrier concentration, and excellent transmittance in the long wavelength band, and is particularly suitable for transparent low-power electronic devices; moreover, the ITO / Cu / ITO laminated high-performance transparent conductive film using Cu as the intermediate layer can effectively reduce the economic cost compared with the traditional Ag intermediate layer structure, and its electrical properties can meet the alternative use of some Ag laminated transparent conductive films, effectively reducing the production cost.

[0081] The above-described embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a high-performance transparent conductive film, characterized in that, It includes the following steps: S1. Place the cleaned substrate in a vacuum chamber and evacuate to the base vacuum degree. S2. Introduce a mixed gas of Ar and O2 into the vacuum chamber, adjust it to a preset pressure, use a first transparent conductive oxide as the coating material, and deposit a first TCO layer on the substrate by physical vapor deposition. S3. Evacuate the vacuum chamber to the base vacuum degree, introduce pure Ar gas, adjust it to a preset pressure, use a metal as the coating material, and deposit a metal layer on the first TCO layer by physical vapor deposition. The metal is at least one of Cu, Ag, Ni, Al, Ti, Zn, and Cr. S4. After the deposition of the metal layer is completed, evacuate the vacuum chamber to the base vacuum degree again, introduce pure Ar gas, adjust it to a preset pressure, use a second transparent conductive oxide as the coating material, and deposit a second TCO layer on the metal layer by physical vapor deposition. S5. Take out the sample after the deposition is completed, perform a first annealing treatment on the sample at a first preset temperature in an oxygen-containing atmosphere, and then perform a second annealing treatment on the sample at a second preset temperature in a vacuum or inert gas atmosphere. The first preset temperature is lower than the second preset temperature.

2. The preparation method of the high-performance transparent conductive film according to claim 1, wherein The process for depositing the first TCO layer, the metal layer, and the second TCO layer is at least one of magnetron sputtering, electron beam evaporation, and vacuum evaporation.

3. The preparation method of the high-performance transparent conductive film according to claim 1, characterized in that, The first transparent conductive oxide or the second transparent conductive oxide is at least one of indium oxide, tin oxide, zinc oxide, indium tin oxide, indium zinc oxide, aluminum zinc oxide, gallium zinc oxide, tin zinc oxide, fluorine-doped tin oxide, and antimony tin oxide.

4. The preparation method of the high-performance transparent conductive film according to claim 1, characterized in that The oxygen-containing atmosphere is one of air, pure oxygen, and a mixture of oxygen and inert gas.

5. The preparation method of the high-performance transparent conductive film according to claim 1, characterized in that, The first TCO layer is indium tin oxide, the metal layer is Cu, and the second TCO layer is indium tin oxide.

6. The preparation method of the high-performance transparent conductive film according to claim 5, characterized in that, In the step S2, the flow ratio of Ar and O2 in the mixed gas is (99:1) - (97:3).

7. The method for preparing a high-performance transparent conductive film according to claim 6, wherein In the step S2, the first TCO layer is deposited by magnetron sputtering. The magnetron sputtering parameters are: working pressure 0.1 - 1 Pa, sputtering power 100 W, pre-sputtering duration 5 - 15 min, and sputtering rate 5 - 10 nm / min.

8. The preparation method of the high-performance transparent conductive film according to claim 5, characterized in that, In the step S3, the metal layer is deposited by magnetron sputtering. The magnetron sputtering parameters are: working pressure 0.1 - 1 Pa, sputtering power 100 W, and sputtering rate 3 - 10 nm / min.

9. The preparation method of the high-performance transparent conductive thin film according to claim 5, wherein, In the step S4, the second TCO layer is deposited by magnetron sputtering. The magnetron sputtering parameters are: working pressure 0.1 - 1 Pa, sputtering power 100 W, pre-sputtering duration 5 - 15 min, and sputtering rate 5 - 10 nm / min.

10. The preparation method of the high-performance transparent conductive film according to claim 5, characterized in that, In the step S5, the first preset temperature is 150°C - 230°C, and the duration of the first annealing treatment is 0.5 - 1 h; the second preset temperature is 280°C - 400°C, and the duration of the second annealing treatment is 0.5 - 1 h.

11. A high-performance transparent conductive thin film prepared by the preparation method according to any one of claims 1 - 10.

12. A transparent low-power electronic device, characterized in that, It includes a high-performance transparent conductive thin film prepared by the preparation method according to any one of claims 1 - 10.

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