A kind of high temperature resistant ITO conductive glass and preparation method thereof

Abstract

The present invention provides a high-temperature resistant ITO conductive glass and a preparation method thereof, which relate to the field of transparent conductive materials. The preparation method of the ITO conductive glass comprises the following steps: first, cleaning a glass substrate, placing the clean glass substrate on a preparation table of a magnetron sputtering device, and simultaneously, respectively installing an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target on different fixed targets of the magnetron sputtering device; then, sequentially depositing a bottom SnO2 film, an ITO film, a middle SnO2 film, a Si3N4 film, and a top SnO2 film on the glass substrate by magnetron sputtering technology, thereby forming a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure on the surface of the glass substrate; the conductive glass prepared by the method of the present invention can still maintain stable electrical properties and high light transmittance in a high-temperature environment, meet the stringent requirements for materials in the fields of semiconductor device manufacturing, solar cells, and promote the development of related industries.

Description

Technical Field

[0001] The present invention relates to the field of transparent conductive materials, in particular to high-temperature resistant ITO conductive glass and a preparation method thereof. Background Art

[0002] In modern technology, transparent conductive materials are core components of many key devices. Indium tungsten (ITO) conductive glass, with its excellent conductivity and high light transmittance, has been widely used in semiconductor device manufacturing, solar cells, flat-panel displays, and other fields. However, with the rapid development of related industries, the performance requirements for materials in high-temperature environments are increasing, and the limitations of traditional ITO conductive glass are becoming increasingly apparent.

[0003] The thermal sensitivity of the ITO film, the core functional layer of indium tin oxide (ITO) glass, presents a major obstacle to its application in high-temperature environments. When operating temperatures exceed 350°C, the film interacts with external oxygen, significantly reducing the internal carrier concentration due to the enhanced migration of oxygen vacancies within the ITO lattice. Simultaneously, the density of defect states at the grain boundaries increases dramatically, further leading to a sharp decrease in the number of free carriers within the film, resulting in a nonlinear, steep increase in the film's sheet resistance. For example, after a 30-minute heat treatment at 350°C, the sheet resistance can increase by 200%-300%. This irreversible degradation of electrical performance directly leads to functional failure of ITO glass-based devices during high-temperature manufacturing processes.

[0004] In semiconductor device manufacturing, the annealing process for thin-film transistor arrays requires the substrate material to maintain stability at 400-450°C for at least one hour. However, under these conditions, the conductivity of traditional ITO glass significantly deteriorates, affecting the performance of the thin-film transistors and causing a drop in overall device performance, making it unable to meet the manufacturing requirements of high-end semiconductor devices.

[0005] During the fabrication of crystalline silicon solar cells, even though masks are used for protection during the extremely high-temperature diffusion process (850-900°C), thermal radiation can still cause abnormal increases in the sheet resistance at the edges of the ITO glass, reaching values as high as 5-8 times the initial value. This severely disrupts the uniformity of the electrode pattern, reduces the solar cell's photoelectric conversion efficiency, increases production costs, and hinders the development of the solar cell industry.

[0006] To address the insufficient high-temperature resistance of ITO glass, researchers and industry have conducted extensive research. Among existing alternatives, fluorine-doped tin oxide (FTO) films utilize fluorine doping to create stable oxygen vacancies, improving their thermal stability to 600°C. However, FTO's inherent conductivity as an n-type semiconductor results in a low intrinsic carrier concentration, and the SnO2-based material exhibits intrinsic absorption in the visible light band. Consequently, FTO films exhibit a sheet resistance generally exceeding 15Ω / sq, while their average visible light transmittance is less than 80%. This imbalance in optoelectronic performance makes it difficult to meet the stringent material performance requirements for industrial large-scale production.

[0007] In addition, other attempts to improve ITO film, such as simply changing the thickness or composition of the film, can improve certain properties to a certain extent, but they cannot fundamentally solve the problem of electrical performance degradation and the balance between photoelectric performance at high temperatures. In practical applications, these improved materials still have problems such as unstable conductivity and significant decrease in light transmittance after long-term high-temperature treatment, which cannot meet the growing market demand. Therefore, the development of ITO conductive glass and its preparation method that can maintain stable electrical properties and good light transmittance in high-temperature environments is urgent. Summary of the Invention

[0008] The present invention aims to overcome the problem of performance degradation of ITO conductive glass in high-temperature environments in the prior art, and provide a high-temperature resistant ITO conductive glass and a preparation method thereof, so that the resulting conductive glass can still maintain stable electrical properties and high light transmittance in high-temperature environments, meeting the stringent material requirements in the fields of semiconductor device manufacturing, solar cells, etc.

[0009] In order to achieve the above object, the specific scheme adopted by the present invention is:

[0010] In one aspect, the present invention provides a method for preparing high-temperature resistant ITO conductive glass, which mainly comprises the following steps:

[0011] Step S1, cleaning the glass substrate and placing the cleaned glass substrate on the preparation table of the magnetron sputtering equipment, while simultaneously installing the ITO ceramic target, the SnO2 ceramic target and the Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment;

[0012] Step S2, depositing a bottom SnO2 film, an ITO film, a middle SnO2 film, a Si3N4 film, and a top SnO2 film on a glass substrate in sequence by magnetron sputtering technology, i.e., forming a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure on the surface of the glass substrate;

[0013] Among them, when magnetron sputtering the bottom SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W;

[0014] When magnetron sputtering ITO thin film, the deposition temperature is 300~400℃, the sputtering gas is argon, the sputtering pressure is 0.8~1.5Pa, and the sputtering power is 100~200W;

[0015] When magnetron sputtering the middle SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W;

[0016] When magnetron sputtering Si3N4 thin films, the deposition temperature is 200~400℃, the sputtering gas is argon, the sputtering pressure is 1~2Pa, and the sputtering power is 80~200W;

[0017] When magnetron sputtering the top SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W.

[0018] Furthermore, before sputtering each layer of film, the background vacuum of the magnetron sputtering equipment was pumped to 3.0×10 - 4 Pa~8.0×10 -4 Pa.

[0019] Furthermore, the mass ratio of In2O3 to SnO2 in the ITO ceramic target is 90:10.

[0020] On the other hand, the present invention provides a high temperature resistant ITO conductive glass, which is prepared by the above method.

[0021] Furthermore, the thickness of each film layer is:

[0022] The thickness of the bottom SnO2 film is 5~10nm;

[0023] The thickness of ITO film is 50~200nm;

[0024] The thickness of the SnO2 film in the middle is 5~10nm;

[0025] The thickness of Si3N4 film is 8~15nm;

[0026] The thickness of the top SnO2 film is 10~15nm.

[0027] Furthermore, the obtained high-temperature resistant ITO conductive glass has a light transmittance of 80% to 86.1%, a sheet resistance of 8 to 50 Ω / sq, and a sheet resistance change rate of no more than 10% after high-temperature annealing at 400°C for 1 hour.

[0028] First, the functions of each layer of film are explained.

[0029] (1) Bottom SnO2 film: As the first film in direct contact with the glass substrate, it acts as a buffer and transition. On the one hand, it improves the roughness and chemical properties of the glass substrate surface, providing more favorable conditions for the subsequent growth of the ITO film, enabling the ITO film to be deposited more uniformly and reducing the generation of defects. On the other hand, it prevents impurities in the glass substrate from diffusing into the upper film, preventing impurities from negatively affecting the conductive and optical properties of the ITO film.

[0030] (2) ITO film: It is the core conductive layer of conductive glass. Its carrier concentration and mobility determine the conductive properties of the glass. In the present invention, by precisely controlling the sputtering process parameters, the ITO film not only has good conductive properties, but also forms a good interface structure with the upper and lower SnO2 films, which is conducive to maintaining stable conductive properties at high temperatures.

[0031] (3) Middle SnO2 film: Under high temperature conditions, the tin ions in the middle SnO2 film diffuse into the ITO film, replenishing the reduction in carriers in the ITO film caused by high temperature, effectively suppressing the increase in the sheet resistance of the ITO film and maintaining the conductive properties of the film. At the same time, it also enhances the stability of the entire composite film structure, and synergizes with the bottom and top SnO2 films to improve the high temperature resistance of the conductive glass.

[0032] (4) Si3N4 film: It has good chemical stability and barrier properties, and can isolate the ITO film from oxygen. In a high-temperature environment, it inhibits the formation and migration of oxygen vacancies, avoiding the degradation of the electrical properties of the ITO film caused by changes in oxygen vacancies, thereby stabilizing the electrical properties of the ITO film. In addition, the Si3N4 film also has a certain mechanical strength, which can enhance the overall mechanical properties of the composite film.

[0033] (5) Top SnO2 film: Located on the outermost layer of the composite film, it protects the inner films. It prevents impurities such as oxygen and moisture from the external environment from corroding the internal ITO film and Si3N4 film, thereby extending the service life of the conductive glass. In high-temperature environments, the top SnO2 film and Si3N4 film work together to further stabilize the entire composite film structure and improve the high-temperature resistance of the conductive glass.

[0034] Secondly, the reaction between two adjacent thin films is explained.

[0035] (1) Bottom SnO2 film and ITO film: During the preparation process, a certain interface diffusion layer will be formed between the bottom SnO2 film and the ITO film. Because the atoms of the two materials have a certain diffusion ability under the high-temperature sputtering environment, some atoms in SnO2 will diffuse into the ITO film, forming a transition structure at the interface. This diffusion helps to strengthen the bonding between the two films, allowing the ITO film to adhere more firmly to the bottom SnO2 film. At the same time, it may also have a certain modulation effect on the electrical properties of the ITO film, optimizing its conductive properties.

[0036] (2) ITO film and middle SnO2 film: Under high temperature conditions, tin ions in the middle SnO2 film diffuse into the ITO film. This diffusion phenomenon is one of the key mechanisms for improving the high-temperature resistance of conductive glass in the present invention. The diffusion of tin ions supplements the reduction in carriers in the ITO film caused by high temperature, maintaining the conductive properties of the ITO film. At the same time, this diffusion also changes the electronic structure at the interface between the ITO film and the middle SnO2 film, further enhancing the interaction between the two films and improving the stability of the composite film structure.

[0037] (3) Middle SnO2 film and Si3N4 film: Although SnO2 and Si3N4 are relatively stable in chemical properties, a certain degree of atomic diffusion and interaction still occurs at the interface during the high-temperature preparation process. This interaction helps to form a stable transition region, enhances the bonding force between the two films, and makes the entire composite film structure more stable. At the same time, the Si3N4 film, through its chemical inertness and dense structure, physically isolates oxygen penetration, reduces ITO oxidation, and indirectly promotes its stabilization of the conductive properties of the ITO film.

[0038] (4) Si3N4 film and top SnO2 film: There is also a certain interaction between the top SnO2 film and the Si3N4 film. The top SnO2 film can protect the Si3N4 film from erosion by the external environment. At the same time, at high temperatures, the atomic diffusion and interaction between the two help to form a stable surface structure. This structure not only enhances the overall stability of the composite film, but also further enhances the protection of the internal ITO film, ensuring that the conductive glass can maintain good performance in high temperature environments. At the same time, by adjusting the thickness (10~15nm) to reduce surface reflection, the transmittance is increased to 80%~86.1%.

[0039] As can be seen, the positions of the various film layers in the present invention are carefully designed based on their functional requirements. The primary function of the bottom SnO2 film is to improve the surface properties of the glass substrate and block impurity diffusion. This function can only be effectively achieved when it is in direct contact with the glass substrate. If it is positioned above other layers, it will not be able to block impurities from the glass substrate, allowing impurities to enter the upper film, affecting the performance of the entire composite film. The ITO film, as the core conductive layer, needs to work closely with the upper and lower SnO2 films to maintain stable conductivity at high temperatures. The middle SnO2 film provides carrier replenishment for the ITO film and must be located in close proximity to the ITO film. The Si3N4 film's oxygen barrier function dictates that it must be located close to the ITO film to isolate it from oxygen. The top SnO2 film protects the inner films and is located as the outermost layer to achieve optimal protection. It should also be noted that during the fabrication process, the deposition order and position of the various film layers are crucial to the structural stability of the entire composite film. Different films have different growth conditions and atomic diffusion characteristics. Changing the film layer positions can lead to a decrease in the bonding strength between the films and the occurrence of delamination. For example, if a Si3N4 film is placed as the bottom layer, the mismatch in thermal expansion coefficient between the film and the glass substrate can easily lead to stress concentration between the film and the glass substrate during subsequent high-temperature processing, causing the entire composite film structure to fail. Furthermore, changing the film layer position can affect the atomic diffusion and interaction between the layers, preventing the formation of the desired stable structure and thus affecting the performance of the conductive glass.

[0040] Beneficial effects:

[0041] The present invention successfully solves the problem of performance degradation of traditional ITO conductive glass in high-temperature environments through unique multi-layer film configuration design and precise preparation process control. The resulting high-temperature resistant ITO conductive glass has excellent electrical properties, high light transmittance and good high-temperature stability, and has broad application prospects in semiconductor device manufacturing, solar cells and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the cross-sectional structure of the prepared high-temperature resistant ITO conductive glass.

[0043] Figure 2 It is a flow chart for the preparation of composite thin film structures.

[0044] Figure 3 This is a comparison chart of the square resistance of the product prepared in Example 1 and ordinary ITO glass after high-temperature annealing. DETAILED DESCRIPTION

[0045] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0046] The present invention discloses a high temperature resistant ITO conductive glass and its preparation method, please refer to Figure 1 The ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure formed on the surface of the glass substrate.

[0047] Please refer to Figure 2 The preparation method of the high temperature resistant ITO conductive glass is as follows:

[0048] Step S1: Clean the glass substrate to ensure that its surface is clean and free of impurities and contaminants. The cleaned glass substrate is placed on the preparation table of the magnetron sputtering equipment. At the same time, the ITO ceramic target, SnO2 ceramic target, and Si3N4 ceramic target are respectively installed on different fixed targets in the magnetron sputtering equipment to prepare for subsequent thin film deposition.

[0049] Step S2, depositing a bottom SnO2 film, an ITO film, a middle SnO2 film, a Si3N4 film and a top SnO2 film on a glass substrate in sequence by magnetron sputtering technology to form a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure;

[0050] S21. Deposition of bottom SnO2 film: When magnetron sputtering the bottom SnO2 film, the deposition temperature is controlled at 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W; the thickness of the bottom SnO2 film deposited under these conditions is 5~10nm. Its main function is to provide a stable growth substrate for the subsequent ITO film, improve the interface bonding performance between the ITO film and the glass substrate, reduce interface defects, and at the same time, to a certain extent, prevent impurities in the glass substrate from diffusing into the ITO film and affecting its performance;

[0051] S22. ITO thin film deposition: When magnetron sputtering ITO thin film, the mass ratio of In2O3 to SnO2 in the ITO ceramic target is 90:10, the deposition temperature is 300-400°C, the sputtering gas is argon, the sputtering pressure is 0.8-1.5 Pa, the sputtering power is 100-200 W, and the obtained ITO film thickness is 50-200 nm. It is the key layer for conductive glass to achieve the conductive function. Its carrier concentration and mobility determine the conductive properties of the glass.

[0052] S23. Deposition of the middle SnO2 film: The process parameters of the magnetron sputtering middle SnO2 film are similar to those of the bottom SnO2 film. The deposition temperature is 200-400°C, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1-10:1, the sputtering pressure is 0.3-1.5 Pa, the sputtering power is 50-200 W, and the thickness is 5-10 nm. The main function of the middle SnO2 film is to allow its tin ions to diffuse into the ITO film under high temperature, replenishing the reduction of carriers in the ITO film caused by high temperature, and maintaining the conductive properties of the film.

[0053] S24, Si3N4 thin film deposition: When magnetron sputtering Si3N4 thin film, the deposition temperature is 200~400℃, the sputtering gas is argon, the sputtering pressure is 1~2Pa, the sputtering power is 80~200W, and the film thickness is 8~15nm; Si3N4 thin film has good chemical stability and barrier properties, which can isolate the ITO film from contact with oxygen and inhibit the formation and migration of oxygen vacancies at high temperatures, thereby stabilizing the electrical properties of the ITO film;

[0054] S25. Deposition of the top SnO2 film: When magnetron sputtering the top SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, the sputtering power is 50~200W, and the thickness is 10~15nm; on the one hand, the top SnO2 film can protect the internal ITO film and Si3N4 film from erosion by the external environment. On the other hand, in a high temperature environment, it works synergistically with the Si3N4 film to further stabilize the entire composite film structure and improve the high temperature resistance of the conductive glass.

[0055] It should be noted that before sputtering each layer of thin film, the background vacuum of the magnetron sputtering equipment must be pumped to 3.0×10 -4 Pa~8.0×10 -4 Pa. Low background vacuum can reduce the mixing of impurity gases during the sputtering process, ensure the purity and quality of the film, and avoid the negative impact of impurities on film performance.

[0056] The high-temperature-resistant ITO conductive glass prepared by the present invention has specific thickness ranges for each film layer: the bottom SnO2 film is 5-10 nm thick, the ITO film is 50-200 nm thick, the middle SnO2 film is 5-10 nm thick, the Si3N4 film is 8-15 nm thick, and the top SnO2 film is 10-15 nm thick. These thickness ranges, verified through extensive experimental validation, ensure that each film layer performs its function while optimizing the overall performance of the composite film. For example, if the ITO film is too thin, it will result in insufficient conductivity; if it is too thick, it will affect light transmittance.

[0057] The high-temperature-resistant ITO conductive glass produced using the above process has a transmittance of 80% to 86% and a sheet resistance of 8 to 50 Ω / sq. After annealing at 400°C for one hour, the sheet resistance change is ≤10%. These performance indicators demonstrate that this conductive glass maintains excellent light transmittance while exhibiting superior high-temperature resistance, meeting the stringent requirements of practical applications.

[0058] Example 1

[0059] This embodiment provides a method for preparing high-temperature resistant ITO conductive glass, which mainly includes the following steps:

[0060] Step S1: After cleaning a 1.1 mm thick glass substrate, place it on the preparation table of a magnetron sputtering device. At the same time, an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target are respectively mounted on different fixed targets in the magnetron sputtering device. The distance between the fixed target and the preparation table is 10 cm.

[0061] Step S2: Pump the background vacuum of the magnetron sputtering equipment to 5.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.99%) oxygen were introduced, the flow ratio of argon to oxygen was 20:1, the pressure adjustment was 0.5 Pa, the deposition temperature was 350 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 100 W, and an 8 nm thick bottom SnO2 film was deposited;

[0062] After step S3 and step S2 are completed, the background vacuum of the magnetron sputtering equipment is pumped to 5.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.0 Pa, the deposition temperature was adjusted to 350 ° C, the ITO ceramic target was sputtered, the sputtering power was 100 W, and a 100 nm thick ITO film was deposited;

[0063] After step S4 and step S3 are completed, step S2 is repeated to obtain a middle SnO2 film with a thickness of 8 nm;

[0064] After step S5 and step S4, the background vacuum of the magnetron sputtering equipment is pumped to 5.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.5 Pa, the deposition temperature was adjusted to 350 ° C, the Si3N4 ceramic target was sputtered, the sputtering power was 100 W, and a 10 nm thick Si3N4 film was deposited;

[0065] After step S6 and step S5, the background vacuum of the magnetron sputtering equipment is pumped to 5.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.999%) oxygen were introduced, the flow ratio of argon to oxygen was 20:1, the pressure adjustment was 0.5 Pa, the deposition temperature was 350℃, the SnO2 ceramic target was sputtered, the sputtering power was 150W, and a top SnO2 film with a thickness of 12nm was deposited;

[0066] After step S7, the deposition is completed, a high-temperature resistant ITO conductive glass can be obtained; the ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure formed on the surface of the glass substrate.

[0067] The resulting ITO conductive glass showed a light transmittance of 84.2% and a sheet resistance of 19.8Ω / sq. After annealing at 400°C for one hour, the sheet resistance changed by 5.6%.

[0068] To further verify the stability of the product obtained in this example at high temperatures, the ITO conductive glass obtained in this example and ordinary ITO glass (commercially available, manufacturer: Kaisheng Information Display Materials (Luoyang) Co., Ltd., model: STN14×16×1.1 mm, batch number 250603313, sheet resistance of 90 Ω / sq) were annealed at 300°C, 350°C, 400°C, 450°C, and 500°C for 1 hour respectively. The sheet resistance of the two products under various annealing conditions was measured, and the sheet resistance change rate was calculated. The results are shown in FIG. Figure 3 As shown in the figure, the resistance change rate of the ITO conductive glass obtained in this embodiment does not exceed 10% after undergoing different annealing conditions. In contrast, the resistance change rate of ordinary ITO glass gradually increases with increasing annealing temperature, reaching 870% when the annealing temperature reaches 500°C. This shows that the product prepared by the present invention has excellent high-temperature resistance.

[0069] Example 2

[0070] This embodiment provides a method for preparing high-temperature resistant ITO conductive glass, which mainly includes the following steps:

[0071] Step S1: After cleaning a 1.1 mm thick glass substrate, place it on the preparation table of a magnetron sputtering device. At the same time, an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target are respectively mounted on different fixed targets in the magnetron sputtering device. The distance between the fixed target and the preparation table is 10 cm.

[0072] Step S2: Pump the background vacuum of the magnetron sputtering equipment to 3.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.99%) oxygen were introduced, the flow ratio of argon to oxygen was 30:1, the pressure adjustment was 0.3 Pa, the deposition temperature was 200 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 50 W, and a 5 nm thick bottom SnO2 film was deposited;

[0073] After step S3 and step S2 are completed, the background vacuum of the magnetron sputtering equipment is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 0.8 Pa, the deposition temperature was adjusted to 300 ° C, the ITO ceramic target was sputtered, the sputtering power was 100 W, and a 50 nm thick ITO film was deposited;

[0074] After step S4 and step S3 are completed, step S2 is repeated to obtain a 5 nm thick middle SnO2 film;

[0075] After step S5 and step S4, the background vacuum of the magnetron sputtering equipment is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.0 Pa, the deposition temperature was adjusted to 200 ° C, the Si3N4 ceramic target was sputtered, the sputtering power was 80 W, and an 8 nm thick Si3N4 film was deposited;

[0076] After step S6 and step S5, the background vacuum of the magnetron sputtering equipment is pumped to 3.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.999%) oxygen were introduced, the flow ratio of argon to oxygen was 30:1, the pressure adjustment was 0.3 Pa, the deposition temperature was 200 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 50 W, and a top SnO2 film with a thickness of 10 nm was deposited;

[0077] After step S7, the deposition is completed, a high-temperature resistant ITO conductive glass can be obtained; the ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure formed on the surface of the glass substrate.

[0078] The light transmittance of the obtained ITO conductive glass was tested to be 86.1%, and the sheet resistance was 49.6Ω / sq. After annealing at 400°C for 1 hour, the sheet resistance change rate was 9.8%.

[0079] Example 3

[0080] This embodiment provides a method for preparing high-temperature resistant ITO conductive glass, which mainly includes the following steps:

[0081] Step S1: After cleaning a 1.1 mm thick glass substrate, place it on the preparation table of a magnetron sputtering device. At the same time, an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target are respectively mounted on different fixed targets in the magnetron sputtering device. The distance between the fixed target and the preparation table is 10 cm.

[0082] Step S2: Pump the background vacuum of the magnetron sputtering equipment to 8.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.99%) oxygen were introduced, the flow ratio of argon to oxygen was 10:1, the pressure adjustment was 1.5 Pa, the deposition temperature was 400 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 200 W, and a 10 nm thick bottom SnO2 film was deposited;

[0083] After step S3 and step S2 are completed, the background vacuum of the magnetron sputtering equipment is pumped to 8.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.5 Pa, the deposition temperature was adjusted to 400 ° C, the ITO ceramic target was sputtered, the sputtering power was 200 W, and a 200 nm thick ITO film was deposited;

[0084] After step S4 and step S3 are completed, step S2 is repeated to obtain a 10 nm thick middle SnO2 film;

[0085] After step S5 and step S4, the background vacuum of the magnetron sputtering equipment is pumped to 8.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 2.0 Pa, the deposition temperature was adjusted to 400 ° C, the Si3N4 ceramic target was sputtered, the sputtering power was 200 W, and a 15 nm thick Si3N4 film was deposited;

[0086] After step S6 and step S5, the background vacuum of the magnetron sputtering equipment is pumped to 8.0×10 -4Pa, high-purity (99.999%) argon and high-purity (99.999%) oxygen were introduced, the flow ratio of argon to oxygen was 10:1, the pressure adjustment was 1.5 Pa, the deposition temperature was 400 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 200 W, and a top SnO2 film with a thickness of 15 nm was deposited;

[0087] After step S7, the deposition is completed, a high-temperature resistant ITO conductive glass can be obtained; the ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure formed on the surface of the glass substrate.

[0088] The light transmittance of the obtained ITO conductive glass was tested to be 80.1%, and the sheet resistance was 8.2Ω / sq. After annealing at 400°C for 1 hour, the sheet resistance change rate was 3.6%.

[0089] Example 4

[0090] This embodiment provides a method for preparing high-temperature resistant ITO conductive glass, which mainly includes the following steps:

[0091] Step S1: After cleaning a 1.1 mm thick glass substrate, place it on the preparation table of a magnetron sputtering device. At the same time, an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target are respectively mounted on different fixed targets in the magnetron sputtering device. The distance between the fixed target and the preparation table is 10 cm.

[0092] Step S2: Pump the background vacuum of the magnetron sputtering equipment to 6.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.999%) oxygen were introduced, the flow ratio of argon to oxygen was 20:1, the pressure adjustment was 1.5 Pa, the deposition temperature was 300 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 100 W, and an 8 nm thick bottom SnO2 film was deposited;

[0093] After step S3 and step S2 are completed, the background vacuum of the magnetron sputtering equipment is pumped to 6.0×10 -4 Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.0 Pa, the deposition temperature was adjusted to 350 ° C, the ITO ceramic target was sputtered, the sputtering power was 150 W, and a 150nm thick ITO film was deposited;

[0094] After step S4 and step S3 are completed, step S2 is repeated to obtain a middle SnO2 film with a thickness of 8 nm;

[0095] After step S5 and step S4, the background vacuum of the magnetron sputtering equipment is pumped to 6.0×10 -4Pa, high-purity (99.999%) argon gas was introduced, the pressure was adjusted to 1.0 Pa, the deposition temperature was adjusted to 300 ° C, the Si3N4 ceramic target was sputtered, the sputtering power was 200 W, and a 13 nm thick Si3N4 film was deposited;

[0096] After step S6 and step S5, the background vacuum of the magnetron sputtering equipment is pumped to 6.0×10 -4 Pa, high-purity (99.999%) argon and high-purity (99.99%) oxygen were introduced, the flow ratio of argon to oxygen was 10:1, the pressure adjustment was 1.0 Pa, the deposition temperature was 300 ° C, the SnO2 ceramic target was sputtered, the sputtering power was 200 W, and a top SnO2 film with a thickness of 13 nm was deposited;

[0097] After step S7, the deposition is completed, a high-temperature resistant ITO conductive glass can be obtained; the ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure formed on the surface of the glass substrate.

[0098] The light transmittance of the obtained ITO conductive glass was tested to be 82.0%, and the sheet resistance was 15Ω / sq. After annealing at 400°C for 1 hour, the sheet resistance change rate was 5.1%.

[0099] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any equivalent changes or modifications made based on the essence of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing high temperature resistant ITO conductive glass, characterized in that: The main steps are as follows: Step S1, cleaning the glass substrate and placing the cleaned glass substrate on the preparation table of the magnetron sputtering equipment, while simultaneously installing the ITO ceramic target, the SnO2 ceramic target and the Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment; Step S2, depositing a bottom SnO2 film, an ITO film, a middle SnO2 film, a Si3N4 film, and a top SnO2 film on a glass substrate in sequence by magnetron sputtering technology, i.e., forming a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure on the surface of the glass substrate; Among them, when magnetron sputtering the bottom SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W; When magnetron sputtering ITO thin film, the deposition temperature is 300~400℃, the sputtering gas is argon, the sputtering pressure is 0.8~1.5Pa, and the sputtering power is 100~200W; When magnetron sputtering the middle SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the argon-oxygen ratio is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W; When magnetron sputtering Si3N4 thin films, the deposition temperature is 200~400℃, the sputtering gas is argon, the sputtering pressure is 1.0~2.0Pa, and the sputtering power is 80~200W; When magnetron sputtering the top SnO2 film, the deposition temperature is 200~400℃, the sputtering gas is a mixture of argon and oxygen, the flow ratio of argon to oxygen is 30:1~10:1, the sputtering pressure is 0.3~1.5Pa, and the sputtering power is 50~200W.

2. The method for preparing a high temperature resistant ITO conductive glass according to claim 1, wherein: Before sputtering each layer of film, the background vacuum of the magnetron sputtering equipment was pumped to 3.0×10 -4 Pa~8.0×10 -4 Pa.

3. The method for preparing a high temperature resistant ITO conductive glass according to claim 1, wherein: The mass ratio of In2O3 to SnO2 in ITO ceramic target is 90:

10.

4. A high temperature resistant ITO conductive glass, characterized in that: It is prepared by the method according to any one of claims 1 to 3.

5. The high temperature resistant ITO conductive glass according to claim 4, characterized in that: The thickness of each film layer is: The thickness of the bottom SnO2 film is 5~10nm; The thickness of ITO film is 50~200nm; The thickness of the SnO2 film in the middle is 5~10nm; The thickness of Si3N4 film is 8~15nm; The thickness of the top SnO2 film is 10~15nm.

6. The high temperature resistant ITO conductive glass according to claim 4, characterized in that: The obtained high-temperature resistant ITO conductive glass has a light transmittance of 80% to 86.1% and a sheet resistance of 8 to 50 Ω / sq. Moreover, after annealing at 400°C for 1 hour, the sheet resistance change rate is no more than 10%.

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