High-temperature-resistant ITO (indium tin oxide) conductive glass and preparation method thereof

Abstract

The invention provides high-temperature-resistant indium tin oxide (ITO) conductive glass and a preparation method thereof, and relates to the field of transparent conductive materials.The preparation method of the ITO conductive glass comprises the steps that firstly, a glass substrate is cleaned, and the clean glass substrate is placed on a magnetron sputtering preparation table; meanwhile, an ITO ceramic target material, a SnO2 ceramic target material and a Si3N4 ceramic target material are installed on different fixed targets of magnetron sputtering equipment respectively, then a bottom layer SnO2 thin film, an ITO thin film, a middle SnO2 thin film, a Si3N4 thin film and a top layer SnO2 thin film are sequentially deposited on the glass substrate through the magnetron sputtering technology, and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure is formed on the surface of the glass substrate; the conductive glass prepared by the method disclosed by the invention can still keep stable electrical properties and relatively high light transmittance in a high-temperature environment, meets the strict requirements on materials in the fields of semiconductor device manufacturing, solar cells and the like, and promotes the development of related industries.

Description

Technical Field

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

[0002] In modern technology industries, transparent conductive materials are the core components of many key devices. Among them, ITO conductive glass has been widely used in the fields of semiconductor device manufacturing, solar cells, flat panel displays, etc. due to its good electrical conductivity and high light transmittance. However, with the rapid development of related industries, the performance requirements for materials in high-temperature environments are increasing day by day, and the limitations of traditional ITO conductive glass are gradually emerging.

[0003] The core functional layer ITO film of indium tin oxide (ITO) glass has a thermal sensitivity characteristic, which becomes the main obstacle to its application in high-temperature environments. When the working temperature exceeds 350 °C, the film interacts with external oxygen, and the internal carrier concentration decreases significantly due to the intensified migration of lattice oxygen vacancies in indium tin oxide. At the same time, the density of defect states at grain boundaries increases sharply, further leading to a sharp decrease in the number of free carriers inside the film, resulting in a non-linear steep increase in the sheet resistance value of the film. For example, after heat treatment at 350 °C for 30 minutes, the increase in its sheet resistance value can reach 200% - 300%. This irreversible decline in electrical properties directly causes the failure of devices based on ITO glass in high-temperature processes.

[0004] In the field of semiconductor device manufacturing, the annealing process of thin-film transistor arrays requires the substrate material to maintain stability in an environment of 400 - 450 °C for more than 1 hour. However, under such conditions, the electrical conductivity of traditional ITO glass will deteriorate significantly, thereby affecting the performance of thin-film transistors and resulting in a decline in the overall performance of the device, unable to meet the manufacturing requirements of high-end semiconductor devices.

[0005] During the preparation process of crystalline silicon solar cells, although the emitter high-temperature diffusion process (850 - 900 °C) uses a mask for protection, the local sheet resistance value of the ITO glass edge region will still increase abnormally due to thermal radiation. The sheet resistance value of the edge region can reach 5 - 8 times the initial value. This seriously damages the uniformity of the electrode pattern, reduces the photoelectric conversion efficiency of the solar cell, increases the production cost, and restricts the development of the solar cell industry.

[0006] To address the problem of insufficient high-temperature resistance of ITO glass, researchers and the industry have conducted extensive explorations. Among existing alternative solutions, fluorine-doped tin oxide (FTO) thin films form a stable oxygen vacancy structure through fluorine doping, enhancing their thermal stability to the 600 °C level. However, the conductive mechanism of FTO, which is essentially an n-type semiconductor, results in a relatively low intrinsic carrier concentration, and SnO2-based materials have intrinsic absorption in the visible light band. This makes the overall performance of FTO thin films generally show a sheet resistance value higher than 15 Ω / sq, while the average visible light transmittance is less than 80%. This imbalance in optoelectronic properties makes it difficult to meet the strict requirements for material properties in large-scale industrial production.

[0007] In addition, some other attempted improvement methods, such as simply changing the thickness or composition ratio of the ITO thin film, can improve certain properties to a certain extent but cannot fundamentally solve the problems of electrical property degradation and optoelectronic property balance at high temperatures. In practical applications, these improved materials still have problems such as unstable conductive performance and significant decrease in light transmittance after long-term high-temperature treatment, unable to meet the growing market demand. Therefore, it is urgent to develop an ITO conductive glass that can maintain stable electrical properties and good light transmittance in a high-temperature environment and its preparation method. Summary of the Invention

[0008] The present invention aims to overcome the problem of performance degradation of ITO conductive glass in a high-temperature environment, and provides a high-temperature resistant ITO conductive glass and its preparation method, so that the obtained conductive glass can still maintain stable electrical properties and high light transmittance in a high-temperature environment, meeting the stringent requirements for materials in fields such as semiconductor device manufacturing and solar cells.

[0009] To achieve the above object, the specific solution adopted in the present invention is as follows: On the one hand, the present invention provides a preparation method of a high-temperature resistant ITO conductive glass, mainly including the following steps: Step S1: Clean the glass substrate, and place the cleaned glass substrate on the preparation table of the magnetron sputtering device. At the same time, install the ITO ceramic target, SnO2 ceramic target, and Si3N4 ceramic target on different fixed targets in the magnetron sputtering device respectively; Step S2: Deposit a bottom SnO2 thin film, an ITO thin film, a middle SnO2 thin film, a Si3N4 thin film, and a top SnO2 thin film on the glass substrate in sequence through magnetron sputtering technology, that is, form a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure on the surface of the glass substrate; Among them, when magnetron sputtering the bottom SnO2 film, the deposition temperature is 200 - 400 °C, the sputtering gas is a mixed gas 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, and the sputtering power is 50 - 200 W; When magnetron sputtering the ITO film, the deposition temperature is 300 - 400 °C, the sputtering gas is argon, the sputtering pressure is 0.8 - 1.5 Pa, and the sputtering power is 100 - 200 W; When magnetron sputtering the middle SnO2 film, the deposition temperature is 200 - 400 °C, the sputtering gas is a mixed gas 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, and the sputtering power is 50 - 200 W; When magnetron sputtering the Si3N4 film, the deposition temperature is 200 - 400 °C, the sputtering gas is argon, the sputtering pressure is 1 - 2 Pa, and the sputtering power is 80 - 200 W; When magnetron sputtering the top SnO2 film, the deposition temperature is 200 - 400 °C, the sputtering gas is a mixed gas 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, and the sputtering power is 50 - 200 W.

[0010] Furthermore, before sputtering each layer of the film, the background vacuum degree of the magnetron sputtering equipment is pumped to 3.0×10 - 4 Pa - 8.0×10 -4 Pa.

[0011] Furthermore, the mass ratio of In2O3 to SnO2 in the ITO ceramic target is 90:10.

[0012] On the other hand, the present invention provides a high-temperature resistant ITO conductive glass, which is prepared by the above method.

[0013] Furthermore, the thickness of each layer of the film is as follows: The thickness of the bottom SnO2 film is 5 - 10 nm; The thickness of the ITO film is 50 - 200 nm; The thickness of the middle SnO2 film is 5 - 10 nm; The thickness of the Si3N4 film is 8 - 15 nm; The thickness of the top SnO2 film is 10 - 15 nm.

[0014] Furthermore, the light transmittance of the obtained high-temperature resistant ITO conductive glass is 80% - 86.1%, the sheet resistance is 8 - 50 Ω / sq, and after annealing at 400 °C for 1 hour, the change rate of the sheet resistance is not higher than 10%.

[0015] First, the functions of each layer of thin film are described.

[0016] (1) Bottom SnO2 thin film: As the first layer of thin film in direct contact with the glass substrate, it plays a buffering and transitional role. On the one hand, it improves the surface roughness and chemical properties of the glass substrate, providing more favorable conditions for the growth of the subsequent ITO thin film, enabling the ITO thin film to be deposited more uniformly and reducing the generation of defects. On the other hand, it blocks the diffusion of impurities in the glass substrate into the upper layer of thin film, avoiding the negative impact of impurities on the conductive and optical properties of the ITO thin film.

[0017] (2) ITO thin film: It is the core conductive layer of the conductive glass, and its carrier concentration and mobility determine the conductive performance of the glass. In the present invention, by precisely controlling the sputtering process parameters, the ITO thin film not only has good conductive performance but also forms a good interfacial structure with the upper and lower layers of SnO2 thin films, which is beneficial to maintaining stable conductive performance at high temperatures.

[0018] (3) Middle SnO2 thin film: In a high-temperature environment, tin ions in the middle SnO2 thin film will diffuse into the ITO thin film, supplementing the reduction of carriers in the ITO thin film caused by high temperature, effectively suppressing the increase in the sheet resistance value of the ITO thin film, and maintaining the conductive performance of the thin film. At the same time, it also enhances the stability of the entire composite thin film structure, and cooperates with the bottom and top SnO2 thin films to improve the high-temperature resistance of the conductive glass.

[0019] (4) Si3N4 thin film: It has good chemical stability and barrier properties, and can isolate the contact between the ITO thin film and oxygen. In a high-temperature environment, it inhibits the formation and migration of oxygen vacancies, avoiding the deterioration of the electrical properties of the ITO thin film caused by changes in oxygen vacancies, thereby stabilizing the electrical properties of the ITO thin film. In addition, the Si3N4 thin film also has a certain mechanical strength, which can enhance the overall mechanical properties of the composite thin film.

[0020] (5) Top SnO2 thin film: Located on the outermost layer of the composite thin film, it plays a role in protecting the internal thin films. It can prevent impurities such as oxygen and moisture in the external environment from eroding the internal ITO thin film and Si3N4 thin film, and extend the service life of the conductive glass. In a high-temperature environment, the top SnO2 thin film and the Si3N4 thin film cooperate to further stabilize the entire composite thin film structure and improve the high-temperature resistance of the conductive glass.

[0021] Secondly, the reactions between adjacent layers of thin films are described.

[0022] (1)Bottom SnO2 thin film and ITO thin film: During the preparation process, a certain interfacial diffusion layer will form between the bottom SnO2 thin film and the ITO thin film. Due to the diffusion ability of the atoms of the two materials in the high-temperature sputtering environment, some atoms in SnO2 will diffuse into the ITO thin film, forming a transition structure at the interface. This diffusion helps to enhance the bonding force between the two thin films, enabling the ITO thin film to adhere more firmly to the bottom SnO2 thin film. At the same time, it may also have a certain modulation effect on the electrical properties of the ITO thin film, optimizing its conductive performance.

[0023] (2)ITO thin film and middle SnO2 thin film: In a high-temperature environment, tin ions in the middle SnO2 thin film will diffuse into the ITO thin film. This diffusion phenomenon is one of the key mechanisms for improving the high-temperature resistance of the conductive glass in this invention. The diffusion of tin ions compensates for the reduction of carriers in the ITO thin film due to high temperature, maintaining the conductive performance of the ITO thin film. At the same time, this diffusion will also change the electronic structure at the interface between the ITO thin film and the middle SnO2 thin film, further enhancing the interaction between the two thin films and improving the stability of the composite thin film structure.

[0024] (3)Middle SnO2 thin film and Si3N4 thin film: Although SnO2 and Si3N4 are relatively stable in chemical properties, during the high-temperature preparation process, a certain degree of atomic diffusion and interaction will still occur at the interface. This interaction helps to form a stable transition region, enhancing the bonding force between the two thin films and making the entire composite thin film structure more stable. At the same time, the Si3N4 thin film physically isolates oxygen penetration through its chemical inertness and dense structure, reducing ITO oxidation, and indirectly promoting its stabilizing effect on the conductive performance of the ITO thin film.

[0025] (4)Si3N4 thin film and top SnO2 thin film: There is also a certain interaction between the top SnO2 thin film and the Si3N4 thin film. The top SnO2 thin film can protect the Si3N4 thin film from the erosion of the external environment. At the same time, at high temperature, 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 thin film but also further improves the protection effect on the internal ITO thin film, ensuring that the conductive glass can maintain good performance in a high-temperature environment. At the same time, by controlling the thickness (10 - 15 nm), the surface reflection is reduced, and the light transmittance is increased to 80% - 86.1%.

[0026] It can be seen from this that the positions of the various film layers in the present invention are carefully designed according to their functional requirements. The main function of the bottom SnO2 thin film is to improve the surface properties of the glass substrate and block the diffusion of impurities. Only by directly contacting the glass substrate can this function be effectively exerted. If its position is adjusted above other layers, the blocking of impurities on the glass substrate cannot be achieved, resulting in impurities entering the upper thin film and affecting the performance of the entire composite thin film. As the core conductive layer, the ITO thin film needs to cooperate closely with the upper and lower SnO2 thin films to maintain stable conductive performance at high temperatures. The middle SnO2 thin film provides carrier supplementation for the ITO thin film and must be adjacent to the ITO thin film. The oxygen barrier function of the Si3N4 thin film determines that it needs to be close to the ITO thin film to isolate the influence of oxygen on the ITO thin film. The top SnO2 thin film is used to protect the internal thin films and can exert its best protection effect when located on the outermost layer. At the same time, it should be noted that during the preparation process, the deposition sequence and position of the various film layers are crucial for the structural stability of the entire composite thin film. The growth conditions and atomic diffusion characteristics of different thin films are different. If the film layer position is changed, it may lead to a decrease in the bonding force between the thin films and problems such as delamination. For example, if the Si3N4 thin film is placed on the bottom layer, due to the mismatch of its thermal expansion coefficient with the glass substrate, during subsequent high-temperature treatment, it is easy to cause stress concentration between the thin film and the glass substrate, resulting in the failure of the entire composite thin film structure. Moreover, changing the film layer position may affect the atomic diffusion and interaction between the thin films of each layer, unable to form the expected stable structure, and thus affecting the performance of the conductive glass.

[0027] Beneficial effects: Through the unique multi-layer film system configuration design and precise preparation process control of the present invention, the problem of performance degradation of traditional ITO conductive glass in high-temperature environments has been successfully solved. The obtained high-temperature-resistant ITO conductive glass has excellent electrical properties, high light transmittance, and good high-temperature stability, and has broad application prospects in the fields of semiconductor device manufacturing, solar cells, etc. Description of the drawings

[0028] Figure 1 It is a schematic cross-sectional structure diagram of the prepared high-temperature-resistant ITO conductive glass.

[0029] Figure 2 It is a preparation flow chart of the composite thin film structure.

[0030] Figure 3 It is a comparison chart of the sheet resistance of the product prepared in Example 1 and ordinary ITO glass after high-temperature annealing. Detailed implementation manners

[0031] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.

[0032] The present invention discloses a high-temperature resistant ITO conductive glass and a preparation method thereof. Please refer to Figure 1 , the ITO conductive glass includes a glass substrate and a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure formed on the surface of the glass substrate.

[0033] Please refer to Figure 2 , the preparation method of the high-temperature resistant ITO conductive glass is as follows: Step S1: Clean the glass substrate to ensure that its surface is clean without impurities and contaminants remaining. The cleaned glass substrate is placed on the preparation table of the magnetron sputtering equipment; at the same time, an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target are respectively installed on different fixed targets in the magnetron sputtering equipment to prepare for subsequent film deposition; Step S2: Deposit a bottom SnO2 film, an ITO film, a middle SnO2 film, a Si3N4 film, and a top SnO2 film on the glass substrate in sequence by magnetron sputtering technology to form a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite film structure; S21: Deposition of the bottom SnO2 film: When magnetron sputtering the bottom SnO2 film, the deposition temperature is controlled at 200 - 400 °C, the sputtering gas is a mixed gas 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, and the sputtering power is 50 - 200 W; the thickness of the bottom SnO2 film deposited under this condition is 5 - 10 nm, and its main function is to provide a stable growth substrate for the subsequent ITO film, improve the interfacial bonding performance between the ITO film and the glass substrate, reduce interfacial defects, and also block the diffusion of impurities in the glass substrate into the ITO film to affect its performance to a certain extent; S22: Deposition of the ITO film: When magnetron sputtering the ITO 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 the conductive glass to achieve the conductive function, and its carrier concentration and mobility determine the conductive performance of the glass; S23. Middle SnO2 thin film deposition: The process parameters for magnetron sputtering the middle SnO2 thin film are similar to those of the bottom SnO2 thin film. The deposition temperature is 200 - 400 °C, the sputtering gas is a mixed gas 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 thin film is that at high temperatures, its tin ions can diffuse into the ITO thin film to supplement the reduction of carriers in the ITO thin film caused by high temperatures and maintain the conductivity of the thin film. S24. Si3N4 thin film deposition: When magnetron sputtering the Si3N4 thin film, the deposition temperature is 200 - 400 °C, the sputtering gas is argon, the sputtering pressure is 1 - 2 Pa, the sputtering power is 80 - 200 W, and the film thickness is 8 - 15 nm. The Si3N4 thin film has good chemical stability and barrier properties, can isolate the contact between the ITO thin film and oxygen, and inhibit the formation and migration of oxygen vacancies at high temperatures, thereby stabilizing the electrical properties of the ITO thin film. S25. Top SnO2 thin film deposition: When magnetron sputtering the top SnO2 thin film, the deposition temperature is 200 - 400 °C, the sputtering gas is a mixed gas 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 10 - 15 nm. On the one hand, the top SnO2 thin film can protect the internal ITO thin film and Si3N4 thin film from being eroded by the external environment. On the other hand, at high temperatures, it acts synergistically with the Si3N4 thin film to further stabilize the entire composite thin film structure and improve the high-temperature resistance of the conductive glass.

[0034] It should be noted that: Before sputtering each layer of the thin film, the background vacuum degree of the magnetron sputtering equipment needs to be pumped to 3.0×10 -4 Pa - 8.0×10 -4 Pa. A low background vacuum degree can reduce the mixing of impurity gases during sputtering, ensure the purity and quality of the thin film, and avoid the negative impact of impurities on the film performance.

[0035] In the high-temperature resistant ITO conductive glass prepared by the present invention, each layer of the thin film has a specific thickness range. The thickness of the bottom SnO2 thin film is 5 - 10 nm, the thickness of the ITO thin film is 50 - 200 nm, the thickness of the middle SnO2 thin film is 5 - 10 nm, the thickness of the Si3N4 thin film is 8 - 15 nm, and the thickness of the top SnO2 thin film is 10 - 15 nm. These thickness ranges are obtained through a large number of experimental verifications, which can not only ensure that each layer of the thin film plays its function but also ensure the optimization of the overall performance of the composite thin film. For example, if the thickness of the ITO thin film is too thin, the conductivity will be insufficient; if the thickness is too thick, the light transmittance will be affected.

[0036] The light transmittance of the high-temperature resistant ITO conductive glass prepared by the above process is 80% - 86%, and the sheet resistance is 8 - 50 Ω / sq. After undergoing a high-temperature annealing at 400 °C for 1 hour, the change rate of the sheet resistance is ≤ 10%. These performance indicators show that while maintaining good light transmittance, the conductive glass has excellent high-temperature resistance and can meet the stringent requirements in practical applications.

[0037] Example 1 This example provides a preparation method for high-temperature resistant ITO conductive glass, mainly including the following steps: Step S1: After cleaning a 1.1 mm thick glass substrate, place it on the preparation table of the magnetron sputtering equipment. At the same time, install the ITO ceramic target, SnO2 ceramic target, and Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment respectively. The distance between the fixed target and the preparation table is 10 cm; Step S2: Pump the background vacuum of the magnetron sputtering equipment to 5.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and high-purity (99.99%) oxygen gas. The flow ratio of argon gas to oxygen gas is 20:1, adjust the pressure to 0.5 Pa, and the deposition temperature is 350 °C. Sputter the SnO2 ceramic target with a sputtering power of 100 W to deposit an 8 nm thick bottom SnO2 thin film; Step S3: After step S2 is completed, pump the background vacuum of the magnetron sputtering equipment to 5.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 1.0 Pa, and adjust the deposition temperature to 350 °C. Sputter the ITO ceramic target with a sputtering power of 100 W to deposit a 100 nm thick ITO thin film; Step S4: After step S3 is completed, repeat step S2 to obtain an 8 nm thick middle SnO2 thin film; Step S5: After step S4 is completed, pump the background vacuum of the magnetron sputtering equipment to 5.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 1.5 Pa, and adjust the deposition temperature to 350 °C. Sputter the Si3N4 ceramic target with a sputtering power of 100 W to deposit a 10 nm thick Si3N4 thin film; Step S6: After step S5 is completed, pump the background vacuum of the magnetron sputtering equipment to 5.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and high-purity (99.999%) oxygen gas. The flow ratio of argon gas to oxygen gas is 20:1, adjust the pressure to 0.5 Pa, and the deposition temperature is 350 °C. Sputter the SnO2 ceramic target with a sputtering power of 150 W to deposit a 12 nm thick top SnO2 thin film; Step S7: After the deposition is completed, a high-temperature resistant ITO conductive glass can be obtained; this 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.

[0038] The measured transmittance of the obtained ITO conductive glass is 84.2%, and the sheet resistance is 19.8 Ω / sq. After annealing at 400 °C for 1 hour, the change rate of the sheet resistance is 5.6%.

[0039] 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 (a commercially available product, manufacturer: Kaisheng Information Display Materials (Luoyang) Co., Ltd., model: STN14×16×1.1 mm, batch number 250603313, sheet resistance 90 Ω / sq) were annealed at 300 °C, 350 °C, 400 °C, 450 °C, and 500 °C for 1 hour respectively, and the sheet resistance of the two products under each annealing condition was measured, and the change rate of the sheet resistance was calculated. The results are as Figure 3 shown. As can be seen from the figure, after the ITO conductive glass obtained in this example undergoes different annealing conditions, the resistance change rate does not exceed 10%, while for ordinary ITO glass, as the annealing temperature increases, the resistance change rate gradually increases. When the annealing temperature reaches 500 °C, the resistance change rate reaches 870%. It can be seen from this that the product prepared by the present invention has excellent high-temperature resistance.

[0040] Example 2 This example provides a preparation method for a high-temperature resistant ITO conductive glass, which mainly includes the following steps: Step S1: After cleaning a 1.1-mm-thick glass substrate, place it on the preparation table of the magnetron sputtering equipment. At the same time, install an ITO ceramic target, a SnO2 ceramic target, and a Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment. The distance between the fixed target and the preparation table is 10 cm; Step S2: Pump the background vacuum of the magnetron sputtering equipment to 3.0×10 -4 Pa, introduce high-purity (99.999%) argon and high-purity (99.99%) oxygen. The flow ratio of argon to oxygen is 30:1, the pressure is adjusted to 0.3 Pa, the deposition temperature is 200 °C, sputter the SnO2 ceramic target, and the sputtering power is 50 W to deposit a 5-nm-thick bottom SnO2 thin film; Step S3: After step S2 is completed, pump the background vacuum of the magnetron sputtering equipment to 3.0×10 -4Ar with a purity of 99.999% is introduced, the pressure is adjusted to 0.8 Pa, the deposition temperature is adjusted to 300 °C, the ITO ceramic target is sputtered, the sputtering power is 100 W, and an ITO thin film with a thickness of 50 nm is deposited; Step S4: After step S3 is completed, step S2 is repeated to obtain a middle SnO2 thin film with a thickness of 5 nm; Step S5: After step S4 is completed, the base vacuum of the magnetron sputtering equipment is pumped to 3.0×10 -4 Pa, Ar with a purity of 99.999% is introduced, the pressure is adjusted to 1.0 Pa, the deposition temperature is adjusted to 200 °C, the Si3N4 ceramic target is sputtered, the sputtering power is 80 W, and an Si3N4 thin film with a thickness of 8 nm is deposited; Step S6: After step S5 is completed, the base vacuum of the magnetron sputtering equipment is pumped to 3.0×10 -4 Pa, Ar with a purity of 99.999% and O2 with a purity of 99.999% are introduced, the flow ratio of Ar to O2 is 30:1, the pressure is adjusted to 0.3 Pa, the deposition temperature is 200 °C, the SnO2 ceramic target is sputtered, the sputtering power is 50 W, and a top SnO2 thin film with a thickness of 10 nm is deposited; Step S7: After the deposition is completed, the 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.

[0041] After testing, the light transmittance of the obtained ITO conductive glass is 86.1%, the sheet resistance is 49.6 Ω / sq, and after annealing at 400 °C for 1 hour, the change rate of the sheet resistance is 9.8%.

[0042] Example 3 This example provides a method for preparing high-temperature resistant ITO conductive glass, which mainly includes the following steps: Step S1: After cleaning a 1.1-mm-thick glass substrate, it is placed on the preparation table of the magnetron sputtering equipment. At the same time, the ITO ceramic target, the SnO2 ceramic target, and the Si3N4 ceramic target are respectively installed on different fixed targets in the magnetron sputtering equipment, and the distance between the fixed target and the preparation table is 10 cm; Step S2: The base vacuum of the magnetron sputtering equipment is pumped to 8.0×10 -4 Pa, Ar with a purity of 99.999% and O2 with a purity of 99.99% are introduced, the flow ratio of Ar to O2 is 10:1, the pressure is adjusted to 1.5 Pa, the deposition temperature is 400 °C, the SnO2 ceramic target is sputtered, the sputtering power is 200 W, and a bottom SnO2 thin film with a thickness of 10 nm is deposited; Step S3: After step S2 ends, pump the base vacuum of the magnetron sputtering equipment to 8.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 1.5 Pa, adjust the deposition temperature to 400 °C, sputter the ITO ceramic target, the sputtering power is 200 W, and deposit an ITO thin film with a thickness of 200 nm; Step S4: After step S3 ends, repeat step S2 to obtain a 10-nm-thick middle SnO2 thin film; Step S5: After step S4 ends, pump the base vacuum of the magnetron sputtering equipment to 8.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 2.0 Pa, adjust the deposition temperature to 400 °C, sputter the Si3N4 ceramic target, the sputtering power is 200 W, and deposit a 15-nm-thick Si3N4 thin film; Step S6: After step S5 ends, pump the base vacuum of the magnetron sputtering equipment to 8.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and high-purity (99.999%) oxygen gas, the flow ratio of argon gas to oxygen gas is 10:1, adjust the pressure to 1.5 Pa, the deposition temperature is 400 °C, sputter the SnO2 ceramic target, the sputtering power is 200 W, and deposit a 15-nm-thick top SnO2 thin film; Step S7: After the deposition is completed, a high-temperature-resistant ITO conductive glass can be obtained; this 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.

[0043] After testing, the light transmittance of the obtained ITO conductive glass is 80.1%, the sheet resistance is 8.2 Ω / sq, and after annealing at 400 °C for 1 hour, the change rate of the sheet resistance is 3.6%.

[0044] Example 4 This example provides a preparation method of a high-temperature-resistant ITO conductive glass, which mainly includes the following steps: Step S1: After cleaning a 1.1-mm-thick glass substrate, place it on the preparation table of the magnetron sputtering equipment. At the same time, install the ITO ceramic target, the SnO2 ceramic target, and the Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment respectively. The distance between the fixed target and the preparation table is 10 cm; Step S2: Pump the base vacuum of the magnetron sputtering equipment to 6.0×10 -4At a pressure of Pa, introduce high-purity (99.999%) argon gas and high-purity (99.999%) oxygen gas. The flow rate ratio of argon gas to oxygen gas is 20:1. Adjust the pressure to 1.5 Pa, the deposition temperature to 300 °C, sputter the SnO2 ceramic target, with a sputtering power of 100 W, and deposit an 8-nm-thick bottom SnO2 thin film. Step S3: After step S2 ends, pump the background vacuum degree of the magnetron sputtering equipment to 6.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 1.0 Pa, adjust the deposition temperature to 350 °C, sputter the ITO ceramic target, with a sputtering power of 150 W, and deposit a 150-nm-thick ITO thin film. Step S4: After step S3 ends, repeat step S2 to obtain an 8-nm-thick middle SnO2 thin film. Step S5: After step S4 ends, pump the background vacuum degree of the magnetron sputtering equipment to 6.0×10 -4 Pa, introduce high-purity (99.999%) argon gas, adjust the pressure to 1.0 Pa, adjust the deposition temperature to 300 °C, sputter the Si3N4 ceramic target, with a sputtering power of 200 W, and deposit a 13-nm-thick Si3N4 thin film. Step S6: After step S5 ends, pump the background vacuum degree of the magnetron sputtering equipment to 6.0×10 -4 Pa, introduce high-purity (99.999%) argon gas and high-purity (99.99%) oxygen gas. The flow rate ratio of argon gas to oxygen gas is 10:1. Adjust the pressure to 1.0 Pa, the deposition temperature to 300 °C, sputter the SnO2 ceramic target, with a sputtering power of 200 W, and deposit a 13-nm-thick top SnO2 thin film. Step S7: After deposition is completed, heat-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.

[0045] After testing, the light transmittance of the obtained ITO conductive glass is 82.0%, the sheet resistance is 15 Ω / sq, and after annealing at 400 °C for 1 hour, the change rate of the sheet resistance is 5.1%.

[0046] As described above, it is only a preferred embodiment of the present invention and does not impose any formal restrictions on the present invention. Any equivalent transformation or modification made according to the essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of high-temperature resistant ITO conductive glass, characterized in that, It mainly includes the following steps: Step S1: Clean the glass substrate, and place the cleaned glass substrate on the preparation table of the magnetron sputtering equipment. At the same time, install the ITO ceramic target, SnO2 ceramic target, and Si3N4 ceramic target on different fixed targets in the magnetron sputtering equipment respectively; Step S2: Deposit a bottom SnO2 thin film, an ITO thin film, a middle SnO2 thin film, a Si3N4 thin film, and a top SnO2 thin film on the glass substrate in sequence by magnetron sputtering technology, that is, form a SnO2 / ITO / SnO2 / Si3N4 / SnO2 composite thin film structure on the surface of the glass substrate; Among them, when magnetron sputtering the bottom SnO2 thin film, the deposition temperature is 200~400°C, the sputtering gas is a mixed gas 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, and the sputtering power is 50~200 W; When magnetron sputtering the ITO thin film, the deposition temperature is 300~400°C, the sputtering gas is argon, the sputtering pressure is 0.8~1.5 Pa, and the sputtering power is 100~200 W; When magnetron sputtering the middle SnO2 thin film, the deposition temperature is 200~400°C, the sputtering gas is a mixed gas of argon and oxygen, the argon-oxygen ratio is 30:1~10:1, the sputtering pressure is 0.3~1.5 Pa, and the sputtering power is 50~200 W; When magnetron sputtering the Si3N4 thin film, the deposition temperature is 200~400°C, the sputtering gas is argon, the sputtering pressure is 1.0~2.0 Pa, and the sputtering power is 80~200 W; When magnetron sputtering the top SnO2 thin film, the deposition temperature is 200~400°C, the sputtering gas is a mixed gas 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, and the sputtering power is 50~200 W.

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

3. The preparation method of a high-temperature resistant ITO conductive glass according to claim 1, characterized in that, The mass ratio of In2O3 to SnO2 in the ITO ceramic target is 90:

10.

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

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

6. A high-temperature resistant ITO conductive glass according to claim 4, characterized in that, The light transmittance of the obtained high-temperature resistant ITO conductive glass is 80%~86.1%, the sheet resistance is 8~50 Ω / sq, and after annealing at 400°C for 1 hour, the change rate of the sheet resistance is not higher than 10%.

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