CN1294098C - Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof - Google Patents

Abstract

The invention discloses a method for preparing titanium silicide coated glass under nitrogen protection and the titanium silicide coated glass. A thin film is deposited on the common float glass substrate or a silicon thin film is deposited between them. By preparing a composite film of titanium silicide and silicon or doping a small amount of active carbon or nitrogen in the film to obtain a composite film of titanium silicide composite silicon carbide or titanium carbide or titanium silicide composite silicon nitride or titanium nitride, the composite film can be made The mechanical strength and chemical resistance of the coated glass are improved. The invention is a new type of coated glass which combines the functions of dimming, heat insulation and low-emissivity glass.

Description

Method for preparing titanium silicide coated glass under nitrogen protection and titanium silicide coated glass

technical field

The invention relates to a preparation technology of titanium silicide coated glass, in particular to a normal pressure pyrolysis chemical vapor deposition method, nitrogen protection, on-line formation of high-performance titanium silicide coated glass and a preparation method thereof.

Background technique

With the improvement of the quality of modern life, people have higher and higher requirements for maintaining a comfortable indoor environment and protecting privacy, so coated glass came into being. At present, there are two main types of coated glass used as architectural glass curtain walls: one is dimming and heat-insulating coated glass, and the other is low-emissivity coated glass.

Dimming and heat-insulating coated glass is mainly used to control sunlight and heat from entering the room in summer. It is known that the wavelength of the solar radiation spectrum is between 300 and 3000nm, and the distribution of the total heat that radiated electromagnetic waves enter through the window is: about 15% in the ultraviolet region less than 425nm, about 40% in the visible spectrum region from 425 to 675nm, and about 40% in the visible spectrum region between 675 and 1200nm. The wavelength range near infrared (NIR) region is about 45%. It can be seen that nearly half of the solar radiation energy in the near-infrared (NIR) region in the wavelength range of 675-1200nm will enter the room. The ability to transmit visible light within the range, on the other hand it is best to have high reflectivity for NIR. At present, films with two modes of reflection and absorption are generally used to control sunlight and heat from entering the room.

Low-emissivity coated glass is mainly used in winter. While sunlight can penetrate well, it can well reflect the mid- and far-infrared rays emitted by indoor objects, reduce heat loss, and achieve energy-saving effects. Low-emissivity coated glass is divided into two categories: one is a dielectric-metal-dielectric composite film, and the other is a transparent conductive film, such as a highly doped wide-bandgap semiconductor. They mainly achieve different reflectivity and absorptivity for electromagnetic radiation of different frequencies by adjusting the carrier concentration in the film (reducing the resistivity of the film), so as to realize the transmission of visible light and the reflection of mid- and far-infrared.

In recent years, people have focused their attention on the development of composite coated glass that has the functions of both light-adjusting and heat-shielding films and low-emissivity films. In fact, this kind of glass can play an energy-saving role in both summer and winter. In summer, the composite coated glass can not only block sunlight from passing through, but also prevent the heat radiated and reflected by outdoor high-temperature objects from entering the room, reducing the indoor temperature in summer. Air-conditioning energy consumption; in winter, it can well reflect the mid-to-far infrared rays emitted by indoor objects and reduce heat loss. At present, it is generally possible to realize the combination of these two functions by making a multi-layer composite film by multi-layer compounding of a light-adjustable heat-insulating film and a low-emissivity film. Titanium silicide (TiSi ₂ ) film is a film that not only shields sunlight but also reflects mid- and far-infrared radiation. Therefore, TiSi ₂ coated glass can combine the functions of solar control and low radiation, and can be made into a new type of coated glass. . TiSi ₂ has two crystal phase structures: one is the bottom center orthogonal structure; the unit cell size is: a = 0.362nm, b = 1.376nm, c = 0.360nm; resistivity ρ = 60 ~ 100μΩ-cm; the other One is a face-centered orthogonal structure, the unit cell size is: a=0.826nm, b=0.480nm, c=0.853nm; the resistivity is ρ=12～20μΩ-cm, and the melting point is 1540°C. The bottom-centered orthorhombic structure transforms into a face-centered orthorhombic structure above 750°C. The TiSi ₂ thin film with face-centered orthogonal structure has very low resistivity, so it has a high reflectivity for low-frequency electromagnetic waves and can shield a large amount of solar heat; and the TiSi ₂ thin film has about the same transmittance in the entire visible light region, It has a neutral color tone and does not distort the scene, so this film is of special importance for the application on window glass.

The preparation methods of existing coated glass can be divided into two categories: one is off-line coating methods, such as vacuum evaporation, DC sputtering, radio frequency sputtering, magnetron sputtering, ion beam sputtering and ion plating, etc., this method The finished glass produced continuously on the glass production line is cut and re-coated by various coating methods (called off-line coating); the other is on-line coating methods, such as chemical vapor deposition (CVD) and spraying technology. In the method, the coating is directly carried out on the glass float production line (called online coating). Vacuum evaporation is only used for substances with low melting point and volatile heating. The film-forming materials are limited, the quality of the coating is not good, and it needs to work under vacuum, so it can only be coated offline; the sputtering method can obtain high-quality films, but the deposition The speed is slow, the equipment is expensive, the operation is complicated, and the cost is high, so it can only be coated offline; the spraying technology has a fast deposition rate, but the uniformity of the sprayed layer is poor; CVD is an excellent coating process with high film quality. APCVD (atmospheric pressure CVD), LPCVD (low pressure CVD), PECVD (plasma enhanced CVD), LICVD (laser induced CVD) etc. are widely used in CVD process. Low-pressure CVD can improve the uniformity of the film, and the quality of the film is better, but the cost is higher, the equipment is complicated, the deposition speed is reduced, and it is difficult to achieve online coating; PECVD and LICVD are similar, can reduce the deposition temperature, improve the uniformity of the film, but the cost High, complex technology and equipment, not suitable for online coating; atmospheric pressure CVD has a large deposition rate, and operates under atmospheric pressure, is an atmospheric process, easy to achieve continuous coating on-line or off-line, suitable for large-area coating, low production cost, The equipment is simple, especially the heat energy in glass production is directly used, which greatly saves energy, and the prepared coated glass can be bent and tempered.

Due to the social and economic significance of the field of coated glass, the research on coated glass has become a hot topic at home and abroad, such as BFG Glass Group, Libbey-Owens-Ford Company, Pilkington Brothers Co., Ltd., PPG Industries, and American Glass Research Inc. , M&T Chemical Co., Ltd. and other multinational companies have successively applied for related coated glass patent rights in China since 1985, and the competition is fierce. In terms of off-line coating technology, since 1985, Shenzhen Southern Glass Group Corporation, Luoyang Glass Group Corporation, Shanghai Yaohua Glass Group Corporation, Qinhuangdao Yaohua Glass Corporation, etc. have successively introduced vacuum magnetron sputtering coating with huge sums of money (such as to AIRCO in the United States). Equipment, the production capacity of each set of equipment is about hundreds of thousands of square meters per year. In terms of online coating process, because of its large production capacity and low cost, it has obvious advantages in the competition. Developed by Qinhuangdao Glass Research Institute, monosilane thermally decomposes in a non-oxidizing atmosphere to form polysilicon and nano-silicon thin films, and realizes continuous production on glass float lines. It is a relatively successful technology in China. This technology is mainly used to prepare all kinds of solar control energy-saving glass. At present, a company in Weihai Bluestar produces nearly 10 million square meters of energy-saving coated glass annually. On the other hand, at present, Qinhuangdao Yaohua Glass Co., Ltd. has introduced the online production technology of low-emissivity coated glass, Zhejiang University Bluestar has also independently developed the online production technology of low-emission coated glass, and started the online production of pure low-emissivity functional glass in China. preparation.

_TiSi2 thin film has compound functional properties of shielding sunlight and reflecting mid- and far-infrared radiation. Gordon has applied for patents US5167986 and WO89/10209 on TiSi ₂ coated glass, but the patent only introduces the application and on-line preparation of TiSi ₂ coated glass as dimming and heat insulating glass. Gordon uses the SiH ₄ -TiCl ₄ -He system to form a TiSi ₂ film on a glass substrate at 650-680°C. The TiSi ₂ film has a neutral tone and a high near-infrared reflectivity. The patent does not point out the structure and resistivity of the generated TiSi ₂ film, which has a very important impact on the infrared reflectivity, especially the mid-to-far infrared reflectivity, that is, the patent does not obtain a high reflectivity to the mid-to-far infrared. TiSi ₂ thin film, that is, TiSi ₂ coated glass that does not obtain low-emissivity characteristics. In addition, Gordon uses helium as the inert protective gas for the reaction, but the inert protective gas in the tin tank on the actual float online coated glass production line is nitrogen, which is different from the actual situation in industrial production, and helium is used as the inert protective gas for the reaction. Shielding gas will greatly increase production costs. In the present invention, from the perspective of combining with actual production, reducing production costs and excellent low-radiation characteristics, nitrogen is developed and utilized as an inert protective gas, which is the same as the inert protective gas in the tin bath, and used as TiCl ₄ Carrier gas, moreover, use a small amount of N atoms to enter the crystal structure during the reaction process to form interstitial solid solution, form silicon compounds, etc., so as to achieve the modification of _TiSi2 film, improve the wear resistance and chemical corrosion resistance of the film , especially the successful preparation of low-resistivity films on glass substrates to obtain high mid- and far-infrared reflectivity coated glass and successful use as high-performance low-emissivity glass. Obviously, the preparation of titanium silicide coated glass by atmospheric pressure CVD under nitrogen protection has more obvious advantages than those prepared under helium protection, and obtains a new type of high-performance coated glass with low radiation/sunlight control composite functions.

In view of the fact that the purpose of this invention is to use the chemical vapor deposition (CVD) process to implement on-line rapid and large-area nitrogen protection industrial scale production of low-radiation/sunshine control composite functional titanium silicide coated glass, the reactants must be easy to gasify, because in relatively Large mass transfer capacity can only be obtained under high vapor pressure. When determining the technical route, the transmission speed of glass production is 5-15m/min, the glass tin bath temperature is 600-1000°C and other basic conditions must be considered. The deposition speed of the designed film and the crystal phase formation conditions should be adapted to it, and take into account The interface between the film and the glass substrate must have a large bonding strength, as well as many factors such as the source of raw materials, cost, production control and environmental pollution control. SiH ₄ -TiCl ₄ -N ₂ atmospheric pressure CVD involved in the present invention can fully meet the above requirements as a basic process route.

Contents of the invention

The object of the present invention is to provide a method for preparing titanium silicide coated glass under nitrogen protection and the titanium silicide coated glass.

The technical scheme that the present invention solves its technical problem adopts is as follows:

1. Titanium silicide coated glass prepared under nitrogen protection:

A thin film is deposited on the common float glass substrate, or a silicon thin film is deposited between the common float glass substrate and the thin film.

The thin film is titanium silicide, titanium silicide composite Si, titanium silicide composite SiC or titanium silicide composite Si ₃ N ₄ .

The titanium silicide in the film has a face-centered orthorhombic crystal structure, and the sheet resistance of the film is 1-100Ω/□.

Two, the preparation method of composite functional titanium silicide coated glass prepared under normal pressure nitrogen protection, the steps of the method are as follows:

1) The reactants are SiH ₄ and TiCl ₄ , N ₂ is used in the reaction chamber during off-line preparation or N 2 , _{H 2 mixed} gas is used as the dilution gas and protective atmosphere in the tin bath during online preparation;

2) SiH ₄ , TiCl ₄ and N ₂ are mixed in the gas mixing chamber; the pressure of each gas at the inlet of the gas mixing chamber is equal, and the pressure is kept between 111325 and 131325 Pa;

3) The constant temperature of TiCl ₄ is 30-70°C; the pipeline through which TiCl ₄ passes is kept warm to 40-80°C;

4) Carrying TiCl ₄ with N ₂ through a gas generator;

5) SiH ₄ , TiCl ₄ and N ₂ are mixed in the gas mixing chamber to obtain reaction gas;

6) The molar concentration of each substance in the reaction gas:

a) SiH ₄ : 1-25%;

b) TiCl ₄ : 0.1-10%;

c) SiH ₄ /TiCl ₄ molar ratio: 1-10;

d) N ₂ or N ₂ , H ₂ mixed gas: 50% to 99%;

7) The pressure of the deposition system is between 101325 and 131325Pa;

8) The temperature of the glass substrate is between 650 and 750°C, and the reaction gas is transported to the glass substrate for reaction to form a TiSi ₂ film. The growth rate of the film is 10 to 50 nanometers per second, and the deposition time is 1 to 15 seconds;

9) The exhaust gas is discharged after absorption treatment.

Adding 1-20% molar concentration of ethylene or methane into the reaction gas forms a TiSi ₂ composite SiC or TiSi ₂ composite TiC film, and the wear resistance and chemical corrosion resistance of the film are further improved.

Adding 1-30% ammonia gas in molar concentration to the reaction gas forms a TiSi ₂ composite Si ₃ N ₄ or TiSi ₂ composite TiN film, and the wear resistance and chemical corrosion resistance of the film are further improved.

The beneficial effect that the present invention has compared with background technology is:

1. Use nitrogen as an inert protective gas to realize online low-cost production of titanium silicide coated glass;

2. Use nitrogen as an inert protective gas to realize online low-cost production of titanium silicide coated glass;

3. Obtain low-resistance face-centered orthorhombic TiSi ₂ coated glass, which has high reflectivity to mid- and far-infrared radiation;

4. The obtained titanium silicide coated glass has a shielding effect on the sunlight, and at the same time, both the reflected light and the transmitted light have a neutral tone. Light gray in transmission and silver in reflection;

5. Modify the titanium silicide coated glass, doping a small amount of active carbon or nitrogen, improve the wear resistance and chemical corrosion resistance of the coated glass, and increase the service life of the coated glass;

6. To modify the titanium silicide coated glass, add excess silicon to improve the bonding firmness of the film and glass;

7. A TiSi ₂ thin film with low resistance is obtained, which has a high reflectivity to the middle and far infrared. At the same time, the reflection and transmission of sunlight are in a neutral tone, eliminating glare interference;

8. Use nitrogen as the inert protective gas to replace Gordon’s use of helium as the inert protective gas for the reaction in US Patent US5167986 and WO89/10209, which greatly reduces production costs, and a small amount of N atoms can also enter the crystal structure during the reaction Interstitial solid solution is formed in the middle, so as to achieve the modification of TiSi ₂ film, and improve the wear resistance and chemical corrosion resistance of the film.

Description of drawings

Fig. 1 is the two-layer structure schematic diagram of coated glass of the present invention;

Fig. 2 is a schematic diagram of the three-layer structure of the coated glass of the present invention.

Detailed ways

As shown in FIG. 1 and FIG. 2 , a thin film 1 is deposited on a common float glass substrate 2 , or a silicon thin film 3 is deposited between the common float glass substrate 2 and the thin film 1 .

The thin film 1 is titanium silicide, titanium silicide composite Si, titanium silicide composite SiC or titanium silicide composite Si ₃ N ₄ .

The titanium silicide in the thin film 1 has a face-centered orthorhombic crystal structure, and the sheet resistance of the thin film 1 is 1-100Ω/□.

Below are embodiments of the present invention:

Embodiment one

The deposition temperature is 680°C, the constant temperature of TiCl ₄ is 60°C, the pipeline through which TiCl ₄ passes is kept warm to 70°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 2, SiH ₄ : 10%, TiCl ₄ : 5%, N ₂ : 85%, the pressure of each gas at the inlet of the gas mixing chamber is 121325Pa, the deposition system pressure is maintained at 105000Pa, and the deposition time is about 10 seconds. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment two

The deposition temperature is 680°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 6, SiH ₄ : 6%, TiCl ₄ : 1%, N ₂ : 93%, the pressure of each gas at the inlet of the gas mixing chamber is 121325Pa, the deposition system pressure is maintained at 105000Pa, and the deposition time is about 10 seconds. A composite thin film of _TiSi2 and Si was formed on a glass substrate. See the attached table for the results.

Embodiment three

The deposition temperature is 680°C, the constant temperature of TiCl ₄ is 35°C, the pipeline through which TiCl ₄ passes is kept warm to 45°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 10, SiH ₄ : 20%, TiCl ₄ : 2%, N ₂ : 78%, the pressure of each gas at the inlet of the gas mixing chamber is 121325Pa, the deposition system pressure is maintained at 105000Pa, and the deposition time is about 10 seconds. A composite thin film of _TiSi2 and Si was formed on a glass substrate. See the attached table for the results.

Embodiment four

The deposition temperature is 650°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 9%, TiCl ₄ : 3%, N ₂ : 88%, the pressure of each gas at the inlet of the gas mixing chamber is 121325Pa, the deposition system pressure is maintained at 105000Pa, and the deposition time is about 10 seconds. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment five

The deposition temperature is 750°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 1.5%, TiCl ₄ : 0.5%, N ₂ : 98%, the pressure of each gas at the inlet of the gas mixing chamber is 121325Pa, the deposition system pressure is maintained at 105000Pa, and the deposition time is about 10 seconds. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment six

The deposition temperature is 700°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 1.5%, TiCl ₄ : 0.5%, N ₂ : 98%, the deposition time is about 10 seconds, the pressure of each gas at the inlet of the gas mixing chamber is 111325Pa, and the deposition system pressure is maintained at 111325Pa. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment seven

The deposition temperature is 700°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 1.5%, TiCl ₄ : 0.5%, N ₂ : 98%, the deposition time is about 10 seconds, the pressure of each gas at the inlet of the gas mixing chamber is 131325Pa, and the deposition system pressure is maintained at 121325Pa. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment eight

The deposition temperature is 680°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 1.5%, TiCl ₄ : 0.5%, N ₂ : 98%, the pressure of each gas at the inlet of the gas mixing chamber is 131325Pa, the pressure of the deposition system is maintained at 121325Pa, and the deposition time is 5 seconds. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment nine

The deposition temperature is 680°C, the constant temperature of TiCl ₄ is 40°C, the pipeline through which TiCl ₄ passes is kept warm to 50°C, and the molar ratio of reaction gas SiH ₄ /TiCl ₄ is adjusted to 3, SiH ₄ : 1.5%, TiCl ₄ : 0.5%, N ₂ : 98%, the pressure of each gas at the inlet of the gas mixing chamber is 131325Pa, the pressure of the deposition system is maintained at 121325Pa, and the deposition time is 15 seconds. Form a _TiSi2 thin film on a glass substrate. See the attached table for the results.

Embodiment ten

The deposition temperature is 700°C, the constant temperature of TiCl _{4 is} 40° _{C, and the pipeline through which TiCl 4 passes is} kept warm to 50 _° C. 10% NH ₃ was injected, N ₂ : 88%, the deposition system pressure was maintained at 121325 Pa, and the deposition time was 10 seconds. A TiSi ₂ /Si ₃ N ₄ composite thin film is formed on a glass substrate. See the attached table for the results.

Embodiment Eleven

The deposition temperature is 700°C, the constant temperature of TiCl ₄ is 40° _{C, and the pipeline through which TiCl 4 passes is kept} warm to 50 _° C. 10% C ₂ H ₄ was injected, N ₂ : 88%, the deposition system pressure was maintained at 121325 Pa, and the deposition time was 10 seconds. A TiSi ₂ /SiC composite thin film is formed on a glass substrate. See the attached table for the results.

Embodiment 12

The deposition temperature is 700°C, the constant temperature of TiCl _{4 is} 40° _{C, and the pipeline through which TiCl 4 passes is} kept warm to 50 _° C. 10% CH ₄ was injected, N ₂ : 88%, the deposition system pressure was maintained at 121325 Pa, and the deposition time was 10 seconds. A TiSi ₂ /SiC composite thin film is formed on a glass substrate. See the attached table for the results.

Embodiment Thirteen

The deposition temperature is 680°C, the temperature of TiCl ₄ is kept at 40°C, the pipeline passed by TiCl ₄ is kept warm to 50°C, and the pressure of the deposition system is maintained at 121325Pa. First, deposit a silicon layer on the glass substrate for 5 seconds, and then adjust the reaction gas SiH ₄ /TiCl ₄ The molar ratio is 2, SiH ₄ : 5%, TiCl ₄ : 2.5%, N ₂ : 97%, and a TiSi ₂ film is deposited for 5 seconds. See the attached table for the results.

Embodiment Fourteen

The deposition temperature is 680°C, the temperature of TiCl ₄ is kept at 40°C, the pipeline passed by TiCl ₄ is kept warm to 50°C, and the pressure of the deposition system is maintained at 121325Pa. First, deposit a silicon layer on the glass substrate for 5 seconds, and then adjust the reaction gas SiH ₄ /TiCl ₄ The molar ratio is 2, SiH ₄ : 5%, TiCl ₄ : 2.5%, doped with 20% NH ₃ , N ₂ : 72.5%, depositing a TiSi ₂ /Si ₃ N ₄ composite film for 5 seconds. See the attached table for the results.

Embodiment 15

The deposition temperature is 680°C, the temperature of TiCl ₄ is kept at 40°C, the pipeline passed by TiCl ₄ is kept warm to 50°C, and the pressure of the deposition system is maintained at 121325Pa. First, deposit a silicon layer on the glass substrate for 5 seconds, and then adjust the reaction gas SiH ₄ /TiCl ₄ The molar ratio is 2, SiH ₄ : 5%, TiCl ₄ : 2.5%, doped with 20% C ₂ H ₄ , N ₂ : 72.5%, and the TiSi ₂ /SiC composite film is deposited for 5 seconds. See the attached table for the results.

Embodiment sixteen

The deposition temperature is 680°C, the temperature of TiCl ₄ is kept at 40°C, the pipeline passed by TiCl ₄ is kept warm to 50°C, and the pressure of the deposition system is maintained at 121325Pa. First, deposit a silicon layer on the glass substrate for 5 seconds, and then adjust the reaction gas SiH ₄ /TiCl ₄ The molar ratio is 2, SiH ₄ : 5%, TiCl ₄ : 2.5%, doped with 20% CH ₄ , N ₂ : 72.5%, and the TiSi ₂ /SiC composite film is deposited for 5 seconds. See the attached table for the results.

Test Results

Schedule I Thin Film Characterization Example crystal phase in thin film Atoms present in thin films Atomic ratio Ti:Si:X in the film membrane thickness Sheet resistance (Ω/□) Embodiment one _TiSi2 Ti, Si 1:1.9 300nm 10 Embodiment two TiSi ₂ , Si Ti, Si 1:3 200nm 28 Embodiment three TiSi ₂ , Si Ti, Si 1:25 260nm 70 Embodiment four _TiSi2 Ti, Si 1:2.2 150nm 45 Embodiment five _TiSi2 Ti, Si 1:2.1 240nm 8 Embodiment six _TiSi2 Ti, Si 1:2.1 170nm 37 Embodiment seven _TiSi2 Ti, Si 1:2.1 140nm 58 Embodiment eight _TiSi2 Ti, Si 1:2.1 100nm 30 Embodiment nine _TiSi2 Ti, Si 1:2.1 300nm 5 Embodiment ten TiSi ₂ , Si ₃ N ₄ Ti, Si,, N 1:1:1 180nm 15 Embodiment Eleven TiSi ₂ , SiC Ti, Si, C 1:1.9:0.05 120nm 30 Embodiment 12 TiSi ₂ , SiC Ti, Si, C 1:1.9:003 140nm 25 Embodiment Thirteen TiSi ₂ , Si Ti, Si 1:4 100nm+80nm 2 Embodiment Fourteen TiSi ₂ , Si, Si ₃ N ₄ Ti, Si, N 1:5:0.3 80nm+80nm 10 Embodiment 15 TiSi ₂ , Si, SiC Ti, Si, C 1:4:0.06 60nm+80nm 30 Embodiment sixteen TiSi ₂ , Si, SiC Ti, Si, C 1:4:0.04 70nm+80nm 25

Attached Table 2 Optical Properties of Films Example UV-visible transmittance (T334nm) UV-visible transmittance (T550nm) Infrared transmittance (T1500nm) Mid-to-far infrared reflectivity Embodiment one 0.5% 15% 11% 90% Embodiment two 0.9% 36% 25% 76% Embodiment Three 1.7% 34% 31% 53% Embodiment four 4% 45% 34% 65% Embodiment five 1.3% 35% 28% 92% Embodiment six 3% 38% 31% 70% Embodiment seven 2% 51% 40% 59% Embodiment eight 3% 38% 31% 75% Embodiment nine 0.3% 15% 10% 95% Embodiment ten 3% 19% 15% 86% Embodiment Eleven 5% 28% 19% 75% Embodiment 12 5% 30% twenty two% 78% Embodiment Thirteen 0.2% 26% 8% 98% Embodiment Fourteen 1.5% 30% 11% 90% Embodiment 15 3.8% 33% 15% 75% Embodiment sixteen 3.4% 31% 14% 78%

Attached Table III Chemical and Mechanical Properties of Thin Films Example Corrosion resistance acid resistance Alkali resistance wear resistance Plating scratch resistance Embodiment one no corrosion no corrosion no corrosion >30000 times no scratches Embodiment two no corrosion no corrosion no corrosion >35000 times no scratches Embodiment Three no corrosion no corrosion no corrosion >35000 times no scratches Embodiment Four no corrosion no corrosion no corrosion >30000 times no scratches Embodiment five no corrosion no corrosion no corrosion >35000 times no scratches Embodiment six no corrosion no corrosion no corrosion >30000 times no scratches Embodiment seven no corrosion no corrosion no corrosion >30000 times no scratches Embodiment eight no corrosion no corrosion no corrosion >30000 times no scratches Embodiment nine no corrosion no corrosion no corrosion >30000 times no scratches Embodiment ten no corrosion no corrosion no corrosion >40000 times no scratches Embodiment Eleven no corrosion no corrosion no corrosion >40000 times no scratches Embodiment 12 no corrosion no corrosion no corrosion >40000 times no scratches Embodiment Thirteen no corrosion no corrosion no corrosion >35000 times no scratches Embodiment Fourteen no corrosion no corrosion no corrosion >40000 times no scratches Embodiment 15 no corrosion no corrosion no corrosion >40000 times no scratches Embodiment sixteen no corrosion no corrosion no corrosion >40000 times no scratches

The crystal phase in the film was tested by X-ray diffractometer.

Film thickness was measured by scanning electron microscopy.

The elements contained in the film and their proportions are tested by EDX.

The mid-to-far infrared reflectivity is calculated by the formula R _IR =(1+0.0053RS ₎ ^-2 , where R _IR and R _S represent the mid-to-far infrared reflectivity and the sheet resistance of the film, respectively.

The corrosion resistance test was soaked in a 5% NaCl solution at room temperature for more than 5 months.

The acid resistance test is to soak in a solution with a pH value of 5 to 60°C for 36 hours.

The alkali resistance test is to soak in a solution with a pH value of 9 to 60°C for 36 hours.

The wear resistance test is to place the sample horizontally on the electric vibrator, the cloth roll moves and rubs on the surface of the sample under the pressure of 100g/cm ² , and check whether the coating is worn with a multimeter, the number of wear resistance = 2 × vibration frequency × time .

The scratch resistance test is to scratch hard with iron nails or pins.

Claims (4)

1. A method for preparing titanium silicide coated glass under nitrogen protection, characterized in that the steps of the method are as follows: 1) The reactants are SiH ₄ and TiCl ₄ , N ₂ is used in the reaction chamber during off-line preparation or N 2 , _{H 2 mixed} gas is used as the dilution gas and protective atmosphere in the tin bath during online preparation; 2) SiH ₄ , TiCl ₄ and N ₂ are mixed in the gas mixing chamber; the pressure of each gas at the inlet of the gas mixing chamber is equal, and the pressure is kept between 111325 and 131325 Pa; 3) The constant temperature of TiCl ₄ is 30-70°C; the pipeline through which TiCl ₄ passes is kept warm to 40-80°C; 4) Carrying TiCl ₄ with N ₂ through a gas generator; 5) SiH ₄ , TiCl ₄ and N ₂ are mixed in the gas mixing chamber to obtain reaction gas; 6) The molar concentration of each substance in the reaction gas: a) SiH ₄ : 1-25%; b) TiCl ₄ : 0.1-10%; c) SiH ₄ /TiCl ₄ molar ratio: 1-10; d) N ₂ or N ₂ , H ₂ mixed gas: 50% to 99%; 7) The pressure of the deposition system is between 101325 and 131325Pa; 8) The temperature of the glass substrate is between 650 and 750°C, and the reaction gas is transported to the glass substrate for reaction to form a TiSi ₂ film. The growth rate of the film is 10 to 50 nanometers per second, and the deposition time is 1 to 15 seconds; 9) The exhaust gas is discharged after absorption treatment. 2. A method for preparing titanium silicide coated glass under nitrogen protection according to claim 1, characterized in that ethylene or methane with a molar concentration of 1 to 20% is added to the reaction gas to form TiSi ₂ composite SiC or TiSi ₂ composite The wear resistance and chemical corrosion resistance of the thin film of TiC are further improved. 3. A method for preparing titanium silicide-coated glass under nitrogen protection according to claim 1, characterized in that: ammonia gas with a molar concentration of 1 to 30% is added to the reaction gas to form TiSi ₂ composite Si ₃ N ₄ or TiSi ₂ Composite TiN film, the wear resistance and chemical corrosion resistance of the film are further improved. 4. The titanium silicide coated glass prepared by the method according to claim 1 is to deposit a layer of thin film (1) on a common float glass substrate (2), or to deposit a layer of thin film (1) on a common float glass substrate (2) and thin film (1). Re-deposit a layer of silicon thin film (3) between; It is characterized in that: The film (1) is titanium silicide, titanium silicide composite Si, titanium silicide composite SiC or titanium silicide composite Si ₃ N ₄ ; The titanium silicide in the film (1) has a face-centered orthorhombic crystal structure, and the sheet resistance of the film (1) is 1-100Ω/□.

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