阅读说明：本技术 一种高透过宽色系盖板玻璃的制备方法 (Preparation method of cover plate glass with high transmittance and wide color system ) 是由 杨扬 李刚 王天齐 姚婷婷 金克武 沈红雪 彭赛奥 夏申江 程海波 王东 甘治平 于 2020-06-01 设计创作，主要内容包括：本发明公开一种高透过宽色系盖板玻璃的制备方法,包括以下步骤：制作玻璃基板、刻蚀织构化结构、沉积SiO2保护层和沉积SiNX介质干涉层；本发明采用液相法对玻璃基板上表面进行刻蚀,使玻璃基板上表面形成短程有序、长程无序的织构化结构,提高了可见光的透过率,增加了通过漫反射衍射效应形成的结构色彩的饱和度；且采用等离子体清洗技术处理玻璃基板织构化结构的上表面及光滑的下表面,能有效提高后续附着膜层的结合力,同时,在高温大气环境下,SiO2保护层能够提高玻璃基板整体的耐磨、耐蚀性,增加对太阳光的有效透过率,另外,通过调整磁控溅射制备的SiNX介质干涉层的厚度,能利用光的干涉效应产生不同的结构色彩。(The invention discloses a preparation method of cover plate glass with high transmittance and wide color system, which comprises the following steps: manufacturing a glass substrate, etching a textured structure, depositing a SiO2 protective layer and depositing a SiNX medium interference layer; according to the invention, the upper surface of the glass substrate is etched by adopting a liquid phase method, so that a short-range ordered and long-range disordered textured structure is formed on the upper surface of the glass substrate, the transmittance of visible light is improved, and the saturation of structural colors formed by a diffuse reflection diffraction effect is increased; the upper surface and the smooth lower surface of the textured structure of the glass substrate are treated by adopting a plasma cleaning technology, the binding force of a subsequent adhesion film layer can be effectively improved, meanwhile, under a high-temperature atmospheric environment, the whole wear resistance and corrosion resistance of the glass substrate can be improved by the SiO2 protective layer, the effective transmittance to sunlight is increased, and in addition, different structural colors can be generated by utilizing the interference effect of light by adjusting the thickness of the SiNX medium interference layer prepared by magnetron sputtering.)

1. A preparation method of cover plate glass with high transmittance and wide color system is characterized in that: the method comprises the following steps:

the method comprises the following steps: manufacture of glass substrate

Preparing two pieces of soda-lime-silica glass, performing edge sealing treatment on four sides of the two pieces of glass by using UV glue, curing the glass by using a curing machine, cleaning the glass to remove edge overflow glue, and removing foreign matters on the surface of the glass by using pure water to prepare a glass substrate;

step two: etching textured structure

Preparing a glass etching solution by a liquid phase method, placing the glass etching solution into an etching groove, heating to 40-50 ℃, placing a glass substrate into the etching groove, etching the upper surface of the glass substrate for 5-30min by using the etching solution, cleaning the etched glass substrate after the etching is finished, and forming a textured structure with concave and convex parts on the upper surface of the glass substrate;

step three: deposition of SiO2 protective layer

Placing the glass substrate with the textured structure into a plasma cleaning chamber, cleaning the textured structure surface of the glass substrate for 10-30min, turning off a radio frequency power supply after cleaning, standing for 30min, transferring the glass substrate to a magnetron sputtering chamber under the condition of not breaking vacuum after the temperature of the upper surface of the glass substrate is cooled to room temperature, and sputtering and growing a SiO2 protective layer with the thickness of 30-90nm on the textured structure surface of the glass substrate by a magnetron sputtering technology;

step four: depositing SiNX medium interference layer

And D, after breaking vacuum and taking out the glass substrate in the step II, turning over and putting the glass substrate into a plasma cleaning chamber, cleaning the lower surface of the glass substrate for 10-30min, turning off a radio frequency power supply after cleaning, standing for 30min, transferring the glass substrate to a magnetron sputtering chamber under the condition of not breaking vacuum after the temperature of the lower surface of the glass substrate is cooled to room temperature, and sputtering and growing a SiNX medium interference layer with the thickness of 30-600nm on the lower surface of the glass substrate by a magnetron sputtering technology.

2. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein the method comprises the following steps: in the first step, two pieces of soda-lime-silica glass with the thickness of 3.2mm are prepared.

3. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein the method comprises the following steps: in the second step, the formula of the glass etching liquid is as follows: the water-soluble hydrogen fluoride is prepared by mixing 60-70% of dilute hydrochloric acid, 10-15% of ammonium hydrogen fluoride, 2-8% of oxalic acid and the balance of water according to the weight ratio.

4. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein in the third step, the glass substrate with textured structure is placed in a plasma cleaning chamber, and the bulk vacuum degree is set to be less than or equal to 5 × 10^{- 3}Pa, working pressure of 1-10 × 10^-1Pa, Ar gas flow of 30-40sccm, incident angle of 20-45 degrees and radio frequency power of 200 w.

5. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein the method comprises the following steps: in the third step, the magnetron sputtering technology specifically comprises the following steps: the method comprises the steps of adopting a SiO2 ceramic target material, Ar gas as a process gas, enabling the flow rate of the process gas to be 40-60sccm, adopting a radio frequency power supply to ionize the Ar gas, enabling the power of the radio frequency power supply to be 100-250w, and enabling the sputtering time to be 5-12 min.

6. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein the method comprises the following steps: in the fourth step, the glass substrate is placed into a plasma cleaning chamber in a turnover mode, the vacuum degree of the body is set to be less than or equal to 5 multiplied by 10 < -3 > Pa, the working pressure is 1 to 10 multiplied by 10 < -1 > Pa, the Ar gas flow is 30 to 40sccm, the incident angle is 20 to 45 degrees, and the radio frequency power is 200 w.

7. The method for preparing cover glass with high transmittance and wide color system according to claim 1, wherein the method comprises the following steps: in the fourth step, the magnetron sputtering technology specifically comprises the following steps: si3N4 ceramic target material is adopted, Ar gas is adopted as process gas, the flow rate of the process gas is 40-60sccm, N2 gas is adopted as reaction gas, the flow rate of the reaction gas is 40-60sccm, a radio frequency power supply is adopted to ionize the Ar gas, the power of the radio frequency power supply is 150-200w, and the reaction sputtering is carried out for 5-90 min.

Technical Field

The invention relates to the technical field of glass preparation, in particular to a preparation method of cover plate glass with high transmittance and wide color system.

Background

The cover plate glass has good light transmission and high strength, and is widely applied to a plurality of fields, such as crystalline silicon solar cells, thin-film solar cells, flat plate collectors, low-E glass and the like, however, the current focus of attention is only limited to the research on the performances such as transmittance, strength, hardness, weather resistance and the like of the glass, and the related reports on how to harmoniously and uniformly apply the material and the surrounding environment are less, for example, the traditional solar module only has two choices of blue and black, which severely restricts the development and application of the cover plate glass in the Building Integrated Photovoltaic (BIPV) industry;

in the application of the solar energy system component, the cover plate glass which does not affect the transmittance of the cover plate glass and has the structural coloring function is endowed with the concept of building aesthetics of the glass which is a traditional material compared with the traditional cover plate glass, and the glass generates various colors through the interference effect of light, so that the large-scale application of the solar energy component in the building field is favorably improved, and the organic combination and the common development of the component and a building are realized;

at present, when preparing the colored cover plate glass, the following methods are generally adopted:

firstly, the colored cover plate glass is obtained by adjusting the components of the cover plate glass, early glass manufacturers add coloring agents into colorless glass to enable the glass to become colored glass, but the technology belongs to chemical coloring, and the transmittance of the glass is sharply reduced due to the selective absorption of the coloring agents to light, so that the visible light transmittance is only 40-50 percent

Secondly, the surface of the cover glass is plated with a dielectric film, the position of the reflection center wavelength is adjusted by adjusting the structural design of a film system of the cover glass, the reflected light is changed on the spectrum, so as to obtain different surface colors of the glass, and a patent of laminated glass window with color reflection and high sunlight transmittance suitable for a solar energy system (publication No. CN 104736338A) discloses a laminated glass window with color reflection, the technical scheme adopted in the patent requires more than two layers of high and low refractive index materials to be stacked to form different colors, the preparation process is complicated, the thickness of each layer of film is difficult to accurately control, therefore, the overall coloring effect is influenced, and in addition, the large-scale production cost is higher, so the invention provides the preparation method of the cover plate glass with high transmittance and wide color system to solve the problems in the prior art.

Disclosure of Invention

In view of the above problems, an object of the present invention is to provide a method for manufacturing a high-transmittance and wide-color cover glass, which has a simple manufacturing process, can obtain a color cover glass with a textured surface structure and controllable coating uniformity, effectively reduces production cost, and is easy to realize industrialization.

In order to realize the purpose of the invention, the invention is realized by the following technical scheme: a preparation method of cover plate glass with high transmittance and wide color system comprises the following steps:

the method comprises the following steps: manufacture of glass substrate

Preparing two pieces of soda-lime-silica glass, performing edge sealing treatment on four sides of the two pieces of glass by using UV glue, curing the glass by using a curing machine, cleaning the glass to remove edge overflow glue, and removing foreign matters on the surface of the glass by using pure water to prepare a glass substrate;

step two: etching textured structure

Preparing a glass etching solution by a liquid phase method, placing the glass etching solution into an etching groove, heating to 40-50 ℃, placing a glass substrate into the etching groove, etching the upper surface of the glass substrate for 5-30min by using the etching solution, cleaning the etched glass substrate after the etching is finished, and forming a textured structure with concave and convex parts on the upper surface of the glass substrate;

step three: deposition of SiO2 protective layer

Placing the glass substrate with the textured structure into a plasma cleaning chamber, cleaning the textured structure surface of the glass substrate for 10-30min, turning off a radio frequency power supply after cleaning, standing for 30min, transferring the glass substrate to a magnetron sputtering chamber under the condition of not breaking vacuum after the temperature of the upper surface of the glass substrate is cooled to room temperature, and sputtering and growing a SiO2 protective layer with the thickness of 30-90nm on the textured structure surface of the glass substrate by a magnetron sputtering technology;

step four: depositing SiNX medium interference layer

And D, after breaking vacuum and taking out the glass substrate in the step II, turning over and putting the glass substrate into a plasma cleaning chamber, cleaning the lower surface of the glass substrate for 10-30min, turning off a radio frequency power supply after cleaning, standing for 30min, transferring the glass substrate to a magnetron sputtering chamber under the condition of not breaking vacuum after the temperature of the lower surface of the glass substrate is cooled to room temperature, and sputtering and growing a SiNX medium interference layer with the thickness of 30-600nm on the lower surface of the glass substrate by a magnetron sputtering technology.

The further improvement lies in that: in the first step, two pieces of soda-lime-silica glass with the thickness of 3.2mm are prepared.

The further improvement lies in that: in the second step, the formula of the glass etching liquid is as follows: the water-soluble hydrogen fluoride is prepared by mixing 60-70% of dilute hydrochloric acid, 10-15% of ammonium hydrogen fluoride, 2-8% of oxalic acid and the balance of water according to the weight ratio.

The further improvement is that in the third step, the glass substrate with the textured structure is placed into a plasma cleaning chamber, and the vacuum degree of the body is set to be less than or equal to 5 × 10^-3Pa, working pressure of 1-10 × 10^-1Pa, Ar gas flow of 30-40sccm, incident angle of 20-45 degrees and radio frequency power of 200 w.

The further improvement lies in that: in the third step, the magnetron sputtering technology specifically comprises the following steps: the method comprises the steps of adopting a SiO2 ceramic target material, Ar gas as a process gas, enabling the flow rate of the process gas to be 40-60sccm, adopting a radio frequency power supply to ionize the Ar gas, enabling the power of the radio frequency power supply to be 100-250w, and enabling the sputtering time to be 5-12 min.

The further improvement lies in that: in the fourth step, the glass substrate is placed into a plasma cleaning chamber in a turnover mode, the vacuum degree of the body is set to be less than or equal to 5 multiplied by 10 < -3 > Pa, the working pressure is 1 to 10 multiplied by 10 < -1 > Pa, the Ar gas flow is 30 to 40sccm, the incident angle is 20 to 45 degrees, and the radio frequency power is 200 w.

The further improvement lies in that: in the fourth step, the magnetron sputtering technology specifically comprises the following steps: si3N4 ceramic target material is adopted, Ar gas is adopted as process gas, the flow rate of the process gas is 40-60sccm, N2 gas is adopted as reaction gas, the flow rate of the reaction gas is 40-60sccm, a radio frequency power supply is adopted to ionize the Ar gas, the power of the radio frequency power supply is 150-200w, and the reaction sputtering is carried out for 5-90 min.

The invention has the beneficial effects that: according to the invention, the upper surface of the glass substrate is etched by adopting a liquid phase method, so that a short-range ordered and long-range disordered textured structure is formed on the upper surface of the glass substrate, the transmittance of visible light is improved, and the saturation of structural colors formed by a diffuse reflection diffraction effect is increased; the plasma cleaning technology is adopted to treat the upper surface and the smooth lower surface of the textured structure of the glass substrate, the binding force of a subsequent adhesion film layer can be effectively improved, meanwhile, under a high-temperature atmospheric environment, the SiO2 protective layer can improve the overall wear resistance and corrosion resistance of the glass substrate and increase the effective transmittance to sunlight, in addition, the thickness of a SiNX medium interference layer prepared by magnetron sputtering is adjusted, the refractive index of the SiNX medium interference layer is changed, different structural colors can be generated by utilizing the interference effect of light, the large-scale application of a glass color assembly in the field of buildings is improved, and the organic combination of the assembly and the buildings is realized.

Drawings

FIG. 1 is a schematic structural view of the present invention;

FIG. 2 is a flow chart of the present invention.

Detailed Description

In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.