CN112499986A - Reflection anti-reflection glass with adjustable reflection wavelength and preparation method thereof - Google Patents
Reflection anti-reflection glass with adjustable reflection wavelength and preparation method thereof Download PDFInfo
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- CN112499986A CN112499986A CN202011560991.0A CN202011560991A CN112499986A CN 112499986 A CN112499986 A CN 112499986A CN 202011560991 A CN202011560991 A CN 202011560991A CN 112499986 A CN112499986 A CN 112499986A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses reflection anti-reflection glass with adjustable reflection wavelength.A transparent dielectric microsphere array structure layer is prepared on the surface of a glass substrate, the diameter of the microsphere is between 100nm and 500nm, and the diameter of the transparent dielectric microsphere determines the light with the reflection corresponding wavelength. The preparation method comprises the following steps: the transparent medium microspheres are dispersed in solvents such as absolute ethyl alcohol and the like, uniformly dispersed by stirring, immersed in a medium microsphere suspension for vertical deposition for 24 hours after the surface of a glass substrate is cleaned and subjected to hydroxylation treatment, and deposited on the surface of the glass, and dried at a high temperature of 100-200 ℃ to obtain the glass with the surface medium microsphere array structure, and the glass can enhance the reflection of light wave display color with specific wavelength related to the diameter of the selected microspheres. The invention has the beneficial effects that: the prepared flat glass has certain color, does not obviously reduce the transmittance of the glass substrate, and can be used for cover plate glass of color solar photovoltaic cells and other occasions requiring effective reduction of light wave transmission of certain wavelength.
Description
Technical Field
The invention relates to the technical field of selective transmission and reflection of a glass surface spectrum, in particular to reflection and anti-reflection glass with adjustable reflection wavelength and a preparation method thereof.
Background
Along with people's concern increasingly to environment and energy problem, new forms of energy include that solar energy wind energy and novel chemical energy more and more receive people's attention, wherein in novel building field, people have proposed the new building structure of the photovoltaic building integration that combines solar photovoltaic cell and building, and this idea is in the same place photovoltaic cell and building whole combination, can effectively utilize the space and provide clean energy, is favorable to alleviating fossil burning and greenhouse gas pollution problem that traditional power consumption brought.
The traditional solar photovoltaic cell, whether a silicon-based solar cell or a copper indium gallium selenide solar cell, has a single color and is dark or black. With the pursuit of building aesthetics, new buildings not only have more complex structures and functions, but also have various and beautiful appearances, and the combination of buildings and photovoltaic cells needs to cover the large-area photovoltaic cells on the outer surfaces of the buildings, so that the requirements of building appearance diversity and beauty are met, and people are prompted to put forward the issue of colorization of the photovoltaic cells.
At present, the colorization of the solar photovoltaic cell is mainly realized by two ideas, namely, an absorption medium layer of the solar photovoltaic cell can absorb corresponding light through the improvement of a preparation process or the preparation of a layer of coating of color paint, so that different colors are displayed; the other idea is to perform special process treatment on the cover plate glass of the photovoltaic cell to reflect sunlight with specific color wavelength to generate color, the former idea can lose more sunlight energy and obviously reduce the efficiency of the solar cell, and the latter idea can reduce the loss of the sunlight as much as possible as long as the energy of the sunlight with the wavelength is lost. The latter concept is that a plurality of transparent films are deposited on the surface of a glass cover plate by a film coating method such as magnetron sputtering, and light is reflected by the transparent films to cause interference of sunlight with special wavelength to generate a reflection color. The method involves complicated calculation and coating design, and has a long coating production period.
Disclosure of Invention
The invention aims to solve the problems that the existing color solar cell is complex in process and can obviously reduce the power generation efficiency of the solar cell, and provides reflection anti-reflection glass with adjustable reflection wavelength and a preparation method thereof.
The basic principle of the invention is as follows:
(1) the transparent medium is utilized to form micron nanometer size microspheres, the microspheres generate optical interference on the surface and reflect sunlight with corresponding wavelength by forming an array structure with a certain number of layers and thickness on the glass surface, the single size microsphere array reflects sunlight with single wavelength, wherein the diameter D of the microspheres and the wavelength lambda of the reflected sunlight have the following corresponding relation:
2rDsinθ = nλ
wherein r is different plane orientation factor and n represents positive integer. When the maximum angle is taken, the sunlight wavelength which can be reflected by the array formed by the microspheres with the diameter D is as follows:
λ = 2rD/n
therefore, the surface microsphere array can generate enhanced reflection for light waves with the solar wavelength of 2rD/n, and the maximum reflection wavelength is taken as the main reflection wavelength when n =1, so that the corresponding color is displayed.
(2) Capillary force is a common acting force in nature, micro particles with micron and nanometer sizes are uniformly gathered on the surface at a solid-liquid-gas three-phase interface under the action of surface tension, the uniformly gathered micro particles are attached to the solid surface at the solid-liquid-gas interface under the action of capillary force, and a tightly arranged ordered array structure is formed on the solid surface.
The technical scheme adopted by the invention is as follows:
a reflection anti-reflection glass with adjustable reflection wavelength comprises a glass substrate and is characterized in that a transparent dielectric microsphere array structure layer is prepared on the surface of the glass substrate, the diameter D of each transparent dielectric microsphere is 100 nm-500 nm, and the specific diameter D of each transparent dielectric microsphere is selected to reflect light with corresponding wavelength.
Further, the transparent medium microspheres are SiO2Microspheres, ZrO2Microspheres or Al2O3One of the microspheres.
Further, the diameter D of the microsphere and the wavelength lambda of the reflected sunlight have the following corresponding relation: 2rDsin θ = n λ; r is different plane orientation factors, n represents a positive integer, and when sin theta takes the maximum angle, the sunlight wavelength which can be reflected by an array formed by the microspheres with the diameter D is as follows: λ =2 rD/n.
The invention also provides a preparation method of the reflection and anti-reflection glass with adjustable reflection wavelength, which is characterized by comprising the following steps:
(1) Preparing a monodisperse suspension of transparent medium microspheres, dispersing the transparent medium microspheres with a certain diameter in any solvent of absolute ethyl alcohol and deionized water to form a suspension of the transparent medium microspheres with the concentration of 0.01-10 mg/ml, stirring for one hour by using a magnetic stirrer or a stirring rod and the like, and standing to form a uniformly dispersed monodisperse suspension of the transparent medium microspheres;
(2) Cleaning the surface of a glass substrate, washing the surface of the glass with a solvent to form a clean and pollution-free glass surface, soaking the surface of the glass with concentrated sulfuric acid for 10-60 minutes, cleaning with deionized water to completely remove surface pollutants, and forming an effective hydroxyl base layer on the surface of the glass substrate;
(3) Preparing an array structure layer of the medium microspheres on the surface of the glass substrate, and preparing at least one layer of transparent medium microsphere array on the surface of the glass substrate after cleaning and hydroxylation treatment;
(4) The method comprises the following steps of carrying out high-temperature treatment on a microsphere array layer and a glass surface, carrying out high-temperature treatment on a glass substrate provided with the transparent dielectric microsphere array layer at the temperature of 100-200 ℃ through a high-temperature oven or a high-temperature furnace, removing a solvent on the surface, and simultaneously enabling the microsphere array layer to be tightly combined with the glass surface, wherein the surface of the glass substrate forming the array structure layer can effectively reflect sunlight with a specific wavelength, and the surface shows a corresponding color.
Further, the preparation method of the dielectric microsphere array can be a vertical deposition method, a spin coating method, a wire bar blade coating method or a roller coating method.
Furthermore, the glass surface hydroxylation treatment comprises concentrated sulfuric acid soaking, hot concentrated sulfuric acid soaking and other methods capable of carrying out surface hydroxylation, such as concentrated sulfuric acid and hydrogen peroxide mixed solution heating soaking, oxygen plasma bombardment surface treatment and the like.
Further, transparent medium microsphere suspensions with different diameters are prepared, and a composite structure with a plurality of sizes of microsphere arrays superposed is prepared according to the method of claim 4, and simultaneously sunlight with various wavelengths is enhanced and reflected to form composite colors. The suspension liquid of microspheres with different diameters is prepared into a composite structure with a superposed microsphere array with various sizes by repeating the steps, and simultaneously, sunlight with various wavelengths is enhanced and reflected to form composite colors, and the composite structure can be used for occasions where light waves with certain colors are effectively reduced to penetrate.
The invention has the beneficial effects that: the invention can simply and effectively prepare the plate glass with a certain color, and simultaneously can not obviously reduce the transmittance of the glass substrate, and experiments prove that the invention can also effectively improve the transmittance of light waves with other wavelengths, thereby having the anti-reflection effect, not only being used for cover plate glass of a color solar photovoltaic cell, but also being used for other occasions needing to effectively reduce the transmittance of light waves with certain wavelength, reducing the transmittance of light waves without losing the transmittance of light waves with other wavelengths, and even enhancing the transmittance of other light waves.
Drawings
FIG. 1 is a spectrum of the spectral reflectance of a glass surface reflecting a specific wavelength prepared according to the method of the present invention in example one;
FIG. 2 is a spectrum of the spectral reflectance of a glass surface reflecting a specific wavelength prepared according to the method of the present invention in example two;
FIG. 3 is a spectrum of the spectral reflectance of three glass surfaces of the example prepared according to the method of the present invention that reflect specific wavelengths;
FIG. 4 is a comparison graph of the surface spectral reflectance of glass prepared according to the present invention before and after the microsphere array is prepared on the surface, wherein the reflectance of light waves of other wavelengths on the surface of the glass is significantly reduced after the array of the present invention is prepared, except for the specific wavelength.
Detailed Description
SiO on glass surface by combining different parameter processes2The preparation of the microsphere array and the test results of the surface spectral reflectivity further illustrate the method provided by the invention.
Example one
(1) SiO with a uniform size of 100nm in diameter2Dispersing the microspheres in an absolute ethyl alcohol solvent to form a suspension with the mass concentration of 1 mg/ml, magnetically stirring at room temperature for 1 hour, and standing for 60min to form a uniformly dispersed suspension.
(2) And (3) washing the cut glass of 50 mm x 2 mm by using deionized water, soaking the glass in concentrated sulfuric acid for 30min, taking out the glass, washing the glass by using the deionized water, and drying the glass by blowing.
(3) The cleaned and hydroxylated glass was immersed vertically in 1 mg/ml SiO2Placing the microsphere suspension in a constant temperature and humidity box with the temperature of 40 ℃ and the relative humidity of 50% RH, standing and depositing for 24 h. After the process is finished, SiO with the thickness of 100nm is obtained by deposition2SiO with microsphere layer number greater than 12An array of microspheres.
(4) Will deposit 100nm SiO2And taking out the glass of the microsphere array, and drying in a drying oven at 100 ℃ for 30 min.
(5) The prepared array layer was subjected to a surface spectrum reflectance test, as shown in fig. 1, in which the reflectance for a light wave having a wavelength of 240nm was 26.1%, a specific wavelength was effectively reflected, and the reflected light was ultraviolet light.
Example two
(1) SiO with a uniform size of 100nm in diameter2Dispersing the microspheres in an absolute ethyl alcohol solvent to form a suspension with the mass concentration of 5mg/ml, magnetically stirring for 1 hour at room temperature, and standing for 60min to form a uniformly dispersed suspension.
(2) And (3) washing the cut glass with 50 mm x 2 mm by using deionized water, soaking the glass in concentrated sulfuric acid at 80 ℃ for 30min, taking out the glass, washing the glass by using the deionized water, and drying the glass by blowing.
(3) The cleaned and hydroxylated glass is vertically immersed5mg/ml SiO2Placing the microsphere suspension in a constant temperature and humidity box with the temperature of 40 ℃ and the relative humidity of 50% RH, standing and depositing for 24 h. To obtain SiO with a thickness of 100nm2SiO with microsphere layer number greater than 12A microsphere array structure.
(4) Will deposit 100nm SiO2And taking out the glass of the microsphere array, and drying in a drying oven at 100 ℃ for 30 min.
(5) The prepared array was tested for surface spectral reflectance as shown in fig. two, where the reflectance for light of wavelength 242nm is 25.6%, which effectively reflects a specific wavelength corresponding to the uv range.
EXAMPLE III
(1) SiO with a uniform size of 500nm in diameter2Dispersing the microspheres in an absolute ethyl alcohol solvent to form a suspension with the mass concentration of 1.5 mg/ml, magnetically stirring for 1 hour at room temperature, and standing for 30min to form a uniformly dispersed suspension.
(2) And (3) washing the cut glass with 50 mm x 2 mm by using deionized water, soaking the glass in concentrated sulfuric acid at 80 ℃ for 10min, taking out the glass, washing the glass by using the deionized water, and drying the glass by blowing.
(3) The cleaned and hydroxylated glass was immersed vertically in 1.5 mg/ml SiO2Placing the microsphere suspension in a constant temperature and humidity box with the relative humidity of 50% RH at 60 ℃, standing and depositing for 24 h. Obtaining SiO with the thickness of 500nm2500nm SiO with microsphere layer number greater than 12A microsphere array structure.
(4) Will deposit 500nm SiO2And taking out the glass of the microsphere array, and drying in a drying oven at 100 ℃ for 60 min.
(5) The prepared array was subjected to surface spectrum reflectance test, as shown in fig. 3, in which the reflectance for a light wave having a wavelength of around 1280nm was 10.5%, a distinct reflection peak appeared, a specific wavelength was efficiently reflected, and the reflected light was near-infrared light.
Example four
The spectral reflectance of the surface of the clean glass without the dielectric microsphere array is tested and compared with the surface reflectance spectrogram of the array in the second embodiment, as shown in the fourth drawing, wherein at the wavelength of λ =2rD, a high reflectance peak appears in the reflectance spectrum of the glass surface with the array structure on the prepared surface, which is obviously higher than the reflectance of the glass surface without the array structure, and in the other wavelength ranges, the spectral reflectance of the glass surface with the array structure is obviously lower than the spectral reflectance of the glass surface without the array structure, and the prepared glass surface with the array structure can enhance and reflect specific wavelengths except at the wavelength of λ =2rD, has obvious anti-reflection and anti-reflection effects on the light waves of the other wavelengths, and can be used in scenes needing anti-reflection.
Claims (7)
1. A reflection anti-reflection glass with adjustable reflection wavelength comprises a glass substrate and is characterized in that a transparent dielectric microsphere array structure layer is prepared on the surface of the glass substrate, the diameter D of each transparent dielectric microsphere is 100 nm-500 nm, and the specific diameter D of each transparent dielectric microsphere is selected to reflect light with corresponding wavelength.
2. A reflective antireflection glass according to claim 1 wherein said transparent dielectric microspheres are SiO2Microspheres, ZrO2Microspheres or Al2O3One of the microspheres.
3. A reflecting anti-reflection glass with adjustable reflection wavelength according to claim 1, wherein the diameter D of the microsphere and the wavelength λ of reflected sunlight have the following corresponding relationship: 2rDsin θ = n λ;
r is different plane orientation factors, n represents a positive integer, and when sin theta takes the maximum angle, the sunlight wavelength which can be reflected by an array formed by the microspheres with the diameter D is as follows: λ =2 rD/n.
4. A method of making a reflective antireflection glass that provides tunable reflection wavelengths according to claim 1, 2 or 3 comprising the steps of:
(1) Preparing a monodisperse suspension of transparent medium microspheres, dispersing the transparent medium microspheres with a certain diameter in any solvent of absolute ethyl alcohol and deionized water to form a suspension of the transparent medium microspheres with the concentration of 0.01-10 mg/ml, stirring for one hour by using a magnetic stirrer or a stirring rod and the like, and standing to form a uniformly dispersed monodisperse suspension of the transparent medium microspheres;
(2) Cleaning the surface of a glass substrate, washing the surface of the glass with a solvent to form a clean and pollution-free glass surface, soaking the surface of the glass with concentrated sulfuric acid for 10-60 minutes, cleaning with deionized water to completely remove surface pollutants, and forming an effective hydroxyl base layer on the surface of the glass substrate;
(3) Preparing an array structure layer of the medium microspheres on the surface of the glass substrate, and preparing at least one layer of transparent medium microsphere array on the surface of the glass substrate after cleaning and hydroxylation treatment;
(4) The method comprises the following steps of carrying out high-temperature treatment on a microsphere array layer and a glass surface, carrying out high-temperature treatment on a glass substrate provided with the transparent dielectric microsphere array layer at the temperature of 100-200 ℃ through a high-temperature oven or a high-temperature furnace, removing a solvent on the surface, and simultaneously enabling the microsphere array layer to be tightly combined with the glass surface, wherein the surface of the glass substrate forming the array structure layer can effectively reflect sunlight with a specific wavelength, and the surface shows a corresponding color.
5. The method for preparing reflection anti-reflection glass with adjustable reflection wavelength according to claim 4, wherein the method for preparing the dielectric microsphere array can be a vertical deposition method, a spin coating method, a wire bar blade coating method or a roller coating method.
6. The method for preparing reflection anti-reflection glass with adjustable reflection wavelength according to claim 4, wherein the hydroxylation treatment on the surface of the glass comprises concentrated sulfuric acid soaking, hot concentrated sulfuric acid soaking, and other methods capable of performing surface hydroxylation, such as concentrated sulfuric acid and hydrogen peroxide mixed solution heating soaking, oxygen plasma bombardment surface treatment, and the like.
7. The method for preparing reflection anti-reflection glass with adjustable reflection wavelength according to claim 4, characterized in that transparent medium microsphere suspensions with different diameters are prepared, and a composite structure with an array of microspheres of multiple sizes superposed is prepared according to the method of claim 4, and simultaneously sunlight with multiple wavelengths is reflected in an enhanced manner to form composite colors.
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| CN202011560991.0A CN112499986A (en) | 2020-12-25 | 2020-12-25 | Reflection anti-reflection glass with adjustable reflection wavelength and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603371A (en) * | 2021-09-06 | 2021-11-05 | 广东中融玻璃科技有限公司 | Preparation method of colored glaze coated glass |
| CN113716882A (en) * | 2021-09-06 | 2021-11-30 | 广东中融玻璃科技有限公司 | Processing technology of Low-e laminated glass |
| CN113921624A (en) * | 2021-11-22 | 2022-01-11 | 上海交通大学 | Colorful solar photovoltaic cell and assembly |
| CN114394767A (en) * | 2021-12-27 | 2022-04-26 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of red glass capable of reducing observation angle influence |
-
2020
- 2020-12-25 CN CN202011560991.0A patent/CN112499986A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603371A (en) * | 2021-09-06 | 2021-11-05 | 广东中融玻璃科技有限公司 | Preparation method of colored glaze coated glass |
| CN113716882A (en) * | 2021-09-06 | 2021-11-30 | 广东中融玻璃科技有限公司 | Processing technology of Low-e laminated glass |
| CN113716882B (en) * | 2021-09-06 | 2023-09-01 | 广东中融玻璃科技有限公司 | Processing Technology of Low-e Laminated Glass |
| CN113921624A (en) * | 2021-11-22 | 2022-01-11 | 上海交通大学 | Colorful solar photovoltaic cell and assembly |
| CN114394767A (en) * | 2021-12-27 | 2022-04-26 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of red glass capable of reducing observation angle influence |
| CN114394767B (en) * | 2021-12-27 | 2023-08-22 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of red glass capable of reducing influence of observation angle |
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