A kind of high stability ITO conductive glass and preparation method thereof

Abstract

The present invention relates to the technical field of functional glass, and specifically to a highly stable ITO conductive glass and a preparation method thereof. An ITO film is first deposited on a glass substrate, and then a styrene-acrylic emulsion coating is prepared and dried. The coating forms a mesh-shaped cracking template consisting of mesh lines and mesh holes. An ATO film is then prepared on the film, with a portion of the ATO film formed on the surface of the styrene-acrylic film filled in the mesh holes and another portion formed in the mesh lines. A ZnO film is then prepared, and the ATO film and the ZnO film on its surface are denoted as an ATO / ZnO film. After ultrasonic cleaning, the styrene-acrylic film is removed, leaving the ATO / ZnO film in the mesh lines. The ITO film in the mesh holes is exposed, and then a Si3N4 film having the same thickness as the ATO film is prepared. The sample is then placed in a sodium hydroxide solution. After the sodium hydroxide reacts with the ZnO film, the ZnO film and the Si3N4 on its surface fall off, while the Si3N4 film formed in the mesh holes remains unchanged, leaving the ATO film in the mesh lines. Finally, a layer of ATO film is prepared, thereby obtaining highly stable ITO conductive glass.

Description

Technical Field

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

[0002] ITO (indium tin oxide) films are inherently heat-sensitive, and ITO conductive glass is susceptible to significant performance degradation under high-temperature conditions. When operating temperatures exceed 350°C, ITO films interact violently with ambient oxygen, significantly increasing the migration rate of oxygen vacancies within the crystal lattice and leading to a sharp drop in carrier concentration. As a result, the film's sheet resistance exhibits a rapid, nonlinear increase. After heat treatment at 350°C for 30 minutes, the sheet resistance can increase by 200% to 300%. This irreversible electrical degradation directly leads to functional failure of ITO-based devices in high-temperature manufacturing environments. Furthermore, prolonged exposure to acidic environments slowly corrodes ITO, causing its resistance to decrease. After aging in an 85°C / 85% relative humidity environment, ITO glass also experiences a decrease in conductivity and transmittance. This instability limits the use of ITO glass in specialized applications.

[0003] Among current alternative materials, fluorine-doped tin oxide (FTO) thin films introduce fluorine to stabilize oxygen vacancies, increasing their thermal stability to over 600°C. Furthermore, FTO films exhibit high chemical and environmental stability. However, due to their n-type semiconductor-based conductivity mechanism, the intrinsic carrier concentration is relatively low. Furthermore, SnO2-based materials exhibit a certain degree of intrinsic absorption in the visible light band, ultimately limiting their overall optoelectronic performance. Specifically, their sheet resistance is typically above 15Ω / □, while their average visible light transmittance is often below 80%. This makes it difficult to achieve a balanced optoelectronic performance, making it difficult to meet the demands of high-performance industrial applications. Summary of the Invention

[0004] To address these issues, the present invention proposes a composite film solution based on film layer protection and hole-drilling technology. This solution, combined with silicon nitride (Si3N4), isolates ITO from oxygen, thereby achieving relative stability of oxygen vacancies. Holes are drilled in the silicon nitride to allow the conductivity of the ITO to be extracted through a Sb-doped SnO2 (ATO) film, achieving surface conductivity in the film layer. This ultimately results in highly stable ITO conductive glass.

[0005] The object of the present invention is to provide a method for preparing highly stable ITO conductive glass, which specifically comprises the following steps:

[0006] (1) After cleaning the glass substrate, a layer of ITO film is prepared on its surface using magnetron sputtering technology;

[0007] (2) Using a roller coating method, a styrene acrylic emulsion coating with a thickness of 5 μm to 10 μm is prepared on the surface of the ITO film obtained in step (1). After drying, the styrene acrylic emulsion coating forms a mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located within the mesh lines is in a bare state;

[0008] (3) using magnetron sputtering coating technology to prepare an ATO film on the surface of the mesh crack template obtained in step (2), that is, a portion of the ATO film is formed on the surface of the styrene acrylic film filled in the mesh, and another portion is formed in the mesh wire (that is, this portion is formed on the surface of the ITO film located in the mesh wire);

[0009] (4) preparing a ZnO film on the surface of the ATO film obtained in step (3) by using a magnetron sputtering coating technique, and the ATO film and the ZnO film on the surface thereof are referred to as an ATO / ZnO film;

[0010] (5) The sample obtained in step (4) is placed in acetone for ultrasonic cleaning, and the styrene-acrylic film filled in the mesh is removed (the ATO / ZnO film located on the surface of the styrene-acrylic film and formed in steps (3) and (4) is also removed along with the removal of the styrene-acrylic film), leaving the ATO / ZnO film located in the mesh line, that is, the ITO film in the mesh is in a bare state, and the ATO / ZnO film located in the mesh line is raised on the surface of the ITO film, the mesh diameter is 10 μm-30 μm, and the mesh line width is 1 μm-3 μm;

[0011] (6) A Si3N4 film is prepared on the surface of the sample obtained in step (5) using magnetron sputtering coating technology. A portion of the Si3N4 film is formed in the mesh, i.e., on the surface of the exposed ITO film, and another portion is formed on the surface of the ATO / ZnO film in the mesh. The thickness of the Si3N4 film is consistent with the thickness of the ATO film prepared in step (3);

[0012] (7) The sample obtained in step (6) is placed in a sodium hydroxide aqueous solution. After 20-30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh wire.

[0013] (8) A layer of ATO thin film is prepared on the surface of the sample obtained in step (7) using magnetron sputtering coating technology. The obtained sample is a highly stable ITO conductive glass.

[0014] Furthermore, when magnetron sputtering technology is used in step (1), the sputtering target is an indium tin oxide ceramic target, wherein 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 pressure is 0.5-2.0 Pa; and the sputtering power is 80-200 W.

[0015] Furthermore, the thickness of the ITO film in step (1) is 100-200 nm.

[0016] Furthermore, the mesh diameter in step (2) is 10 μm to 30 μm, and the mesh line width is 1 μm to 3 μm.

[0017] Furthermore, when magnetron sputtering coating technology is used 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 to SnO2 in the ATO target is 1:9; the deposition temperature is room temperature, the deposition gas is an argon-oxygen mixed gas, 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.

[0018] Furthermore, the thickness of the ATO film in step (3) is 20-40 nm, and the thickness is controlled by the deposition time.

[0019] Furthermore, when magnetron sputtering coating technology is used 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.

[0020] Furthermore, the thickness of the ZnO film in step (4) is 100-300 nm, and the thickness is controlled by the deposition time.

[0021] Furthermore, the thickness of the Si3N4 film in step (6) is 20-40 nm, and the thickness is controlled by the deposition time. When using 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.

[0022] Furthermore, the mass fraction of the sodium hydroxide aqueous solution in step (7) is 5%.

[0023] Furthermore, in step (8), when magnetron sputtering coating technology is used, the sputtering target is an ATO target with a purity of 99.99%, wherein the molar ratio of Sb to SnO2 is 1:9, the sputtering power is 50-200W, the deposition gas is an argon-oxygen mixed gas with an argon-oxygen ratio of 20:1, and the sputtering pressure is 0.8-1.2Pa; the deposition temperature is 400-500°C. The obtained ATO film has a thickness of 20-40nm, and the thickness is controlled by the deposition time.

[0024] The present invention also provides a highly stable ITO conductive glass obtained according to the preparation method.

[0025] In the composite structure of the highly stable ITO conductive glass of the present invention, the ATO in the mesh serves as an electron extraction layer. Electrons in the ITO film can be extracted through this ATO layer and then conducted to the ATO film on the surface, imparting excellent conductivity. Si3N4, with its dense film structure, acts as a protective layer for the ITO, isolating it from the outside world and imparting excellent thermal stability. The outermost ATO film acts as both a conductive layer and a chemical protection layer. Due to the excellent chemical and environmental stability of the ATO film, the glass also possesses excellent chemical and environmental stability.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention utilizes film protection and hole-digging electricity-leading technology to provide highly stable ITO conductive glass and its preparation method. The glass has high visible light transmittance (visible light transmittance ≥ 80%), low square resistance (square resistance 8-20Ω / □), and high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 1 is a schematic structural diagram of a cross section of the highly stable ITO conductive glass of the present invention;

[0029] Figure 2 It is a schematic flow chart of the preparation method of the highly stable ITO conductive glass of the present invention. DETAILED DESCRIPTION

[0030] In order to better understand the content of the present invention, the present invention will be further described below in conjunction with specific examples and drawings. The following examples are implemented based on the technology of the present invention and provide detailed implementation methods and operating steps, but the scope of protection of the present invention is not limited to the following examples.

[0031] Please combine Figure 1-2 In the embodiment, the material purity of the ITO target is 99.99%, wherein the indium-tin ratio is 9:1; the purity of the ATO target is 99.99%, wherein the molar ratio of Sb to SnO2 is 1:9.

[0032] Example 1:

[0033] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0034] The vacuum degree of the chamber was reduced to 3.0×10 -4 Pa, high-purity argon (purity of 99.999%) was introduced, the sputtering pressure was 1.0 Pa, the ITO ceramic target was sputtered at a deposition temperature of 350 ° C, a sputtering pressure of 1.0 Pa, and a sputtering power of 120 W. A 150 nm thick ITO film was deposited on a glass substrate;

[0035] (2) Using a roller coating method, a 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 mesh cracking template, wherein the mesh cracking template is composed of a plurality of mesh lines and mesh holes that intersect each other. The mesh holes are located between adjacent mesh lines and are filled with styrene acrylic film. The ITO film located in the mesh lines is in a bare state. The mesh diameter is 12 μm and the mesh line width is 1.5 μm.

[0036] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 1.0 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 120 W. A 30 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed inside the mesh wire;

[0037] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 120 W. A 200 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were denoted as ATO / ZnO film;

[0038] (5) The sample obtained in step (4) was placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film were removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh was exposed, and the ATO / ZnO film in the mesh line protruded from the surface of the ITO film. The mesh diameter was 12 μm and the mesh line width was 1.5 μm.

[0039] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, that is, on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1 and a pressure adjustment of 1.5 Pa. Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 120 W to deposit a 30 nm thick Si3N4 film.

[0040] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0041] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1. The pressure was adjusted to 1.0 Pa, and the ATO ceramic target was sputtered at 500°C with a sputtering power of 120 W. A 30 nm thick ATO film was deposited, and the obtained sample was a highly stable ITO conductive glass.

[0042] The ITO conductive glass obtained through testing has an average transmittance of 83% in the visible light region and a sheet resistance of 15Ω / □. After being kept in air at 500°C for 30 minutes, the sheet resistance change rate is 16.3%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remains unchanged.

[0043] Example 2:

[0044] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0045] The vacuum degree of the chamber was reduced to 2.0×10 -4 Pa, high-purity (purity of 99.999%) argon gas was introduced, the sputtering pressure was adjusted to 0.5 Pa, the ITO ceramic target was sputtered at a deposition temperature of 300 ° C, a sputtering pressure of 0.5 Pa, and a sputtering power of 80 W. A 100 nm thick ITO film was deposited on a glass substrate;

[0046] (2) Using a roller coating method, a 5 μm thick styrene acrylic emulsion coating is prepared on the surface of the ITO film obtained in step (1). After drying, the styrene acrylic emulsion coating forms a mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, wherein the mesh holes are located between adjacent mesh lines and the mesh holes are filled with a styrene acrylic film, and the ITO film located within the mesh lines is in a bare state, wherein the mesh diameter is 10 μm and the mesh line width is 1 μm;

[0047] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 0.5 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 80 W. A 20 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0048] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 0.5 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 50 W. A 100 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were recorded as ATO / ZnO film;

[0049] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 10 μm and the mesh width is 1 μm.

[0050] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, i.e., on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1, the pressure was adjusted to 1.0 Pa, and the Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 80 W to deposit a 20 nm thick Si3N4 film;

[0051] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 20 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so a composite film with a smooth surface is obtained;

[0052] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen 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. A 20 nm thick ATO film was deposited, and the obtained sample was a highly stable ITO conductive glass.

[0053] The average transmittance of the glass in the visible light region was 85%, and the sheet resistance was 19.6Ω / □. After being kept in air at 500℃ for 30 minutes, the sheet resistance changed by 18.3%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0054] Example 3:

[0055] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0056] The vacuum degree of the chamber was reduced to 3.0×10 -4Pa, high-purity (purity of 99.999%) argon gas was introduced, the sputtering pressure was adjusted to 2.0 Pa, the ITO ceramic target was sputtered at a deposition temperature of 400 ° C and a sputtering pressure of 2.0 Pa, the sputtering power was 120 W, and a 200 nm thick ITO film was deposited on a glass substrate;

[0057] (2) Using a roller coating method, a 10 μm thick styrene acrylic emulsion coating is prepared on the surface of the ITO film obtained in step (1). After drying, the styrene acrylic emulsion coating forms a mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, wherein the mesh holes are located between adjacent mesh lines and the mesh holes are filled with a styrene acrylic film, and the ITO film located within the mesh lines is in a bare state, wherein the mesh diameter is 20 μm and the mesh line width is 3 μm;

[0058] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 1.2 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 40 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0059] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 300 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were recorded as ATO / ZnO film;

[0060] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 20 μm and the mesh width is 3 μm.

[0061] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, i.e., on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1, the pressure was adjusted to 2.0 Pa, and the Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 150 W to deposit a 40 nm thick Si3N4 film;

[0062] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0063] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced, the argon-oxygen ratio was 20:1, the pressure was adjusted to 1.2 Pa, the ATO ceramic target was sputtered at 450 ° C, the sputtering power was 200 W, and a 40 nm thick ATO film was deposited. The obtained sample is a highly stable ITO conductive glass.

[0064] The average transmittance of the glass in the visible light region was 80%, and the sheet resistance was 9Ω / □. After being kept in air at 500°C for 30 minutes, the sheet resistance changed by 13.1%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0065] Example 4:

[0066] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0067] The vacuum degree of the chamber was reduced to 3.0×10 -4Pa, high-purity (purity of 99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, the ITO ceramic target was sputtered at a deposition temperature of 350 ° C and a sputtering pressure of 1.0 Pa, the sputtering power was 120 W, and a 120 nm thick ITO film was deposited on a glass substrate;

[0068] (2) Using a roller coating method, a 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 mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located in the mesh lines is in a bare state, the mesh diameter is 13 μm, and the mesh line width is 2 μm;

[0069] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 1.1 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 35 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0070] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 180 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were denoted as ATO / ZnO film;

[0071] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 13 μm and the mesh line width is 2 μm.

[0072] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, that is, on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1 and a pressure adjustment of 2.0 Pa. Si3N4 ceramic targets were sputtered at room temperature with a sputtering power of 150 W to deposit a 35 nm thick Si3N4 film.

[0073] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0074] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced, the argon-oxygen ratio was 20:1, the pressure was adjusted to 1.2 Pa, the ATO ceramic target was sputtered at 450 ° C, the sputtering power was 200 W, and a 30 nm thick ATO film was deposited. The obtained sample was a highly stable ITO conductive glass.

[0075] The average transmittance of the glass in the visible light region was 82.8%, and the sheet resistance was 17.2Ω / □. After being kept in air at 500°C for 30 minutes, the sheet resistance changed by 15.3%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0076] Example 5:

[0077] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0078] The vacuum degree of the chamber was reduced to 3.0×10 -4Pa, high-purity argon (purity of 99.999%) was introduced, the sputtering pressure was adjusted to 1.2 Pa, the ITO ceramic target was sputtered at a deposition temperature of 350 ° C, a sputtering pressure of 1.2 Pa, and a sputtering power of 120 W. A 150 nm thick ITO film was deposited on a glass substrate;

[0079] (2) Using a roller coating method, a 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 mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located in the mesh lines is in a bare state, the mesh diameter is 13 μm, and the mesh line width is 2 μm;

[0080] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 2.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 1.1 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 20 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0081] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.2 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 200 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were recorded as ATO / ZnO film;

[0082] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 13 μm and the mesh line width is 2 μm.

[0083] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, that is, on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1, the pressure was adjusted to 1.0 Pa, and the Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 150 W to deposit a 20 nm thick Si3N4 film;

[0084] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0085] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced, the argon-oxygen ratio was 20:1, the pressure was adjusted to 1.2 Pa, the ATO ceramic target was sputtered at 400 ° C, the sputtering power was 200 W, and a 30 nm thick ATO film was deposited. The obtained sample is a highly stable ITO conductive glass.

[0086] The average transmittance of the glass in the visible light region was 84.1%, and the sheet resistance was 14.6Ω / □. After being kept in air at 500°C for 30 minutes, the sheet resistance changed by 17.9%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0087] Example 6:

[0088] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0089] The vacuum degree of the chamber was reduced to 5.0×10 -4Pa, high-purity (purity of 99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, the ITO ceramic target was sputtered at a deposition temperature of 350 ° C and a sputtering pressure of 1.2 Pa, the sputtering power was 120 W, and a 120 nm thick ITO film was deposited on a glass substrate;

[0090] (2) Using a roller coating method, a 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 mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located in the mesh lines is in a bare state, the mesh diameter is 13 μm, and the mesh line width is 2 μm;

[0091] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 5.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 1.0 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 100 W. A 20 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0092] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 200 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were recorded as ATO / ZnO film;

[0093] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 13 μm and the mesh line width is 2 μm.

[0094] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, that is, on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1, the pressure was adjusted to 1.0 Pa, and the Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 120 W to deposit a 20 nm thick Si3N4 film;

[0095] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0096] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced, the argon-oxygen ratio was 20:1, the pressure was adjusted to 1.2 Pa, the ATO ceramic target was sputtered at 500 ° C, the sputtering power was 200 W, and a 30nm thick ATO film was deposited. The obtained sample is a highly stable ITO conductive glass.

[0097] The average transmittance of the glass in the visible light region was 85.6%, and the sheet resistance was 16.9Ω / □. After being kept in air at 500℃ for 30 minutes, the sheet resistance changed by 18.5%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0098] Example 7:

[0099] (1) After the glass substrate is cleaned, it is fixed in the preparation chamber of the magnetron sputtering, and the ITO ceramic target, ATO ceramic target, and ZnO ceramic target are installed on the corresponding sputtering target heads;

[0100] The vacuum degree of the chamber was reduced to 3.0×10 -4Pa, high-purity (purity of 99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, the ITO ceramic target was sputtered at a deposition temperature of 350 ° C, a sputtering pressure of 0.8 Pa, and a sputtering power of 100 W. A 200 nm thick ITO film was deposited on a glass substrate;

[0101] (2) Using a roller coating method, a 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 mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located in the mesh lines is in a bare state, the mesh diameter is 13 μm, and the mesh line width is 2 μm;

[0102] (3) ATO thin film was prepared on the surface of the mesh crack template obtained in step (2) using magnetron sputtering coating technology, and the vacuum degree of the chamber was pumped to 5.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1, and the sputtering pressure was adjusted to 0.8 Pa. The ATO ceramic target was sputtered at room temperature with a sputtering power of 100 W. A 35 nm thick ATO film was deposited on the surface of the mesh crack template, that is, part of the ATO film was formed on the surface of the styrene-acrylic film filled in the mesh, and the other part was formed in the mesh wire;

[0103] (4) Using magnetron sputtering coating technology, a ZnO film was prepared on the surface of the ATO film obtained in step (3), and the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the sputtering pressure was adjusted to 1.0 Pa, and the ZnO ceramic target was sputtered at room temperature with a sputtering power of 200 W. A 300 nm thick ZnO film was deposited on the ATO film. The ATO film and the ZnO film on its surface were recorded as ATO / ZnO film;

[0104] (5) The sample obtained in step (4) is placed in acetone and ultrasonically cleaned for ten minutes. The styrene acrylic film filled in the mesh and the ATO / ZnO film on the surface of the styrene acrylic film are removed, leaving the ATO / ZnO film in the mesh line. That is, the ITO film in the mesh is exposed, and the ATO / ZnO film in the mesh line is raised on the surface of the ITO film. The mesh diameter is 13 μm and the mesh line width is 2 μm.

[0105] (6) Using magnetron sputtering coating technology, a Si3N4 film is prepared on the surface of the sample obtained in step (5). A portion of the Si3N4 film is formed in the mesh, that is, on the surface of the exposed ITO film, and the other portion is formed on the surface of the ATO / ZnO film in the mesh. When using magnetron sputtering coating technology, the vacuum degree of the chamber is first pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and nitrogen were introduced with an argon-nitrogen ratio of 30:1, the pressure was adjusted to 1.0 Pa, and the Si3N4 ceramic target was sputtered at room temperature with a sputtering power of 120 W to deposit a 35 nm thick Si3N4 film;

[0106] (7) The sample obtained in step (6) is placed in a 5% by mass sodium hydroxide aqueous solution. After 30 minutes, the sodium hydroxide reacts with the ZnO film in the sample, and 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 remains unchanged, and the ATO film remains in the mesh line. The thickness of the Si3N4 film is consistent with that of the ATO film, so the surface of the obtained composite film is smooth.

[0107] (8) A layer of ATO film was prepared on the surface of the sample obtained in step (7) by using magnetron sputtering coating technology. When using magnetron sputtering coating technology, the vacuum degree of the chamber was pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and oxygen were introduced with an argon-oxygen ratio of 20:1. The pressure was adjusted to 1.0 Pa, and the ATO ceramic target was sputtered at 500°C with a sputtering power of 150 W. A 30 nm thick ATO film was deposited, and the obtained sample was a highly stable ITO conductive glass.

[0108] The average transmittance of the glass in the visible light region was 81.1%, and the sheet resistance was 8.5Ω / □. After being kept in air at 500°C for 30 minutes, the sheet resistance changed by 14.3%. After being immersed in hydrochloric acid with a pH of 1 for 1 hour, its sheet resistance remained unchanged.

[0109] Table 1 shows the visible light transmittance and sheet resistance of high-stable ITO conductive glass under different preparation conditions.

[0110] Table 1

[0111]

[0112] The above description is merely an embodiment of the present invention and does not constitute any form of limitation to the present invention. The present invention may also have other forms of embodiments based on the above structures and functions, which are not listed here one by one. Therefore, any simple modification, equivalent changes, and modifications made to the above embodiments by any person skilled in the art in accordance with the technical essence of the present invention without departing from the scope of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing highly stable ITO conductive glass, characterized in that: The specific steps include: (1) After cleaning the glass substrate, a layer of ITO film is prepared on its surface using magnetron sputtering technology; (2) Using a roller coating method, a styrene acrylic emulsion coating with a thickness of 5 μm to 10 μm is prepared on the surface of the ITO film obtained in step (1). After drying, the styrene acrylic emulsion coating forms a mesh cracking template, wherein the mesh cracking template is composed of a plurality of intersecting mesh lines and mesh holes, the mesh holes are located between adjacent mesh lines and the mesh holes are filled with styrene acrylic film, and the ITO film located within the mesh lines is in a bare state; (3) using magnetron sputtering coating technology to prepare an ATO film on the surface of the mesh crack template obtained in step (2), wherein a portion of the ATO film is formed on the surface of the styrene acrylic film and a portion is formed inside the mesh line; (4) preparing a ZnO film on the surface of the ATO film obtained in step (3) by using a magnetron sputtering coating technique, and the ATO film and the ZnO film on the surface thereof are referred to as an ATO / ZnO film; (5) The sample obtained in step (4) is ultrasonically cleaned in acetone, and the styrene-acrylic film filled in the mesh is removed, that is, the ITO film in the mesh is exposed, and the ATO / ZnO film located in the mesh line is raised on the surface of the ITO film; (6) A Si3N4 film is prepared on the surface of the sample obtained in step (5) using magnetron sputtering coating technology, wherein a portion of the Si3N4 film is formed in the mesh, and another portion is formed on the surface of the ATO / ZnO film in the mesh line. The thickness of the Si3N4 film is consistent with the thickness of the ATO film prepared in step (3); (7) Place the sample obtained in step (6) into a sodium hydroxide aqueous solution and react for 20-30 minutes; (8) A layer of ATO thin film is prepared on the surface of the sample obtained in step (7) using magnetron sputtering coating technology. The obtained sample is a highly stable ITO conductive glass.

2. The method for preparing the highly stable ITO conductive glass according to claim 1, wherein When magnetron sputtering technology is used in step (1), the sputtering target is an indium tin oxide ceramic target, wherein 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; and the sputtering power is 80-200 W.

3. The preparation method of the highly stable ITO conductive glass as claimed in claim 1, wherein The thickness of the ITO film in step (1) is 100-200 nm; the thickness of the ATO film in step (3) is 20-40 nm; and the thickness of the ZnO film in step (4) is 100-300 nm.

4. The method for preparing the highly stable ITO conductive glass according to claim 1, wherein The mesh diameter in step (2) is 10 μm to 30 μm, and the mesh line width is 1 μm to 3 μm.

5. The method for preparing the highly stable ITO conductive glass according to claim 1, wherein When magnetron sputtering coating technology is used 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 to SnO2 in the ATO target is 1:9; the deposition temperature is room temperature, the deposition gas is an argon-oxygen mixed gas, 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 method for preparing the highly stable ITO conductive glass according to claim 1, wherein When the magnetron sputtering coating technology is used 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.

7. The method for preparing the highly stable ITO conductive glass according to claim 1, wherein: The thickness of the Si3N4 film in step (6) is 20-40 nm; when using magnetron sputtering coating technology, the sputtering target is 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 method for preparing the highly stable ITO conductive glass according to claim 1, wherein The mass fraction of the sodium hydroxide aqueous solution in step (7) is 5%.

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

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

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