阅读说明：本技术 抗紫外和近红外辐射的增透玻璃的制备方法 (Preparation method of anti-reflection glass capable of resisting ultraviolet and near infrared radiation ) 是由 黄仕华 丁月珂 李兴达 于 2019-09-20 设计创作，主要内容包括：本发明公开了一种抗紫外和近红外辐射的增透玻璃的制备方法,首先利用铝诱导玻璃粗化的方法在玻璃表面制备绒面结构,增加玻璃对可见光的透射；其次在绒面上生长锡掺杂的氧化锌纳米薄膜,吸收近红外辐射；最后生长钇掺杂的二氧化钛薄膜,吸收紫外辐射。铝诱导玻璃粗化、吸收近红外和紫外辐射薄膜的制备方法全部采用磁控溅射,具有工艺简单、成本低廉等特点,镀膜玻璃对波长小于380nm的紫外光的吸收超过96％,对波长大于760nm的近红外光的反射率大于65％,对波长为400～760nm的可见光的透射率大于92％,在建筑玻璃材料、汽车玻璃材料和照明灯具玻璃材料等方面具有广泛的应用前景。(The invention discloses a preparation method of anti-reflection glass for resisting ultraviolet and near infrared radiation, which comprises the steps of firstly preparing a suede structure on the surface of glass by using an aluminum-induced glass roughening method, and increasing the transmission of the glass to visible light; secondly, growing a tin-doped zinc oxide nano film on the suede to absorb near-infrared radiation; finally, growing a yttrium-doped titanium dioxide film to absorb ultraviolet radiation. The preparation method of the aluminum-induced glass coarsening and near infrared and ultraviolet radiation absorbing film adopts magnetron sputtering, and has the characteristics of simple process, low cost and the like, the coated glass absorbs more than 96% of ultraviolet light with the wavelength of less than 380nm, has the reflectivity of more than 65% of near infrared light with the wavelength of more than 760nm, has the transmissivity of more than 92% of visible light with the wavelength of 400-760 nm, and has wide application prospects in the aspects of building glass materials, automobile glass materials, lighting lamp glass materials and the like.)

1. The preparation method of the anti-reflection glass for resisting ultraviolet and near infrared radiation is characterized by comprising the following steps: the method comprises the following steps:

1) preparing an aluminum-induced glass textured structure: putting the cleaned glass substrate into a vacuum chamber of a magnetron sputtering instrument, sputtering an aluminum film, annealing for 2-5 hours at the temperature of 550-600 ℃ under the protection of argon, and naturally cooling to room temperature after annealing; placing the annealed substrate into 85% phosphoric acid solution, soaking for 10 minutes at the temperature of 110 ℃, washing with deionized water, and then using 1: 2-5 HF: HNO₃Soaking the solution for 30 seconds, washing with deionized water, and drying with nitrogen for later use;

2) preparing a tin-doped zinc oxide nano film: adopting a magnetron sputtering method, wherein the target material is mixed ceramic of zinc oxide and tin oxide, and the mass ratio of the zinc oxide to the tin oxide is 85.0-95.0: 5.0-15.0; putting the glass substrate obtained in the step 1) into a vacuum chamber of a magnetron sputtering instrument, wherein the sputtering working gas is a mixed gas of argon and oxygen, the mass ratio is 1.0: 0.5-2.0, the sputtering pressure is 0.1-0.3 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the thickness of the sputtered tin-doped zinc oxide film is 150-200 nm; then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 350-450 ℃, and the annealing time is 2 hours;

3) preparing the yttrium-doped titanium dioxide film: adopting a magnetron sputtering method, wherein the target material is yttrium oxide and titanium dioxide mixed ceramic, and the mass ratio of yttrium oxide to titanium dioxide is 2.0-5.0: 95.0-98.0; placing the glass substrate obtained in the step 2) into a vacuum chamber of a magnetron sputtering instrument, wherein the sputtering working gas is a mixed gas of argon and oxygen, the mass ratio is 1.0: 0.5-2.0, the sputtering pressure is 0.3-0.8 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the thickness of the sputtered tin-doped zinc oxide film is 200-250 nm; and then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 450-550 ℃, and the annealing time is 2 hours.

Technical Field

The invention belongs to the technical field of glass materials for buildings, automobiles and illumination. In particular to a method for preparing anti-reflection glass with ultraviolet and near infrared radiation resistance by a magnetron sputtering method.

Background

Energy conservation and environmental protection are the focus of global attention at present, and are the premise of maintaining sustainable development of human society, and the reasonable utilization of sunlight has important significance for improving the life quality of people. In sunlight on the surface of the earth, most solar radiation energy is distributed in a wave band of 200-2500 nm, wherein ultraviolet light with the wavelength of 200-400 nm accounts for about 9% of the total solar radiation energy, visible light with the wavelength of 400-760 nm accounts for about 43%, and near infrared light with the wavelength of 760-2500 nm accounts for about 45%. Ultraviolet light has great damage to human skin, accelerates the aging of high polymer polymers such as plastics, films and the like, and near infrared light can generate obvious thermal effect. For buildings and automobiles lighting through large-area glass, only visible light in sunlight needs to be partially transmitted, and the transmission of near infrared light can cause the temperature in a room or an automobile to rise, so that the refrigeration energy of an air conditioner consumed in summer is increased, and therefore, an important problem of how to isolate ultraviolet light and the near infrared light is to reasonably utilize the sunlight.

When the photon energy (h v) of the incident light is larger than or equal to the forbidden band width (E) of the material_g) Incident light is absorbed by the material, and hv<E_gThe incident light is transmitted. Therefore, a wide bandgap semiconductor material can be used to absorb the ultraviolet portion of sunlight. The reflectivity (R) at the interface of the electromagnetic radiation is, according to maxwell's electromagnetic field equation: r1- (8 omega epsilon)₀/σ)^1/2Where ω is the circular frequency of the electromagnetic radiation, ε₀Is the dielectric constant in vacuum; σ is the conductivity of the material. The larger the free carrier concentration of the material is, the larger the conductivity is, and the larger the reflectance thereof is, and therefore, the infrared reflective film is actually a transparent conductive film whose optical characteristics are closely related to the electrical properties. According to Drude theory, there is one maximum plasmon wavelength (λ) for free carrier absorption_m) The higher the carrier concentration (N), λ_mThe larger. Adjusting the magnitude of N such that λ_mLocated near the visible near infrared. If the wavelength (λ) of the incident light is greater than (λ)_m) Reflected by the material; if λ<λ_mThen incident lightThrough the material. That is, a material having a high free carrier concentration can reflect near-infrared light and transmit visible light.

Besides the high conductivity of metals such as gold, silver, copper, aluminum and the like, the conductivity of the Transparent Conductive Oxide (TCO) film is also high and the TCO film is transparent in a visible light region, so that the TCO film is widely applied to various photoelectronic devices. The TCO film mainly comprises three systems of tin oxide, indium oxide and zinc oxide base at present, and has the characteristics of high carrier concentration, high conductivity, high visible light transmittance and the like, so that the TCO film is a good near-infrared reflecting material. The nanoparticles composing the TCO film have reflection and scattering effects on visible light and near infrared light, so that the regulation and control of the size and distribution of the nanoparticles to realize the near infrared blocking effect on the enhanced TCO film are also very important. The metal oxide is mostly wide bandgap semiconductor, such as zinc oxide (ZnO), titanium dioxide (Ti)₂O), tin dioxide (Sn)₂O) in the ultraviolet region, which respectively corresponds to 400nm, 376nm and 345nm, so that the ultraviolet light absorption is strong, and the visible light absorption is weak, and the material is suitable for resisting ultraviolet radiation.

The conventional solution of sunscreen and heat insulation of glass comprises a metal coating film and a film, wherein the visible light transmittance of the metal coating film and the film is low, the light pollution caused by high reflectivity is serious, the oxidation characteristic of the metal coating film causes reduction of heat insulation performance, and meanwhile, the metal coating film generates interference on telecommunication signals.

Disclosure of Invention

The invention aims to provide a method for preparing anti-reflection glass with ultraviolet resistance and near infrared radiation by utilizing a magnetron sputtering method.

The technical scheme adopted by the invention is as follows:

the preparation method of the anti-reflection glass for resisting ultraviolet and near infrared radiation comprises the following steps:

1) preparing an aluminum-induced glass textured structure: putting the cleaned glass substrate into a vacuum chamber of a magnetron sputtering instrument, sputtering an aluminum film, annealing for 2-5 h at the temperature of 550-600 ℃ under the protection of argon, and naturally cooling after annealingCooling to room temperature; placing the annealed substrate into 85% phosphoric acid solution, soaking for 10 minutes at the temperature of 110 ℃, washing with deionized water, and then using 1: 2-5 HF: HNO₃Soaking the solution for 30 seconds, washing with deionized water, and drying with nitrogen for later use;

2) preparing a tin-doped zinc oxide nano film: adopting a magnetron sputtering method, wherein the target material is mixed ceramic of zinc oxide and tin oxide, and the mass ratio of the zinc oxide to the tin oxide is 85.0-95.0: 5.0-15.0; putting the glass substrate obtained in the step 1) into a vacuum chamber of a magnetron sputtering instrument, wherein the sputtering working gas is a mixed gas of argon and oxygen (the mass ratio is 1.0: 0.5-2.0), the sputtering pressure is 0.1-0.3 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the thickness of the sputtered tin-doped zinc oxide film is 150-200 nm; then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 350-450 ℃, and the annealing time is 2 hours;

3) preparing the yttrium-doped titanium dioxide film: adopting a magnetron sputtering method, wherein the target material is yttrium oxide and titanium dioxide mixed ceramic, and the mass ratio of yttrium oxide to titanium dioxide is 2.0-5.0: 95.0-98.0; putting the glass substrate obtained in the step 2) into a vacuum chamber of a magnetron sputtering instrument, wherein the sputtering working gas is a mixed gas of argon and oxygen (the mass ratio is 1.0: 0.5-2.0), the sputtering pressure is 0.3-0.8 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the thickness of the sputtered tin-doped zinc oxide film is 200-250 nm; and then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 450-550 ℃, and the annealing time is 2 hours.

Firstly, preparing a suede structure on the surface of glass by using an aluminum-induced glass roughening method, and increasing the transmission of the glass to visible light; secondly, growing a tin-doped zinc oxide (Sn: ZnO) nano film on the suede to absorb near-infrared radiation; finally growing yttrium-doped titanium dioxide film (Y: TiO)₂) Absorbing ultraviolet radiation. The preparation method of the aluminum-induced glass coarsening and near-infrared and ultraviolet radiation absorbing film adopts magnetron sputtering, and has the characteristics of simple process, low cost and the like, the coated glass absorbs more than 96 percent of ultraviolet light with the wavelength of less than 380nm and reflects near-infrared light with the wavelength of more than 760nmThe refractive index is more than 65%, the transmittance to visible light with the wavelength of 400-760 nm is more than 92%, and the glass has wide application prospects in the aspects of building glass materials, automobile glass materials, lighting lamp glass materials and the like.

Drawings

The following detailed description is made with reference to the accompanying drawings and embodiments of the present invention

FIG. 1 shows an absorption spectrum of an antireflection glass for ultraviolet and near-infrared radiation resistance.

Detailed Description

1. Preparation of aluminum-induced glass texture structure

Sputtering a layer of metal aluminum on the glass, annealing at a temperature lower than the softening temperature of the glass, and removing reaction products of aluminum oxide, silicon and unreacted aluminum by using a corrosive liquid, so that a textured structure is formed on the surface of the glass. The glass substrate used in the experiment is common commercial float borosilicate glass, the visible light transmittance is more than 88 percent, and the size is 20 multiplied by 20mm². The purity of the metallic aluminum target is more than 99.99 percent, the diameter is 60mm, and the thickness is 1.5 mm.

1) Glass substrate cleaning

Firstly, ultrasonically cleaning for 10min by using a detergent solution, repeatedly washing with tap water until no bubbles exist, repeatedly cleaning with deionized water, finally ultrasonically cleaning for 30min by using acetone and absolute ethyl alcohol, and drying by using nitrogen for later use.

2) Metallic aluminum film growth

The glass substrate is put into a vacuum chamber of a magnetron sputtering instrument, and the background vacuum of the chamber is superior to 8 multiplied by 10^-4Pa. Before sputtering the aluminum film, the substrate is reversely sputtered for 10min to remove the adsorbed water vapor and impurities on the surface of the substrate. The sputtering working gas is argon (the purity is more than 99.99%), the sputtering pressure is 1-5 Pa, the substrate temperature is room temperature, the sputtering power is 120Pa, the film thickness is monitored by a quartz oscillator, and the typical aluminum film thickness is 80-150 nm.

3) Annealing of thin films

Annealing the grown aluminum film at the temperature of 550-600 ℃ for 2-5 h under the protection of argon, and naturally cooling to the room temperature after the annealing is finished.

4) Textured structure formation on glass surfaces

Placing the annealed substrate into 85% phosphoric acid solution, soaking for 10 minutes at the temperature of 110 ℃, washing with deionized water, and then using 1: 2-5 HF: HNO₃The solution was soaked for 30 seconds, rinsed with deionized water, and dried with nitrogen for future use.

2. Preparation of tin-doped zinc oxide nano-film

The tin-doped zinc oxide film is a transparent conductive oxide film with a carrier concentration of 10¹⁸～10²¹cm^-3Conductivity of 10²～10⁵S.cm, because it has high carrier concentration and high conductivity, the tin-doped zinc oxide film is a very efficient near-infrared reflective material according to Drude free carrier absorption theory.

The film growth adopts a magnetron sputtering method, the target material is mixed ceramic of zinc oxide and tin oxide, and the mass ratio of the zinc oxide to the tin is 85.0-95.0 percent to 5.0-15.0 percent. And putting the glass substrate with the suede structure on the surface into a vacuum chamber of a magnetron sputtering instrument. The sputtering working gas is a mixed gas of argon and oxygen (the mass ratio is 1.0: 0.5-2.0), the sputtering pressure is 0.1-0.3 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the typical thickness of the sputtered tin-doped zinc oxide film is 150-200 nm. And then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 350-450 ℃, and the annealing time is 2 hours.

3. Preparation of yttrium-doped titanium dioxide film

The radius of the yttrium ions is similar to that of the titanium ions, so that the yttrium ions can enter titanium dioxide crystal lattices more easily and are distributed in the titanium dioxide more uniformly. The titanium dioxide can absorb ultraviolet light with the wavelength less than 400nm, and the yttrium ion energy level is close to the titanium dioxide conduction band, so the yttrium-doped titanium dioxide can completely absorb the ultraviolet light.

The film is grown by adopting a magnetron sputtering method, the target material is mixed ceramic of yttrium oxide and titanium dioxide, and the mass ratio of yttrium to titanium dioxide is 2.0-5.0% to 95.0-98.0%. The glass substrate with tin-doped zinc oxide nano film grown on the surface is put into a vacuum chamber of a magnetron sputtering instrument. The sputtering working gas is a mixed gas of argon and oxygen (the mass ratio is 1.0: 0.5-2.0), the sputtering pressure is 0.3-0.8 Pa, the substrate temperature is room temperature, the sputtering power is 25-50 Pa, and the typical thickness of the sputtered tin-doped zinc oxide film is 200-250 nm. And then, carrying out in-situ annealing treatment on the film under the protection of argon, wherein the annealing temperature is 450-550 ℃, and the annealing time is 2 hours.

4. Performance testing and analysis

The glass substrate treated by the above process steps was subjected to an optical transmittance test using an ultraviolet-visible-infrared spectrometer, and the results are shown in fig. 1. The average transmittance of the film in the wavelength ranges of 200-380 nm, 400-760 nm and 760-1700 nm is 3.42%, 92.56% and 34.65%, respectively. Therefore, the anti-reflection glass designed and prepared by the invention has the advantages that the absorption of ultraviolet light with the wavelength of less than 380nm exceeds 96%, the reflectivity of near infrared light with the wavelength of more than 760nm is more than 65%, and the transmissivity of visible light with the wavelength of 400-760 nm is more than 92%. Compared with the conventional ultraviolet and infrared radiation resistant glass, the visible light transmittance is greatly improved, and the ultraviolet and infrared light reflecting performance is good.