High-stability ITO conductive glass and preparation method thereof

Abstract

The invention relates to the technical field of functional glass, in particular to high-stability ITO conductive glass and a preparation method thereof. Firstly, an ITO film is deposited on a glass substrate, then a styrene-acrylic emulsion coating is prepared and dried, the coating forms a net-shaped cracking template composed of net lines and net holes, then an ATO film is prepared on the net-shaped cracking template, one part of the ATO film is formed on the surface of the styrene-acrylic film filled in the net holes, the other part of the ATO film is formed in the net lines, and then a ZnO film is prepared. The ATO film and the ZnO film on the surface of the ATO film are marked as ATO / ZnO films, the styrene-acrylic film is removed after ultrasonic cleaning, the ATO / ZnO film located in the net lines and the ITO film located in the net holes are in an exposed state, then a Si3N4 film with the thickness consistent with that of the ATO film is prepared, then a sample is put into a sodium hydroxide solution, the ZnO film and Si3N4 on the surface of the ZnO film fall off along with the reaction of sodium hydroxide and the ZnO film, and finally the ATO / ZnO film is obtained. The Si3N4 thin film formed in the meshes is kept unchanged, the ATO thin film is left in the net lines, and finally a layer of ATO thin film is prepared, namely the high-stability ITO conductive glass is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of functional glass, and specifically relates to a highly stable ITO conductive glass and a preparation method thereof. Background Art

[0002] ITO (indium tin oxide) thin film itself has thermal sensitivity characteristics, and ITO conductive glass is prone to significant performance degradation under high temperature conditions. When the working temperature exceeds 350 °C, ITO thin film has a violent interaction with oxygen in the environment, and the migration rate of oxygen vacancies in the lattice increases significantly, thereby leading to a sharp drop in the carrier concentration. Affected by this, the sheet resistance of the thin film shows a non-linear rapid growth trend. After heat treatment at 350 °C for 30 minutes, the increase in its sheet resistance can reach 200% to 300%. Such irreversible electrical performance degradation directly causes the device based on ITO glass to malfunction in a high temperature process environment. In addition, when ITO is exposed to an acidic environment for a long time, it will be slowly corroded, causing its resistance to decrease. After aging for a period of time in an environment of 85 °C / 85% relative humidity, the conductivity and light transmittance of ITO glass will also decrease. This instability limits the application of ITO glass in special application scenarios.

[0003] Among the current alternative materials, fluorine-doped tin oxide (FTO) thin film introduces a stable oxygen vacancy structure through fluorine element, so that its thermal stability can be improved to above 600 °C, and the FTO film layer has high chemical stability and environmental stability. However, due to its conductive mechanism based on n-type semiconductors, the intrinsic carrier concentration is low, and there is a certain degree of intrinsic absorption of SnO2-based materials in the visible light band. Eventually, its comprehensive optoelectronic performance is limited. Specifically, the sheet resistance is usually higher than 15 Ω / □, and the average visible light transmittance is often lower than 80%. It is difficult to balance the optoelectronic performance and it is still difficult to meet the requirements of high-performance industrial applications. Summary of the Invention

[0004] To solve the above problems, the present invention proposes a composite film system solution based on film layer protection technology and hole-drilling power conduction technology. By compounding with silicon nitride (Si3N4), the contact between ITO and oxygen is isolated, thereby realizing the relative stability of oxygen vacancies. Holes are drilled on the silicon nitride, and the conductivity of ITO is led out through Sb-doped SnO2 (ATO) thin film to achieve surface conduction of the film layer, and finally a highly stable ITO conductive glass is obtained.

[0005] The purpose of the present invention is to provide a preparation method of a highly stable ITO conductive glass, which specifically includes the following steps: (1) After cleaning the glass substrate, a layer of ITO thin film is prepared on its surface by magnetron sputtering technology; (2)Using the roll coating method, a styrene-acrylic emulsion coating with a thickness of 5 μm - 10 μm is prepared on the surface of the ITO thin film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticular cracking template. The above-mentioned reticular cracking template is composed of multiple intersecting wire meshes and mesh holes. The mesh holes are located between adjacent wire meshes and the mesh holes are filled with styrene-acrylic thin films. The ITO thin film located within the wire meshes is in an exposed state; (3)Using the magnetron sputtering coating technology, an ATO thin film is prepared on the surface of the reticular cracking template obtained in step (2). That is, a part of the ATO thin film is formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and another part is formed within the wire meshes (i.e., this part is formed on the surface of the ITO thin film located within the wire meshes); (4)Using the magnetron sputtering coating technology, a ZnO thin film is prepared on the surface of the ATO thin film obtained in step (3). The ATO thin film and the ZnO thin film on its surface are denoted as ATO / ZnO thin film; (5)The sample obtained in step (4) is put into acetone for ultrasonic cleaning. Then, the styrene-acrylic thin film filled in the mesh holes is removed (the ATO / ZnO thin film formed on the surface of the styrene-acrylic thin film in steps (3) and (4) is also removed along with the removal of the styrene-acrylic thin film), leaving the ATO / ZnO thin film within the wire meshes. That is, the ITO thin film within the mesh holes is in an exposed state, and the ATO / ZnO thin film within the wire meshes protrudes on the surface of the ITO thin film. The mesh hole diameter is 10 μm - 30 μm, and the wire mesh width is 1 μm - 3 μm; (6)Using the magnetron sputtering coating technology, a Si3N4 thin film is prepared on the surface of the sample obtained in step (5). Then, a part of the Si3N4 thin film is formed within the mesh holes, that is, on the surface of the exposed ITO thin film, and another part is formed on the surface of the ATO / ZnO thin film within the wire meshes. The thickness of the Si3N4 thin film is the same as the thickness of the ATO thin film prepared in step (3); (7)The sample obtained in step (6) is put into an aqueous sodium hydroxide solution. After 20 - 30 minutes, the reaction between sodium hydroxide and the ZnO thin film in the sample is completed. Then, the ZnO thin film and the Si3N4 thin film on its surface fall off. In the sample obtained in this step, the Si3N4 thin film formed within the mesh holes remains unchanged, and the ATO thin film remains within the wire meshes; (8)Using the magnetron sputtering coating technology, an ATO thin film is prepared on the surface of the sample obtained in step (7). The obtained sample is the high-stability ITO conductive glass.

[0006] Furthermore, when using the magnetron sputtering technology in step (1), the sputtering target is an indium tin oxide ceramic target, where the indium-tin ratio is 9:1 and the material purity is 99.99%; the deposition temperature is 300 - 400 °C, the deposition gas is argon; the sputtering gas pressure is 0.5 - 2.0 Pa; the sputtering power is 80 - 200 W.

[0007] Further, the thickness of the ITO thin film in step (1) is 100 - 200 nm.

[0008] Further, the mesh diameter in step (2) is 10 μm to 30 μm, and the wire width is 1 μm to 3 μm.

[0009] Further, when using the magnetron sputtering coating technology in step (3), the sputtering target is an ATO target, the purity of the ATO target is 99.99%, the molar ratio of Sb to SnO₂ in the ATO target is 1:9; the deposition temperature is room temperature, the deposition gas is a mixed gas of argon and oxygen, and the argon - oxygen ratio is 20:1; the sputtering pressure is 0.5 - 1.2 Pa, and the sputtering power is 50 - 200 W.

[0010] Further, the thickness of the ATO thin film in step (3) is 20 - 40 nm, and the thickness is controlled by the deposition time.

[0011] Further, when using the magnetron sputtering coating technology in step (4), the sputtering target is a zinc oxide target, the sputtering atmosphere is argon, the sputtering pressure is 0.5 - 2.0 Pa, the sputtering power is 50 - 200 W, and the deposition temperature is room temperature.

[0012] Further, the thickness of the ZnO thin film in step (4) is 100 - 300 nm, and the thickness is controlled by the deposition time.

[0013] Further, the thickness of the Si₃N₄ thin film in step (6) is 20 - 40 nm, and the thickness is controlled by the deposition time. When using the magnetron sputtering coating technology, the sputtering target is a Si₃N₄ target, the sputtering power is 80 - 150 W; the sputtering atmosphere is argon and nitrogen, the argon - nitrogen ratio is 30:1, the sputtering pressure is 1 - 2 Pa, and the deposition temperature is room temperature.

[0014] Further, the mass fraction of the sodium hydroxide aqueous solution in step (7) is 5%.

[0015] Further, when using the magnetron sputtering coating technology in step (8), the sputtering target is an ATO target, the purity of the ATO target is 99.99%, the molar ratio of Sb to SnO₂ therein is 1:9, the sputtering power is 50 - 200 W, the deposition gas is a mixed gas of argon and oxygen, the argon - oxygen ratio is 20:1, the sputtering pressure is 0.8 - 1.2 Pa; the deposition temperature is 400 - 500 °C. The thickness of the obtained ATO thin film is 20 - 40 nm, and the thickness is controlled by the deposition time.

[0016] The present invention also provides a highly stable ITO conductive glass obtained by the above - mentioned preparation method.

[0017] In the composite structure of the highly stable ITO conductive glass of the present invention, ATO in the mesh wire serves as an electron extraction layer, and electrons in the ITO thin film can be extracted through this ATO layer and then conducted to the ATO thin film on the surface, endowing it with good electrical conductivity. Due to its dense film structure, Si3N4 serves as a protective layer for ITO, isolating the contact between ITO and the outside world and endowing it with good thermal stability. The outermost ATO thin film serves as a conductive layer and a chemical protective layer. Due to the excellent chemical and environmental stability of the ATO thin film, the glass has excellent chemical and environmental stability.

[0018] Compared with the prior art, the present invention has the following beneficial effects: The present invention utilizes film layer protection and hole-drilling electricity conduction technology to provide a highly stable ITO conductive glass and its preparation method. This glass has a high visible light transmittance (visible light transmittance ≥ 80%), a low sheet resistance (sheet resistance 8 - 20 Ω / square), and high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a schematic structural diagram of the cross-section of the highly stable ITO conductive glass of the present invention; Figure 2 is a schematic flow diagram of the preparation method of the highly stable ITO conductive glass of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] To better understand the content of the present invention, the present invention will be further elaborated below in conjunction with specific embodiments and the drawings. The following embodiments are implemented based on the technology of the present invention, and detailed implementation methods and operation steps are given, but the protection scope of the present invention is not limited to the following embodiments.

[0021] Please refer to Figure 1-2 , in the embodiment, the material purity of the ITO target is 99.99%, and the indium-tin ratio is 9:1; the purity of the ATO target is 99.99%, and the molar ratio of Sb and SnO2 is 1:9.

[0022] Example 1: (1) After cleaning the glass substrate, fix it in the preparation chamber of magnetron sputtering. At the same time, install the ITO ceramic target, ATO ceramic target, and ZnO ceramic target on the corresponding sputtering heads; Pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (purity 99.999%) argon gas, and the sputtering pressure is 1.0 Pa. Sputter the ITO ceramic target at a deposition temperature of 350 °C and a sputtering pressure of 1.0 Pa, and the sputtering power is 120 W. Deposit a 150-nm-thick ITO thin film on the glass substrate; (2) Using the roller coating method, a poly(styrene-acrylate) emulsion coating with a thickness of 8 μm is prepared on the surface of the ITO thin film obtained in step (1). After drying, the poly(styrene-acrylate) emulsion coating forms a reticulated cracking template. The above-mentioned reticulated cracking template is composed of multiple intersecting wire meshes and mesh holes. The mesh holes are located between adjacent wire meshes and the mesh holes are filled with poly(styrene-acrylate) thin films. The ITO thin film within the wire meshes is in an exposed state. The mesh hole diameter is 12 μm and the wire mesh width is 1.5 μm; (3) Using magnetron sputtering coating technology, an ATO thin film is prepared on the surface of the reticulated cracking template obtained in step (2). The chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen are introduced, the argon-oxygen ratio is 20:1, the sputtering pressure is adjusted to 1.0 Pa, the ATO ceramic target is sputtered at room temperature, the sputtering power is 120 W, and a 30-nm-thick ATO thin film is deposited on the surface of the reticulated cracking template. That is, a part of the ATO thin film is formed on the surface of the poly(styrene-acrylate) thin film filled in the mesh holes, and the other part is formed within the wire meshes; (4) Using magnetron sputtering coating technology, a ZnO thin film is prepared on the surface of the ATO thin film obtained in step (3). The chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon is introduced, the sputtering pressure is adjusted to 1.0 Pa, the ZnO ceramic target is sputtered at room temperature, the sputtering power is 120 W, and a 200-nm-thick ZnO thin film is deposited on the ATO thin film. The ATO thin film and the ZnO thin film on its surface are denoted as ATO / ZnO thin film; (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. Then, the poly(styrene-acrylate) thin film filled in the mesh holes and the ATO / ZnO thin film on the surface of the poly(styrene-acrylate) thin film are both removed, leaving the ATO / ZnO thin film within the wire meshes. That is, the ITO thin film within the mesh holes is in an exposed state, and the ATO / ZnO thin film within the wire meshes protrudes on the surface of the ITO thin film. The mesh hole diameter is 12 μm and the wire mesh width is 1.5 μm; (6) Using magnetron sputtering coating technology, an Si3N4 thin film is prepared on the surface of the sample obtained in step (5). Then, a part of the Si3N4 thin film is formed within the mesh holes, that is, on the surface of the exposed ITO thin film, and the other part is formed on the surface of the ATO / ZnO thin film within the wire meshes. Among them, when using magnetron sputtering coating technology, first the chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen are introduced, the argon-nitrogen ratio is 30:1, the pressure is adjusted to 1.5 Pa, the Si3N4 ceramic target is sputtered at room temperature, the sputtering power is 120 W, and a 30-nm-thick Si3N4 thin film is deposited; (7) Put the sample obtained in step (6) into an aqueous sodium hydroxide solution with a mass fraction of 5%. After 30 minutes, the reaction between sodium hydroxide and the ZnO film in the sample is completed, and then the ZnO film and the Si3N4 film on its surface fall off. In the sample obtained in this step, the Si3N4 film formed in the mesh holes remains unchanged, and the ATO film remains in the wire meshes. The Si3N4 film and the ATO film have the same thickness, so the surface of the obtained composite film is flat. (8) Prepare a layer of ATO film on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, evacuate the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon and oxygen, with an argon-oxygen ratio of 20:1, adjust the pressure to 1.0 Pa, sputter the ATO ceramic target at 500 °C, with a sputtering power of 120 W, and deposit a 30-nm-thick ATO film. The obtained sample is the high-stability ITO conductive glass.

[0023] After testing, the average visible light transmittance of the obtained ITO conductive glass is 83%, the sheet resistance is 15 Ω / square, after being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 16.3%, and after being soaked in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0024] Example 2: After cleaning the glass substrate, fix it in the preparation chamber of magnetron sputtering, and at the same time install the ITO ceramic target, ATO ceramic target, and ZnO ceramic target on the corresponding sputtering heads; Evacuate the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (with a purity of 99.999%) argon, adjust the sputtering gas pressure to 0.5 Pa, sputter the ITO ceramic target at a deposition temperature of 300 °C and a sputtering gas pressure of 0.5 Pa, with a sputtering power of 80 W, and deposit a 100-nm-thick ITO film on the glass substrate; (2) Use the spin-coating method to prepare a 5-μm-thick styrene-acrylic emulsion coating on the surface of the ITO film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticulated cracking template. The above reticulated cracking template is composed of multiple intersecting wire meshes and mesh holes. The mesh holes are located between adjacent wire meshes and the mesh holes are filled with styrene-acrylic films, and the ITO film in the wire meshes is in an exposed state. The mesh hole diameter is 10 μm and the wire mesh width is 1 μm; (3) Use magnetron sputtering coating technology to prepare an ATO film on the surface of the reticulated cracking template obtained in step (2). Evacuate the chamber vacuum to 2.0×10 -4Pa, introduce high-purity (99.999%) argon and oxygen, with an argon-oxygen ratio of 20:1. Adjust the sputtering pressure to 0.5 Pa. Sputter the ATO ceramic target at room temperature with a sputtering power of 80 W to deposit a 20-nm-thick ATO thin film on the surface of the reticulated cracking template. That is, part of the ATO thin film is formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and the other part is formed within the wire mesh; (4) Use magnetron sputtering coating technology to prepare a ZnO thin film on the surface of the ATO thin film obtained in step (3). Pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon, adjust the sputtering pressure to 0.5 Pa. Sputter the ZnO ceramic target at room temperature with a sputtering power of 50 W to deposit a 100-nm-thick ZnO thin film on the ATO thin film. Denote the ATO thin film and the ZnO thin film on its surface as ATO / ZnO thin film; (5) Put the sample obtained in step (4) into acetone and ultrasonically clean it for ten minutes. Then, the styrene-acrylic thin film filled in the mesh holes and the ATO / ZnO thin film on the surface of the styrene-acrylic thin film are both removed, leaving the ATO / ZnO thin film within the wire mesh. That is, the ITO thin film within the mesh holes is in a bare state, and the ATO / ZnO thin film within the wire mesh protrudes on the surface of the ITO thin film. The mesh hole diameter is 10 μm, and the wire mesh width is 1 μm; (6) Use magnetron sputtering coating technology to prepare a Si3N4 thin film on the surface of the sample obtained in step (5). Then, part of the Si3N4 thin film is formed within the mesh holes, that is, on the surface of the bare ITO thin film, and the other part is formed on the surface of the ATO / ZnO thin film within the wire mesh. Among them, when using magnetron sputtering coating technology, first pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon and nitrogen, with an argon-nitrogen ratio of 30:1. Adjust the pressure to 1.0 Pa. Sputter the Si3N4 ceramic target at room temperature with a sputtering power of 80 W to deposit a 20-nm-thick Si3N4 thin film; (7) Put the sample obtained in step (6) into a 5% sodium hydroxide aqueous solution. After 20 minutes, the reaction between sodium hydroxide and the ZnO thin film in the sample is completed, and then the ZnO thin film and the Si3N4 thin film on its surface fall off. In the sample obtained in this step, the Si3N4 thin film formed within the mesh holes remains unchanged, and the ATO thin film left within the wire mesh. The Si3N4 thin film and the ATO thin film have the same thickness, so a composite thin film with a flat surface is obtained; (8) Use magnetron sputtering coating technology to prepare a layer of ATO thin film on the surface of the sample obtained in step (7). When using magnetron sputtering coating technology, pump the chamber vacuum to 2.0×10 -4Ar with a purity of 99.999% and O₂ were introduced with an Ar:O₂ ratio of 20:1. The pressure was adjusted to 0.8 Pa, and the ATO ceramic target was sputtered at 400 °C with a sputtering power of 50 W to deposit a 20-nm-thick ATO thin film. The obtained sample was the highly stable ITO conductive glass.

[0025] The average visible light transmittance of the obtained glass was 85%, the sheet resistance was 19.6 Ω / sq. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance was 18.3%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0026] Example 3: After the glass substrate was cleaned, it was fixed in the preparation chamber of the magnetron sputtering. At the same time, the ITO ceramic target, ATO ceramic target, and ZnO ceramic target were installed on the corresponding sputtering heads; The chamber vacuum was pumped to 3.0×10 -4 Pa, and high-purity (with a purity of 99.999%) Ar was introduced. The sputtering pressure was adjusted to 2.0 Pa, and the ITO ceramic target was sputtered at a deposition temperature of 400 °C and a sputtering pressure of 2.0 Pa with a sputtering power of 120 W to deposit a 200-nm-thick ITO thin film on the glass substrate; (2) Using the spin-coating method, a 10-μm-thick styrene-acrylic emulsion coating was prepared on the surface of the ITO thin film obtained in step (1). After drying, the styrene-acrylic emulsion coating formed a reticulated cracking template. The above reticulated cracking template was composed of multiple intersecting wires and mesh holes. The mesh holes were located between adjacent wires and the mesh holes were filled with styrene-acrylic thin films, and the ITO thin film within the wires was in an exposed state. The mesh hole diameter was 20 μm and the wire width was 3 μm; (3) Using the magnetron sputtering coating technology, an ATO thin film was prepared on the surface of the reticulated cracking template obtained in step (2). The chamber vacuum was pumped to 2.0×10 -4 Pa, and high-purity (99.999%) Ar and O₂ were introduced with an Ar:O₂ ratio of 20:1. The sputtering pressure was adjusted to 1.2 Pa, and the ATO ceramic target was sputtered at room temperature with a sputtering power of 200 W to deposit a 40-nm-thick ATO thin film on the surface of the reticulated cracking template, that is, a part of the ATO thin film was formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and the other part was formed within the wires; (4) Using the magnetron sputtering coating technology, a ZnO thin film was prepared on the surface of the ATO thin film obtained in step (3). The chamber vacuum was pumped to 2.0×10 -4Pa, introduce high-purity (99.999%) argon gas, adjust the sputtering pressure to 1.0 Pa, sputter the ZnO ceramic target at room temperature, with a sputtering power of 200 W, deposit a 300-nm-thick ZnO film on the ATO film, and denote the ATO film and the ZnO film on its surface as the ATO / ZnO film; (5) Put the sample obtained in step (4) into acetone for ultrasonic cleaning for ten minutes. Then, the poly(styrene-acrylic acid) film filled in the mesh holes and the ATO / ZnO film on the surface of the poly(styrene-acrylic acid) film are both removed, leaving the ATO / ZnO film inside the wire mesh. That is, the ITO film in the mesh holes is in a bare state, and the ATO / ZnO film inside the wire mesh protrudes on the surface of the ITO film. The mesh hole diameter is 20 μm, and the wire width is 3 μm; (6) Use magnetron sputtering coating technology to prepare a Si3N4 film on the surface of the sample obtained in step (5). Then, a part of the Si3N4 film is formed inside the mesh holes, that is, on the surface of the bare ITO film, and another part is formed on the surface of the ATO / ZnO film inside the wire mesh. Among them, when using magnetron sputtering coating technology, first pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and nitrogen gas, with an argon-nitrogen ratio of 30:1, adjust the pressure to 2.0 Pa, sputter the Si3N4 ceramic target at room temperature, with a sputtering power of 150 W, and deposit a 40-nm-thick Si3N4 film; (7) Put the sample obtained in step (6) into a 5% sodium hydroxide aqueous solution. After 30 minutes, the reaction between sodium hydroxide and the ZnO film in the sample is completed. Then, the ZnO film and the Si3N4 film on its surface fall off. In the sample obtained in this step, the Si3N4 film formed inside the mesh holes remains unchanged, and the ATO film remains inside the wire mesh. The Si3N4 film and the ATO film have the same thickness. Therefore, the surface of the obtained composite film is flat; (8) Use magnetron sputtering coating technology to prepare a layer of ATO film on the surface of the sample obtained in step (7). When using magnetron sputtering coating technology, pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and oxygen gas, with an argon-oxygen ratio of 20:1, adjust the pressure to 1.2 Pa, sputter the ATO ceramic target at 450 °C, with a sputtering power of 200 W, and deposit a 40-nm-thick ATO film. The obtained sample is the high-stability ITO conductive glass.

[0027] After testing, the average visible light transmittance of the obtained glass is 80%, the sheet resistance is 9 Ω / □. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 13.1%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0028] Example 4: After cleaning the glass substrate, fix it in the preparation chamber of magnetron sputtering. At the same time, install the ITO ceramic target, ATO ceramic target, and ZnO ceramic target on the corresponding sputtering targets. Pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (purity of 99.999%) argon gas, adjust the sputtering pressure to 1.0 Pa, sputter the ITO ceramic target at a deposition temperature of 350 °C and a sputtering pressure of 1.0 Pa, with a sputtering power of 120 W, and deposit a 120-nm-thick ITO film on the glass substrate. (2) Using the spin-coating method, prepare a 8-μm-thick styrene-acrylic emulsion coating on the surface of the ITO film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticular cracking template. The above reticular cracking template is composed of multiple intersecting mesh wires and mesh holes. The mesh holes are located between adjacent mesh wires and the mesh holes are filled with styrene-acrylic films. The ITO film within the mesh wires is in an exposed state. The mesh hole diameter is 13 μm and the mesh wire width is 2 μm. (3) Using magnetron sputtering coating technology, prepare an ATO film on the surface of the reticular cracking template obtained in step (2). Pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and oxygen gas, with an argon-oxygen ratio of 20:1, adjust the sputtering pressure to 1.1 Pa, sputter the ATO ceramic target at room temperature, with a sputtering power of 200 W, and deposit a 35-nm-thick ATO film on the surface of the reticular cracking template. That is, a part of the ATO film is formed on the surface of the styrene-acrylic film filled in the mesh holes, and the other part is formed within the mesh wires. (4) Using magnetron sputtering coating technology, prepare a ZnO film on the surface of the ATO film obtained in step (3). Pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the sputtering pressure to 1.0 Pa, sputter the ZnO ceramic target at room temperature, with a sputtering power of 200 W, and deposit an 180-nm-thick ZnO film on the ATO film. Denote the ATO film and the ZnO film on its surface as the ATO / ZnO film. (5) Put the sample obtained in step (4) into acetone and perform ultrasonic cleaning for ten minutes. Then, the styrene-acrylic film filled in the mesh holes and the ATO / ZnO film on the surface of the styrene-acrylic film are both removed, leaving the ATO / ZnO film within the mesh wires. That is, the ITO film within the mesh holes is in an exposed state, and the ATO / ZnO film within the mesh wires protrudes on the surface of the ITO film. The mesh hole diameter is 13 μm and the mesh wire width is 2 μm. (6) Prepare a Si3N4 thin film on the surface of the sample obtained in step (5) by magnetron sputtering coating technology. A part of the Si3N4 thin film is formed inside the mesh holes, that is, on the surface of the exposed ITO thin film, and the other part is formed on the surface of the ATO / ZnO thin film inside the wire. When using the magnetron sputtering coating technology, first pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon and nitrogen, with an argon-nitrogen ratio of 30:1, adjust the pressure to 2.0 Pa, sputter the Si3N4 ceramic target at room temperature, with a sputtering power of 150 W, and deposit a 35-nm-thick Si3N4 thin film; (7) Put the sample obtained in step (6) into a 5% sodium hydroxide aqueous solution. After 30 minutes, the reaction between sodium hydroxide and the ZnO thin film in the sample is completed, and then the ZnO thin film and the Si3N4 thin film on its surface fall off. In the sample obtained in this step, the Si3N4 thin film formed inside the mesh holes remains unchanged, and the ATO thin film remains in the wire. The Si3N4 thin film and the ATO thin film have the same thickness, so the surface of the obtained composite thin film is flat; (8) Prepare a layer of ATO thin film on the surface of the sample obtained in step (7) by magnetron sputtering coating technology. When using the magnetron sputtering coating technology, pump the chamber vacuum to 2.0×10 -4 Pa, introduce high-purity (99.999%) argon and oxygen, with an argon-oxygen ratio of 20:1, adjust the pressure to 1.2 Pa, sputter the ATO ceramic target at 450 °C, with a sputtering power of 200 W, and deposit a 30-nm-thick ATO thin film. The obtained sample is the high-stability ITO conductive glass.

[0029] After testing, the average visible light transmittance of the obtained glass is 82.8%, the sheet resistance is 17.2 Ω / □. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 15.3%. After being soaked in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0030] Example 5: After cleaning the glass substrate, fix it in the preparation chamber of the magnetron sputtering, and at the same time install the ITO ceramic target, ATO ceramic target, and ZnO ceramic target on the corresponding sputtering heads; Pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (purity of 99.999%) argon, adjust the sputtering gas pressure to 1.2 Pa, sputter the ITO ceramic target at a deposition temperature of 350 °C and a sputtering gas pressure of 1.2 Pa, with a sputtering power of 120 W, and deposit a 150-nm-thick ITO thin film on the glass substrate; (2) By using the roller coating method, a styrene-acrylic emulsion coating with a thickness of 8 μm is prepared on the surface of the ITO thin film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticulated cracking template. The above-mentioned reticulated cracking template is composed of multiple intersecting mesh wires and mesh holes. The mesh holes are located between adjacent mesh wires and the mesh holes are filled with styrene-acrylic thin films. The ITO thin film within the mesh wires is in an exposed state. The diameter of the mesh holes is 13 μm and the width of the mesh wires is 2 μm; (3) An ATO thin film is prepared on the surface of the reticulated cracking template obtained in step (2) by using magnetron sputtering coating technology. The chamber vacuum is pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen are introduced, the argon-oxygen ratio is 20:1, the sputtering gas pressure is adjusted to 1.1 Pa, the ATO ceramic target is sputtered at room temperature, the sputtering power is 200 W, and a 20-nm-thick ATO thin film is deposited on the surface of the reticulated cracking template. That is, a part of the ATO thin film is formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and the other part is formed within the mesh wires; (4) A ZnO thin film is prepared on the surface of the ATO thin film obtained in step (3) by using magnetron sputtering coating technology. The chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon is introduced, the sputtering gas pressure is adjusted to 1.2 Pa, the ZnO ceramic target is sputtered at room temperature, the sputtering power is 200 W, and a 200-nm-thick ZnO thin film is deposited on the ATO thin film. The ATO thin film and the ZnO thin film on its surface are denoted as ATO / ZnO thin film; (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. Then, the styrene-acrylic thin film filled in the mesh holes together with the ATO / ZnO thin film on the surface of the styrene-acrylic thin film are removed, leaving the ATO / ZnO thin film within the mesh wires. That is, the ITO thin film within the mesh holes is in an exposed state, and the ATO / ZnO thin film within the mesh wires protrudes on the surface of the ITO thin film. The diameter of the mesh holes is 13 μm and the width of the mesh wires is 2 μm; (6) An Si3N4 thin film is prepared on the surface of the sample obtained in step (5) by using magnetron sputtering coating technology. Then, a part of the Si3N4 thin film is formed within the mesh holes, that is, on the surface of the exposed ITO thin film, and the other part is formed on the surface of the ATO / ZnO thin film within the mesh wires. Among them, when using magnetron sputtering coating technology, first the chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen are introduced, the argon-nitrogen ratio is 30:1, the pressure is adjusted to 1.0 Pa, the Si3N4 ceramic target is sputtered at room temperature, the sputtering power is 150 W, and a 20-nm-thick Si3N4 thin film is deposited; (7) The sample obtained in step (6) is placed in an aqueous sodium hydroxide solution with a mass fraction of 5%. After 30 minutes, the reaction between sodium hydroxide and the ZnO film in the sample is completed, and then the ZnO film and the Si3N4 film on its surface fall off. In the sample obtained in this step, the Si3N4 film formed in the mesh holes remains unchanged, and the ATO film remains in the wire. The Si3N4 film and the ATO film have the same thickness, so the surface of the obtained composite film is flat. (8) A layer of ATO film is prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the chamber vacuum is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen are introduced, the argon-oxygen ratio is 20:1, the pressure is adjusted to 1.2 Pa, the ATO ceramic target is sputtered at 400 °C, the sputtering power is 200 W, and a 30-nm-thick ATO film is deposited. The obtained sample is the high-stability ITO conductive glass.

[0031] After testing, the average light transmittance of the obtained glass in the visible light region is 84.1%, the sheet resistance is 14.6 Ω / □. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 17.9%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0032] Example 6: After the glass substrate is cleaned, it is fixed in the preparation chamber of magnetron sputtering. At the same time, the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering heads; The chamber vacuum is pumped to 5.0×10 -4 Pa, high-purity (purity of 99.999%) argon is introduced, the sputtering gas pressure is adjusted to 1.0 Pa, the ITO ceramic target is sputtered at a deposition temperature of 350 °C and a sputtering gas pressure of 1.2 Pa, and the sputtering power is 120 W. A 120-nm-thick ITO film is deposited on the glass substrate; (2) By using the spin-coating method, a layer of styrene-acrylic emulsion coating with a thickness of 8 μm is prepared on the surface of the ITO film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticular cracking template. The above-mentioned reticular cracking template is composed of multiple intersecting wires and mesh holes. The mesh holes are located between adjacent wires and the mesh holes are filled with styrene-acrylic films. The ITO film in the wires is in an exposed state. The mesh hole diameter is 13 μm and the wire width is 2 μm; (3) An ATO film is prepared on the surface of the reticular cracking template obtained in step (2) by using magnetron sputtering coating technology. The chamber vacuum is pumped to 5.0×10 -4Pa, introduce high-purity (99.999%) argon and oxygen, with an argon-oxygen ratio of 20:1. Adjust the sputtering pressure to 1.0 Pa. Sputter the ATO ceramic target at room temperature with a sputtering power of 100 W to deposit a 20-nm-thick ATO thin film on the surface of the reticulated cracking template. That is, a part of the ATO thin film is formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and the other part is formed within the wire mesh; (4) Use magnetron sputtering coating technology to prepare a ZnO thin film on the surface of the ATO thin film obtained in step (3). Pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon. Adjust the sputtering pressure to 1.0 Pa. Sputter the ZnO ceramic target at room temperature with a sputtering power of 200 W to deposit a 200-nm-thick ZnO thin film on the ATO thin film. Denote the ATO thin film and the ZnO thin film on its surface as ATO / ZnO thin film; (5) Put the sample obtained in step (4) into acetone for ultrasonic cleaning for ten minutes. Then, the styrene-acrylic thin film filled in the mesh holes and the ATO / ZnO thin film on the surface of the styrene-acrylic thin film are both removed, leaving the ATO / ZnO thin film within the wire mesh. That is, the ITO thin film within the mesh holes is in a bare state, and the ATO / ZnO thin film within the wire mesh protrudes on the surface of the ITO thin film. The mesh hole diameter is 13 μm and the wire width is 2 μm; (6) Use magnetron sputtering coating technology to prepare a Si3N4 thin film on the surface of the sample obtained in step (5). Then, a part of the Si3N4 thin film is formed within the mesh holes, that is, on the surface of the bare ITO thin film, and the other part is formed on the surface of the ATO / ZnO thin film within the wire mesh. Among them, when using magnetron sputtering coating technology, first pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon and nitrogen, with an argon-nitrogen ratio of 30:1. Adjust the pressure to 1.0 Pa. Sputter the Si3N4 ceramic target at room temperature with a sputtering power of 120 W to deposit a 20-nm-thick Si3N4 thin film; (7) Put the sample obtained in step (6) into a 5% sodium hydroxide aqueous solution. After 30 minutes, the reaction between sodium hydroxide and the ZnO thin film in the sample is completed. Then, the ZnO thin film and the Si3N4 thin film on its surface fall off accordingly. In the sample obtained in this step, the Si3N4 thin film formed within the mesh holes remains unchanged, and the ATO thin film left within the wire mesh has the same thickness as the Si3N4 thin film. Therefore, the surface of the obtained composite thin film is flat; (8) Use magnetron sputtering coating technology to prepare a layer of ATO thin film on the surface of the sample obtained in step (7). When using magnetron sputtering coating technology, pump the chamber vacuum to 3.0×10 -4Ar with a purity of 99.999% and O₂ are introduced, and the Ar:O₂ ratio is 20:1. The pressure is adjusted to 1.2 Pa. The ATO ceramic target is sputtered at 500 °C with a sputtering power of 200 W to deposit a 30-nm-thick ATO thin film. The obtained sample is the highly stable ITO conductive glass.

[0033] The average visible light transmittance of the obtained glass is 85.6%, and the sheet resistance is 16.9 Ω / sq. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 18.5%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0034] Example 7: After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering. At the same time, the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering heads. The chamber vacuum is pumped to 3.0×10 -4 Pa, and high-purity (with a purity of 99.999%) Ar is introduced. The sputtering pressure is adjusted to 1.0 Pa. The ITO ceramic target is sputtered at a deposition temperature of 350 °C and a sputtering pressure of 0.8 Pa with a sputtering power of 100 W to deposit a 200-nm-thick ITO thin film on the glass substrate. (2) By means of spin coating, a 8-μm-thick styrene-acrylic emulsion coating is prepared on the surface of the ITO thin film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticular cracking template. The above-mentioned reticular cracking template is composed of multiple intersecting mesh wires and mesh holes. The mesh holes are located between adjacent mesh wires and the mesh holes are filled with styrene-acrylic thin films. The ITO thin film within the mesh wires is in an exposed state. The diameter of the mesh holes is 13 μm and the width of the mesh wires is 2 μm. (3) The ATO thin film is prepared on the surface of the reticular cracking template obtained in step (2) by means of magnetron sputtering coating technology. The chamber vacuum is pumped to 5.0×10 -4 Pa, and high-purity (99.999%) Ar and O₂ are introduced. The Ar:O₂ ratio is 20:1. The sputtering pressure is adjusted to 0.8 Pa. The ATO ceramic target is sputtered at room temperature with a sputtering power of 100 W to deposit a 35-nm-thick ATO thin film on the surface of the reticular cracking template. That is, a part of the ATO thin film is formed on the surface of the styrene-acrylic thin film filled in the mesh holes, and the other part is formed within the mesh wires. (4) The ZnO thin film is prepared on the surface of the ATO thin film obtained in step (3) by means of magnetron sputtering coating technology. The chamber vacuum is pumped to 3.0×10 -4Pa, introduce high-purity (99.999%) argon gas, adjust the sputtering pressure to 1.0 Pa, sputter the ZnO ceramic target at room temperature, with a sputtering power of 200 W, and deposit a 300-nm-thick ZnO film on the ATO film. Denote the ATO film and the ZnO film on its surface as the ATO / ZnO film; (5) Put the sample obtained in step (4) into acetone and ultrasonically clean it for ten minutes. Then, the poly(styrene-acrylic acid) film filled in the mesh holes and the ATO / ZnO film on the surface of the poly(styrene-acrylic acid) film are both removed, leaving the ATO / ZnO film inside the wire mesh. That is, the ITO film in the mesh holes is in a bare state, and the ATO / ZnO film inside the wire mesh protrudes on the surface of the ITO film. The mesh hole diameter is 13 μm and the wire width is 2 μm; (6) Use magnetron sputtering coating technology to prepare a Si3N4 film on the surface of the sample obtained in step (5). Then, a part of the Si3N4 film is formed inside the mesh holes, that is, on the surface of the bare ITO film, and another part is formed on the surface of the ATO / ZnO film inside the wire mesh. Among them, when using magnetron sputtering coating technology, first pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and nitrogen gas, with an argon-nitrogen ratio of 30:1, adjust the pressure to 1.0 Pa, sputter the Si3N4 ceramic target at room temperature, with a sputtering power of 120 W, and deposit a 35-nm-thick Si3N4 film; (7) Put the sample obtained in step (6) into a 5% sodium hydroxide aqueous solution. After 30 minutes, the reaction between sodium hydroxide and the ZnO film in the sample is completed, and then the ZnO film and the Si3N4 film on its surface fall off. In the sample obtained in this step, the Si3N4 film formed inside the mesh holes remains unchanged, and the ATO film remains inside the wire mesh. The Si3N4 film and the ATO film have the same thickness, so the surface of the obtained composite film is flat; (8) Use magnetron sputtering coating technology to prepare a layer of ATO film on the surface of the sample obtained in step (7). When using magnetron sputtering coating technology, pump the chamber vacuum to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and oxygen gas, with an argon-oxygen ratio of 20:1, adjust the pressure to 1.0 Pa, sputter the ATO ceramic target at 500 °C, with a sputtering power of 150 W, and deposit a 30-nm-thick ATO film. The obtained sample is the high-stability ITO conductive glass.

[0035] After testing, the average light transmittance of the obtained glass in the visible light region is 81.1%, the sheet resistance is 8.5 Ω / □. After being kept in air at 500 °C for 30 minutes, the change rate of the sheet resistance is 14.3%. After being soaked in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0036] Table 1 shows the visible light transmittance and sheet resistance of highly stable ITO conductive glass under different preparation conditions.

[0037] Table 1 The above are only the embodiments of the present invention, and do not impose any form of limitation on the present invention. The present invention may also have other forms of embodiments based on the above structure and function, which will not be enumerated one by one. Therefore, any person skilled in the art, without departing from the scope of the technical solution of the present invention, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A preparation method of a highly stable ITO conductive glass, characterized in that, Specifically, it includes the following steps: (1) After cleaning the glass substrate, a layer of ITO thin film is prepared on its surface by magnetron sputtering technology; (2) By using the spin-coating method, a layer of styrene-acrylic emulsion coating with a thickness of 5 μm - 10 μm is prepared on the surface of the ITO thin film obtained in step (1). After drying, the styrene-acrylic emulsion coating forms a reticulated cracking template. The above-mentioned reticulated cracking template is composed of multiple intersecting wire meshes and mesh holes. The mesh holes are located between adjacent wire meshes and the mesh holes are filled with styrene-acrylic thin films. The ITO thin film within the wire meshes is in an exposed state; (3) By using magnetron sputtering coating technology, an ATO thin film is prepared on the surface of the reticulated cracking template obtained in step (2). A part of the ATO thin film is formed on the surface of the styrene-acrylic thin film and a part is formed within the wire meshes; (4) By using magnetron sputtering coating technology, a ZnO thin film is prepared on the surface of the ATO thin film obtained in step (3). The ATO thin film and the ZnO thin film on its surface are denoted as ATO / ZnO thin film; (5) The sample obtained in step (4) is put into acetone for ultrasonic cleaning, then the styrene-acrylic thin film filled in the mesh holes is removed, that is, the ITO thin film within the mesh holes is in an exposed state, and the ATO / ZnO thin film within the wire meshes protrudes on the surface of the ITO thin film; (6) By using magnetron sputtering coating technology, a Si3N4 thin film is prepared on the surface of the sample obtained in step (5). A part of the Si3N4 thin film is formed within the mesh holes and another part is formed on the surface of the ATO / ZnO thin film within the wire meshes. The thickness of the Si3N4 thin film is the same as the thickness of the ATO thin film prepared in step (3); (7) The sample obtained in step (6) is put into an aqueous sodium hydroxide solution and reacted for 20 - 30 minutes; (8) By using magnetron sputtering coating technology, a layer of ATO thin film is prepared on the surface of the sample obtained in step (7). The obtained sample is the highly stable ITO conductive glass.

2. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, When using magnetron sputtering technology in step (1), the sputtering target is an indium tin oxide ceramic target, where the indium-tin ratio is 9:1 and the material purity is 99.99%; the deposition temperature is 300 - 400 °C, and the deposition gas is argon; the sputtering pressure is 0.5 - 2.0 Pa; the sputtering power is 80 - 200 W.

3. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, The thickness of the ITO thin film in step (1) is 100 - 200 nm; the thickness of the ATO thin film in step (3) is 20 - 40 nm; the thickness of the ZnO thin film in step (4) is 100 - 300 nm.

4. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, The mesh hole diameter in step (2) is 10 μm - 30 μm and the wire mesh width is 1 μm - 3 μm.

5. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, When using magnetron sputtering coating technology in step (3), the sputtering target is an ATO target, the purity of the ATO target is 99.99%, and the molar ratio of Sb and SnO2 in the ATO target is 1:9; the deposition temperature is room temperature, the deposition gas is a mixed gas of argon and oxygen, and the argon-oxygen ratio is 20:1; the sputtering pressure is 0.5 - 1.2 Pa, and the sputtering power is 50 - 200 W.

6. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, In step (4), when using the magnetron sputtering coating technology, the sputtering target is a zinc oxide target, the sputtering atmosphere is argon, the sputtering pressure is 0.5 - 2.0 Pa, the sputtering power is 50 - 200 W, and the deposition temperature is room temperature.

7. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, In step (6), the thickness of the Si3N4 film is 20 - 40 nm; when using the magnetron sputtering coating technology, the sputtering target is a Si3N4 target, the sputtering power is 80 - 150 W; the sputtering atmosphere is argon and nitrogen, the argon-nitrogen ratio is 30:1, the sputtering pressure is 1 - 2 Pa, and the deposition temperature is room temperature.

8. The preparation method of the highly stable ITO conductive glass according to claim 1, wherein In step (7), the mass fraction of the sodium hydroxide aqueous solution is 5%.

9. The preparation method of the highly stable ITO conductive glass according to claim 1, characterized in that, In step (8), when using the magnetron sputtering coating technology, the sputtering target is an ATO target, the purity of the ATO target is 99.99%, the molar ratio of Sb to SnO2 is 1:9, the sputtering power is 50 - 200 W, the deposition gas is a mixed gas of argon and oxygen, the argon-oxygen ratio is 20:1, the sputtering pressure is 0.8 - 1.2 Pa; the deposition temperature is 400 - 500 °C; the thickness of the obtained ATO film is 20 - 40 nm.

10. A highly stable ITO conductive glass prepared by the preparation method according to any one of claims 1 - 9.

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