阅读说明：本技术 一种镀膜玻璃的制备方法及装置 (Preparation method and device of coated glass ) 是由 李佳明 颜悦 姜良宝 李晓宇 潘兴洁 刘家希 付子怡 于 2021-07-27 设计创作，主要内容包括：本发明是一种镀膜玻璃的制备方法及装置,本发明技术方案通过优化红外灯阵辐射的红外波长,选择一个功能层薄膜与化学强化玻璃对红外光吸收度差异最大的波长范围,提高了功能层薄膜对红外光吸收的同时降低强化玻璃对红外波长的吸收,导致功能薄膜温度高于化学强化玻璃温度,既改善功能层薄膜光电性能,又降低加热过程对强化玻璃力学性能的不利影响,极大地降低了化学强化玻璃强度衰减。红外灯阵与温度反馈调节装置连接,温度反馈调节装置可以实时监测基底材料的温度并控制加热功率,精准按照加热工艺进行调控。(The invention relates to a preparation method and a device of coated glass, which are characterized in that infrared wavelength radiated by an infrared lamp array is optimized, a wavelength range with the largest difference between infrared absorption degrees of a functional layer film and chemically strengthened glass is selected, the absorption of the functional layer film on infrared light is improved, the absorption of the strengthened glass on the infrared wavelength is reduced, the temperature of the functional layer film is higher than that of the chemically strengthened glass, the photoelectric property of the functional layer film is improved, the adverse effect of a heating process on the mechanical property of the strengthened glass is reduced, and the intensity attenuation of the chemically strengthened glass is greatly reduced. The infrared lamp array is connected with the temperature feedback adjusting device, and the temperature feedback adjusting device can monitor the temperature of the substrate material in real time and control the heating power, and can accurately regulate and control according to the heating process.)

1. A preparation method of coated glass adopts an infrared heating mode to heat a substrate material (11), a magnetron sputtering cathode target head (5) clamped by a robot arm moves according to a preset coating path to coat the surface of the substrate material (11), and is characterized in that: the substrate material (11) is chemically strengthened glass, and when an ITO film or an AZO film is prepared on the substrate material, the infrared heating wavelength is set to be 2000nm-2700nm, so that the forming temperature of the ITO film or the AZO film is 150 ℃ to 250 ℃ higher than that of the substrate material (11).

2. The method for producing a coated glass according to claim 1, characterized in that: the coated glass is arranged on a substrate (11) from inside to outsideSecond preparation of SiO as transition layer (12)₂Or TiO₂Film, ITO or AZO film as functional layer (13), Nb as antireflection layer (14)₂O₅Or SiO₂Film, Si as wear-resistant layer (15)₃N₄A film.

3. The method for producing a coated glass according to claim 1, characterized in that: the thickness of the base material (11) is 1.5mm-5.0 mm.

4. The method for producing a coated glass according to claim 1 or 3, characterized in that: the thickness of the ITO or AZO film is 250nm-350 nm.

5. The method for producing a coated glass according to claim 4, characterized in that: SiO as a transition layer (12)₂Or TiO₂Nb as an anti-reflection layer (14) having a film thickness of 20nm to 40nm₂O₅Or SiO₂The thickness of the film is 30nm-40nm, and Si is used as the wear-resistant layer (15)₃N₄The thickness of the film is 80nm-150 nm.

6. The device for preparing the coated glass according to claim 1, which comprises a vacuum chamber (1), a vacuum pump set (2), a stage and driving system (4), a magnetron sputtering target system, an infrared heating system, a water cooling system, an inflation system and a control system, and is characterized in that: a mechanical arm (3) is arranged in the vacuum chamber (1) to clamp the magnetron sputtering cathode target head (5) and move according to a set coating path, and a target frame (6) is arranged at the back of the mechanical arm (3) to fix the cathode target head (7);

the vacuum chamber (1) is internally provided with an upright object stage (8) with A, B double faces, the object stage (8) is driven to rotate through the object stage and a driving system (4), an infrared lamp array (9) is arranged on the object stage and is connected with a temperature feedback adjusting device (10) to heat a substrate material (11).

7. The apparatus of claim 6, wherein: the surface of the A, B double-sided objective table (8) is a plane or a curved surface.

8. The apparatus of claim 6, wherein: an air inlet pipeline for process gas is arranged on the inner wall of the vacuum chamber (1).

9. The apparatus of claim 6, wherein: the target frame (6) is fixed on the base of the mechanical arm (3) and moves along with the base.

10. The apparatus of claim 6, wherein: the heating temperature of the infrared lamp array (9) is 100-600 ℃, and the temperature of the substrate material (11) is monitored in real time through a temperature measuring device.

Technical Field

The invention relates to a preparation method and a device of coated glass, belonging to the technical field of surface treatment of materials.

Background

Coated glass with low resistance and low optical loss is widely applied to the fields of liquid crystal displays, electrochromic windows, curtain wall glass of high-rise buildings, heat-conducting glass (anti-icing and demisting) of airplanes and high-speed trains and the like. The electrical property and the optical property of a common single-layer functional film are difficult to meet the use requirement at the same time, and multiple layers of thin films are required to be superposed to form a composite structure to realize the properties of low resistance (5-8 omega/□), high light transmittance (80%), good chemical stability and the like. At present, the conventional heating elements such as metal wires, metal strips and the like are often used for plating the thin film glass with low resistance and low optical loss at high temperature. However, the high-temperature coating device adopting the traditional heating mode has some disadvantages, such as long time for heating and cooling and low efficiency. For strengthened glass, exposure to high temperatures for extended periods of time reduces the glass surface stress and reduces the glass' service strength. When the traditional heating element is used for heating glass, the temperature rise of the inner structure of the cavity is large, but the temperature of the coating device adopting the traditional heating element is limited to be generally not more than 250 ℃ because the mechanical arm, the vacuum motor and other parts are not resistant to high temperature, and the optical performance and the electrical performance of the coated film cannot meet the use requirements. In addition, for plating a low-resistance and low-optical-loss film on curved glass, the uniformity of the film sputtered by using a position-fixed cathode target is poor. If 1 objective table is arranged in the coating device, only 1 piece of glass can be coated in each furnace, and the coating device has the defects of long time consumption, low efficiency, high cost and the like. If a plurality of object stages are arranged in the coating device, the coating efficiency can be improved, but the space size of the coating device is increased, the equipment cost is increased, and the occupied area of the device is increased. Therefore, there is an urgent need for a coating apparatus that can improve the coating efficiency, save the production cost, increase the temperature range of high-temperature coating, and produce multi-layer thin film glass having good uniformity, low resistance, and low optical loss.

Disclosure of Invention

The invention provides a method and a device for preparing coated glass aiming at the defects in the prior art, and aims to solve the problem of contradiction between the photoelectric property of a functional layer film and the mechanical property of chemically strengthened glass in the high-temperature coating process. The preparation method of the invention ensures that the film has the advantages of good uniformity, low resistance, high light transmittance, good wear resistance and better mechanical property of glass, and in addition, the technical scheme of the invention also utilizes the high-temperature film coating device capable of turning samples on two sides to prepare the film glass which is hopeful to be used in the fields of liquid crystal displays, electrochromic windows, curtain wall glass of high-rise buildings, heat-conducting glass (anti-icing and demisting) of airplanes and high-speed trains, electromagnetic shielding glass and the like.

The purpose of the invention is realized by the following technical scheme:

in the preparation method of the coated glass in the technical scheme of the invention, the substrate material 11 is heated in an infrared heating mode, the magnetron sputtering cathode target head 5 clamped by a robot arm moves according to a preset coating path to coat the surface of the substrate material 11, and the preparation method is characterized in that: the substrate material 11 in the method is chemically strengthened glass, when an ITO film or an AZO film is prepared on the substrate material 11, the wavelength of infrared heating is set to be 2000nm-2700nm, and the setting enables the forming temperature of the ITO film or the AZO film to be 150 ℃ to 250 ℃ higher than the temperature of the substrate material 11.

In one embodiment, the coated glass is prepared by sequentially preparing SiO as a transition layer 12 on a substrate material 11 from inside to outside₂Or TiO₂Film, ITO or AZO film as functional layer 13, Nb as antireflection layer 14₂O₅Or SiO₂Film, Si as wear-resistant layer 15₃N₄A film.

In one implementation, the base material 11 has a thickness of 1.5mm to 5.0 mm.

Further, the thickness of the ITO or AZO film is 250nm-350 nm.

Further, SiO as the transition layer 12₂Or TiO₂A film thickness of 20nm to 40nm, Nb as the antireflection layer 14₂O₅Or SiO₂The film has a thickness of 30nm-40nm and is used as the wear-resistant layer 15Si of (2)₃N₄The thickness of the film is 80nm-150 nm.

The technical scheme of the invention provides a device for the preparation method of the coated glass, which comprises a vacuum chamber 1, a vacuum pump group 2, an objective table and driving system 4, a magnetron sputtering target system, an infrared heating system, a water cooling system, an inflation system and a control system, and is characterized in that: a mechanical arm 3 is arranged in the vacuum chamber 1 to clamp the magnetron sputtering cathode target 5 and move according to a set coating path, and a target frame 6 is arranged at the back of the mechanical arm 3 to fix a cathode target 7;

a vertical A, B double-sided objective table 8 is arranged in the vacuum chamber 1, the objective table 8 is driven to rotate through an objective table and driving system 4, an infrared lamp array 9 is arranged on the objective table, and the infrared lamp array is connected with a temperature feedback adjusting device 10 to heat a substrate material 11.

In practice, the A, B double-sided stage 8 has a flat or curved surface.

In practice, an inlet line for process gas is provided on the inner wall of the vacuum chamber 1.

In practice, the target 6 is fixed to the base of the robot arm 3 and moves with it.

In the implementation, the heating temperature of the infrared lamp array 9 is 100-600 ℃, the temperature of the substrate material 11 is monitored in real time through a temperature measuring device, and the output heating power is adjusted in real time according to the heating process parameters.

The infrared lamp arrays adopted by the technical scheme of the invention are arranged according to the surface shape of the substrate material, and the shape of the infrared lamp arrays can be regular or irregular, so that the curved glass can be uniformly heated in the film coating process, and the uniform performance of the coated film is finally ensured. In the experimental process, an applicant uses an ultraviolet-visible-near infrared spectrophotometer to respectively test the absorption spectrum of the ITO film or the AZO film and the absorption spectrum of the chemically strengthened glass, and the wavelength range with the largest difference value of the infrared absorbances of the ITO film or the AZO film and the chemically strengthened glass is calculated from the spectra to be 2000nm-2700 nm. The coated glass is heated in the infrared wavelength range, so that the temperature of the ITO film or the AZO film can be raised to 150-250 ℃ higher than that of the chemically strengthened glass. The higher temperature of the functional layer film is beneficial to improving the crystallinity of the plated film, thereby improving the optical property and the electrical property of the film. The chemically strengthened glass at a relatively low temperature is beneficial to reducing the surface stress attenuation and the strength attenuation of the glass caused by temperature rise in the high-temperature plating process.

According to the technical scheme, the infrared wavelength radiated by the infrared lamp array is optimized, the wavelength range with the largest difference between the infrared absorption degrees of the functional layer film and the chemically strengthened glass is selected, the absorption of the functional layer film to the infrared light is improved, the absorption of the strengthened glass to the infrared wavelength is reduced, the temperature of the functional layer film is higher than that of the chemically strengthened glass, the photoelectric property of the functional layer film is improved, the adverse effect of the heating process on the mechanical property of the strengthened glass is reduced, and the intensity attenuation of the chemically strengthened glass is greatly reduced. The infrared lamp array is connected with the temperature feedback adjusting device, and the temperature feedback adjusting device can monitor the temperature of the substrate material in real time and control the heating power, and can accurately regulate and control according to the heating process.

In addition, the technical scheme of the invention also designs a high-temperature coating device capable of turning samples on two sides to match the implementation of the method, the device is provided with a robot arm in a vacuum chamber, different magnetron sputtering cathode target heads can be clamped, the robot arm moves according to the woven coating path, when the coating is carried out on the curved glass, the target base distance between the magnetron sputtering cathode target heads and the surface of the glass can be kept unchanged, and the uniformity of the prepared film is good. The target stand is arranged on the back of the robot and used for fixing the cathode target heads, so that different types of cathode target heads can be automatically replaced on the premise of not damaging the vacuum environment, and the plating efficiency of the multilayer film is improved. Contain a two-sided objective table of A, B of erectting inside the vacuum chamber, drive the objective table through the motion of vacuum motor and rotate, improved coating film efficiency under the space size prerequisite that does not increase the coating film device, practiced thrift manufacturing cost. The infrared lamp array is arranged on the objective table, and compared with the traditional resistance wire heating mode and other modes, the infrared heating technology has the characteristics of directional heating (mainly heating coated glass), high heating and cooling rates and the like, reduces the temperature rise of a mechanical arm and a vacuum motor in the heating process, and can realize plating at a higher temperature than the traditional heating mode.

The heating temperature of the device is 100-600 ℃, compared with the defect that the directional heating in the traditional resistance heating mode is poor, the device adopts the mode of heating the whole interior of the coating device, so that the problem of temperature limitation of parts which cannot resist high temperature, such as a mechanical arm, a vacuum motor and the like, is solved, and in the traditional resistance heating mode, the heating temperature generally cannot exceed 250 ℃ so as to meet the temperature requirement of the parts which cannot resist high temperature, such as the mechanical arm, the vacuum motor and the like. The solution of the technical scheme of the invention to the temperature realizes higher coating temperature and lower ambient temperature, has great benefits for improving the optical performance and the electrical performance of the film, can reduce the thickness of the film, simultaneously has the performances of low resistance (5-8 omega/□), high light transmittance (80%), good chemical stability and the like, reduces the heating energy loss and the waste of coating materials, and improves the quality of the coated glass. The method has the advantages of energy conservation, environmental protection, high efficiency, low cost, excellent performance, suitability for industrial production and the like.

Drawings

FIG. 1 is a schematic structural view of a high-temperature coating device capable of overturning a sample on two sides according to the present invention;

FIG. 2 is a schematic view of a reversible A, B double-sided carrier structure according to the present invention;

FIG. 3 is a coated glass prepared by the high temperature coating apparatus capable of turning samples on both sides according to the present invention;

Detailed Description

The technical scheme of the invention is further detailed in the following by combining the drawings and the embodiment:

referring to attached drawings 1 and 2, the device for preparing the coated glass comprises a vacuum chamber 1, a vacuum pump set 2, a stage and driving system 4, a magnetron sputtering target system, an infrared heating system, a water cooling system, an inflation system and a control system, and is characterized in that: a mechanical arm 3 is arranged in the vacuum chamber 1 to clamp the magnetron sputtering cathode target 5 and move according to a set coating path, and a target frame 6 is arranged at the back of the mechanical arm 3 to fix a cathode target 7; the target frame 6 is fixed on the base of the robot arm 3 and moves along with the same, a vertical A, B double-sided stage 8 is arranged in the vacuum chamber 1, the surface of the A, B double-sided stage 8 is a curved surface,

the objective table 8 is driven to rotate through the objective table and driving system 4, the infrared lamp array 9 is arranged on the objective table and is connected with the temperature feedback adjusting device 10, and the substrate material 11 is heated.

An inlet pipe for process gas is provided on the inner wall of the vacuum chamber 1.

Example one

The preparation of the coated glass by adopting the device comprises the following steps:

step one, respectively clamping two pieces of chemically strengthened glass with the surface compressive stress of 850MPa and the thickness of 2.0mm on a reversible double-sided objective table 8, closing a vacuum chamber door of a high-temperature coating device, and opening a vacuum pump set 2 to vacuumize a vacuum chamber 1;

step two, adjusting the position of the object stage 8 until the surface A of the object stage faces the mechanical arm (3);

step three, turning on a power supply of an infrared lamp array with the wavelength of 2400nm on the A-surface objective table, setting heating process parameters through a temperature feedback device, heating the substrate material 11, wherein the heating parameters are that the temperature is increased to 350 ℃ at the heating rate of 50 ℃/min, then keeping the temperature at 350 ℃, and measuring that the temperature of the chemically strengthened glass is increased to 180 ℃ in the process;

setting coating process parameters including sputtering power and power supply duty ratio, and introducing process gases Ar and O₂Gas, turn on magnetron sputtering SiO₂A direct current pulse power supply of the cathode target head 5 starts the robot arm 3 at the same time, and moves according to the programmed coating path;

step five, coating a layer of SiO₂After the film is coatedTurn off magnetron sputtering of SiO₂The power supply of the cathode target head is turned off, the process gas is turned off, the power supply of the infrared lamp array is turned off, the path of the cathode target head is automatically taken and changed, and the robot arm clamps the clamped SiO₂The cathode target is placed on the target frame, and then the cathode target for plating the next layer of ITO film is clamped;

step six, the step three, the step four and the step five can be repeated, and SiO is plated on the surface of the glass arranged on the surface A of the objective table₂/ITO/Nb₂O₅/Si₃N₄A film;

turning on a vacuum motor to turn over the objective table, and enabling the surface B of the objective table to face the robot arm;

step eight, turning on a power supply of an infrared lamp array with the wavelength of 2400nm on a B-surface objective table, setting heating process parameters through a temperature feedback device, heating the substrate material, wherein the heating parameters are increased to 500 ℃ at the heating rate of 100 ℃/min, then keeping the temperature at 500 ℃, and measuring the temperature rise of the chemically strengthened glass to 335 ℃ in the process;

step nine, setting coating process parameters including sputtering power and power supply duty ratio, and introducing process gases Ar and O₂Gas, turn on magnetron sputtering SiO₂A direct-current pulse power supply of the cathode target head starts a robot arm at the same time, and the robot arm moves according to the programmed coating path;

step ten, coating a layer of SiO₂After the film is formed, the magnetron sputtering SiO is closed₂The power supply of the cathode target head is turned off, the process gas is turned off, the power supply of the infrared lamp array is turned off, the path of the cathode target head is automatically taken and changed, and the robot arm clamps the clamped SiO₂The cathode target is placed on the target frame, and then the cathode target for plating the next layer of ITO film is clamped; as shown in fig. 3;

eleventh, the eighth, ninth and tenth steps can be repeated, and SiO is plated on the surface of the glass arranged on the surface B of the objective table₂/ITO/Nb₂O₅/Si₃N₄A thin film;

step twelve, after the film coating is finished, introducing Ar gas until the temperature of the two pieces of chemically strengthened glass is reduced to 70 ℃, closing the Ar gas, closing a vacuum pump set, introducing air to an atmospheric state, opening a door of a vacuum chamber, and taking out the two pieces of coated glass after the coating is finished;

the properties of the glass with low resistance and low optical loss prepared by the method and the properties of the glass prepared by the traditional coating device under the same process parameters are shown in the following table.

As can be seen from the table above, compared with the coated glass prepared by the traditional coating device, the coated glass prepared by the double-side-turning high-temperature coating device provided by the invention has the advantages that the surface resistance of the coated glass prepared by the method provided by the invention is superior to that of the coated glass prepared by the traditional coating method, the transmittance in a visible light range is higher, the surface compressive stress attenuation of the chemically strengthened glass substrate is only 43.28% and 36.32% of that of the chemically strengthened glass substrate, and the strength of the chemically strengthened glass is improved.

Example two

The method for preparing the coated glass by using the double-side turnover high-temperature coating device comprises the following steps:

respectively clamping two pieces of chemically strengthened glass with the surface compressive stress of 900MPa and the thickness of 5.0mm on a reversible double-sided objective table, closing a vacuum chamber door of the high-temperature coating device, and opening a vacuum pump set to vacuumize a vacuum chamber.

And step two, adjusting the position of the object stage until the surface A of the object stage faces the robot arm.

And step three, turning on a power supply of an infrared lamp array with the wavelength of 2500nm on the A-surface objective table, setting heating process parameters through a temperature feedback device, heating the substrate material, wherein the heating parameters are increased to 200 ℃ at the heating rate of 50 ℃/min, then keeping the temperature at 200 ℃, and measuring the temperature rise of the chemically strengthened glass to 53 ℃ in the process.

Setting coating process parameters including sputtering power and power supply duty ratio, and introducing process gases Ar and O₂Gas, turn on magnetron sputtering SiO₂DC pulse power supply of cathode target head, and starting at the same timeAnd (4) moving the robot arm according to the woven coating path.

Step five, coating a layer of SiO₂After the film is formed, the magnetron sputtering SiO is closed₂The power supply of the cathode target head is turned off, the process gas is turned off, the power supply of the infrared lamp array is turned off, the path of the cathode target head is automatically taken and changed, and the robot arm clamps the clamped SiO₂The cathode target is placed on the target frame, and then the cathode target for plating the next layer of ITO film is clamped.

Step six, the step three, the step four and the step five can be repeated, and SiO is plated on the surface of the glass arranged on the surface A of the objective table₂/ITO/SiO₂/Si₃N₄A film.

And step seven, turning on the vacuum motor to turn over the objective table, and enabling the surface B of the objective table to face the robot arm.

And step eight, turning on a power supply of an infrared lamp array with the wavelength of 2500nm on the B-surface objective table, setting heating process parameters through a temperature feedback device, heating the substrate material, wherein the heating parameters are increased to 600 ℃ at the heating rate of 100 ℃/min, then keeping the temperature at 600 ℃, and measuring the temperature rise of the chemically strengthened glass to 407 ℃ in the process.

Step nine, setting coating process parameters including sputtering power and power supply duty ratio, and introducing process gases Ar and O₂Gas, turn on magnetron sputtering SiO₂And a direct-current pulse power supply of the cathode target head starts the robot arm at the same time, and the robot arm moves according to the programmed coating path.

Step ten, coating a layer of SiO₂After the film is formed, the magnetron sputtering SiO is closed₂The power supply of the cathode target head is turned off, the process gas is turned off, the power supply of the infrared lamp array is turned off, the path of the cathode target head is automatically taken and changed, and the robot arm clamps the clamped SiO₂The cathode target is placed on the target frame, and then the cathode target for plating the next layer of ITO film is clamped. As shown in fig. 3.

Eleventh, the eighth, ninth and tenth steps can be repeated, and SiO is plated on the surface of the glass arranged on the surface B of the objective table₂/ITO/SiO₂/Si₃N₄A thin film.

And step twelve, introducing Ar gas after the film coating is finished until the temperature of the two pieces of chemically strengthened glass is reduced to 70 ℃, closing the Ar gas, closing a vacuum pump set, introducing air to an atmospheric state, opening a door of the vacuum chamber, and taking out the two pieces of coated glass after the coating is finished.

The properties of the glass with low resistance and low optical loss prepared by the method and the properties of the glass prepared by the traditional coating device under the same process parameters are shown in the following table.

As can be seen from the above table, compared with the coated glass prepared by the traditional coating device, the coated glass prepared by the double-side-overturning high-temperature coating device provided by the invention has the advantages that the surface resistance of the coated glass prepared by the method provided by the invention is lower than that of the coated glass prepared by the traditional coating method, the transmittance in a visible light range is higher, the surface compressive stress attenuation of the chemically strengthened glass substrate is only 25.0% and 34.0% of that of the chemically strengthened glass substrate, and the strength of the chemically strengthened glass is improved.