阅读说明：本技术 一种用于玻璃基底的增透减反复合膜及其制备方法 (Anti-reflection and anti-reflection composite film for glass substrate and preparation method thereof ) 是由 徐照英 肖艳红 张腾飞 王锦标 于 2020-07-27 设计创作，主要内容包括：本发明提供一种用于玻璃基底的增透减反复合膜及其制备方法,该方法先通过离子束进行基片轰击,然后通过离子源辅助磁控溅射的方法分别制备掺钨VO<Sub>2</Sub>薄膜层、Si<Sub>3</Sub>N<Sub>4</Sub>薄膜层(3)以及SiO<Sub>2</Sub>薄膜层(4),最后通过紫外高温烘烤,得到由七层薄膜层结构组成的增透减反复合膜；该七层薄膜层结构从玻璃基底(1)表面向外依次为第一掺钨VO<Sub>2</Sub>薄膜层(21)、Si<Sub>3</Sub>N<Sub>4</Sub>薄膜层(3)、第二掺钨VO<Sub>2</Sub>薄膜层(22)、Si<Sub>3</Sub>N<Sub>4</Sub>薄膜层(3)、第三掺钨VO<Sub>2</Sub>薄膜层(23)、Si<Sub>3</Sub>N<Sub>4</Sub>薄膜层(3)以及SiO<Sub>2</Sub>薄膜层(4)。本发明制得的复合膜有效解决现有技术中低反射率和高力学性能不能同时兼顾的问题,具有较小的吸收、散射和反射特性,可见光透性好；薄膜结构牢固稳定、不易脱落。(The invention provides an anti-reflection and anti-reflection composite film for a glass substrate and a preparation method thereof 2 Thin film layer, Si 3 N 4 Thin film layer (3) and SiO 2 Finally, the thin film layer (4) is baked at high temperature through ultraviolet rays to obtain an anti-reflection and anti-reflection composite film consisting of seven thin film layer structures; the seven-layer film layer structure is a first tungsten-doped VO from the surface of a glass substrate (1) to the outside in sequence 2 Thin film layer (21), Si 3 N 4 Thin film layer (3) and second tungsten-doped VO 2 A thin film layer (22), Si 3 N 4 Thin film layer (3) and third tungsten-doped VO 2 Thin film layer (23), Si 3 N 4 Thin film layer (3) and SiO 2 A film layer (4). The composite film prepared by the invention effectively solves the problem that low reflectivity and high mechanical property can not be simultaneously considered in the prior art, has smaller absorption, scattering and reflection characteristics and good visible light permeability; the film structure is firm and stable and is not easy to fall off.)

1. An antireflection composite film for a glass substrate, characterized in that: it is composed of seven thin film layer structures; the first tungsten-doped VO is arranged from the surface of the glass substrate (1) to the outside in sequence₂Thin film layer (21), Si₃N₄Thin film layer (3) and second tungsten-doped VO₂A thin film layer (22), Si₃N₄Thin film layer (3) and third tungsten-doped VO₂Thin film layer (23), Si₃N₄Thin film layer (3) and SiO₂A film layer (4); wherein the first tungsten-doped VO₂A thin film layer (21) and a second tungsten-doped VO₂A thin film layer (22) and a third tungsten-doped VO₂The tungsten content of the thin film layer (23) is increased in sequence and is between 1.5 and 3.5 at.%.

2. An antireflection composite film for a glass substrate according to claim 1, wherein: the front side and the back side of the glass substrate (1) are plated with the seven-layer film layer structure.

3. An antireflection composite film for a glass substrate according to claim 1, wherein: the first tungsten-doped VO₂A thin film layer (21) and a second tungsten-doped VO₂A thin film layer (21) and a third tungsten-doped VO₂The thickness of the thin film layer (23) can be 45-55 nm.

4. An antireflection composite film for a glass substrate according to claim 1, wherein: said Si₃N₄The thickness of the thin film layer (3) can be 100-120 nm.

5. An antireflection composite film for a glass substrate according to claim 1, wherein: the SiO₂The thickness of the thin film layer (4) can be 200-260 nm.

6. A method of making an antireflective composite film for a glass substrate according to claim 1, wherein:

firstly, pretreating a glass substrate material, and bombarding a pretreated glass base surface for 8-12 min by using an ion beam; then, preparing a first tungsten-doped VO by sequentially carrying out a direct-current magnetron sputtering method by adopting an ion source assisted deposition method₂Preparation of Si by thin film layer and intermediate frequency magnetron sputtering method₃N₄Thin film layer and second tungsten-doped VO₂Thin film layer and Si₃N₄Thin film layer, third doped tungsten VO₂Thin film layer and Si₃N₄A thin film layer for forming W-doped VO on the glass base surface₂Thin film layer and Si₃N₄Six composite film layers with alternately superposed film layers; then adopting the radio frequency magnetron sputtering method of ion source auxiliary deposition to form Si on the outermost layer₃N₄Preparation of SiO on the surface of the thin film layer₂A thin film layer; finally, obtaining SiO by magnetron sputtering₂And (4) placing the glass sheet behind the thin film layer under an ultraviolet lamp, and baking at high temperature to obtain the anti-reflection and anti-reflection composite film.

7. The method for preparing an antireflection composite film for a glass substrate according to claim 6, wherein: the glass substrate is a QK3 substrate.

8. The method for preparing an antireflection composite film for a glass substrate according to claim 6, wherein: the direct current magnetron sputtering method is used for preparing tungsten-doped VO₂The film layer is specifically as follows: the direct current magnetron sputtering method is used for preparing tungsten-doped VO₂The film layer is specifically as follows: introducing oxygen into a metal vanadium target and a tungsten target, wherein the oxygen flow is 38-42 sccm; the deposition temperature is 440-460 ℃, and the deposition time is 42-48 min; wherein, the power of magnetron sputtering is controlled to control each layer of the VO doped with tungsten₂The content of tungsten in the thin film layer, the first tungsten-doped VO₂The sputtering power of the thin film layer is 210-220W, and the second tungsten-doped VO₂The sputtering power of the thin film layer is 225-235W, and the third tungsten-doped VO₂The sputtering power of the thin film layer is 240-250W.

9. The method for preparing an antireflection composite film for a glass substrate according to claim 6, wherein: the intermediate frequency magnetron sputtering method is used for preparing Si₃N₄The film layer is specifically as follows: introducing nitrogen into a silicon target with the purity of 99.99% at a flow rate of 58-62 sccm; the sputtering power is 200-220W, the deposition temperature is room temperature, and the deposition time is 28 ℃32min。

10. The method for preparing an antireflection composite film for a glass substrate according to claim 6, wherein: the radio frequency magnetron sputtering method is used for preparing SiO₂The film layer is specifically as follows: introducing oxygen into a silicon target with the purity of 99.99%, wherein the oxygen flow is 55-65 sccm; the sputtering power is 170-190W, the deposition temperature is 360-400 ℃, and the deposition time is 45-55 min.

Technical Field

The invention relates to the technical field of optical films, in particular to an anti-reflection and anti-reflection composite film for a glass substrate and a preparation method thereof.

Background

At present, the frame mounting glass, the showcase glass and the like of the calligraphy and painting all adopt common plate glass, but due to the mirror effect formed by the reflection function of the glass surface, the glass reflects the surrounding influence, light and the like, and the ornamental effect of the calligraphy and painting, the showcase and the like is directly influenced.

With the continuous development of economic construction and the progress of science and technology, the application of the glass curtain wall to large buildings is more and more frequent. The glass curtain wall has excellent visual effect, meanwhile, the indoor artificial illumination intensity of the glass curtain wall can be greatly reduced in the daytime due to the light transmission performance of the glass, and the existing glass curtain wall also has the effects of heat preservation, heat insulation, noise reduction and the like; however, urban light pollution is also aggravated by the reflective properties of the glass curtain wall glass itself.

The antireflection film, also called as an antireflection film, has the main function of reducing or eliminating the reflected light from optical surfaces such as lenses, prisms, plane mirrors and the like, thereby increasing the light transmission of the elements and reducing or eliminating the stray light of the system. In the prior art, a single-layer or multi-layer optical film is prepared on the surface of a device by using a sol-gel liquid film-making method and the like so as to reduce the reflection of the optical surface, but the problems of mismatched refractive index, mismatched stress and the like exist between air and a substrate material, so that the glass still has larger residual reflection, the bonding strength between the film layer and the substrate and between the film layers is low, and the film has poor structural stability, is easy to fall off and the like; in addition, the method for preparing the single-layer or multi-layer antireflection film in the prior art also has the problems of limited selection of film layer materials, high cost of the film layer materials, unsuitability for batch production, low application range and the like.

Disclosure of Invention

In view of the problems in the prior art, the present invention aims to provide an anti-reflection and anti-reflection composite film for a glass substrate, which improves the transmittance of the glass in a visible light region, i.e., reduces the reflectivity of visible light, is transparent in a visible light band, and has small absorption and scattering properties; meanwhile, the composite membrane is stable in structure, high in bonding strength between the membrane layer and the basal layer and between the membrane layer and the membrane layer, not easy to fall off, and high in mechanical firmness and chemical stability.

Another object of the invention is to provide a preparation method of an anti-reflection and anti-reflection composite film for a glass substrate, which is used for preparing the anti-reflection and anti-reflection composite film.

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

an antireflection composite film for a glass substrate, characterized in that: it is composed of seven thin film layer structures; the first tungsten-doped VO is arranged from the surface of the glass substrate to the outside in sequence₂Thin film layer, Si₃N₄Thin film layer and second tungsten-doped VO₂Thin film layer, Si₃N₄Thin film layer, third doped tungsten VO₂Thin film layer, Si₃N₄Thin film layer and SiO₂A thin film layer; wherein the first tungsten-doped VO₂Thin film layer and second tungsten-doped VO₂Thin film layer, third doped tungsten VO₂The tungsten content of the thin film layers is increased in sequence and is between 1.5 and 3.5 at.%.

By using a tungsten-doped VO exhibiting a compressive stress₂The thin film layer is firmly and stably combined with the substrate, and simultaneously, Si in the form of tensile stress is matched and expressed₃N₄Thin film layer of Si₃N₄Film layer and SiO₂The thin film layers are tightly combined, and at the same time, the tungsten-doped VO₂Thin film layer and Si₃N₄The mutual cooperation of thin layer for stress between each layer stress matches well, effectual release multilayer complex film between inside, thereby makes between membrane and the basement, membrane and the membrane bond strength high, and the rete is difficult for droing, is difficult for appearing the membrane phenomenon of splitting.

And, passing through VO₂A thin film layer (refractive index of 2.2-2.7, transparent region of 0.35-12), Si₃N₄A thin film layer (refractive index of 1.8-2.5) and SiO₂The multilayer composite film with the refractive index from high to low, which is formed by combining the film layers (the refractive index is about 1.46), is matched with the tungsten content to increase and change the light transmittance of each layer from inside to outside in sequence, so that the reflectivity of the whole bandwidth is reduced to the maximum extent, the final film layer has better thermotropic phase change characteristics, transparency in a visible light wave band is ensured, and the final film layer has smaller absorption and scattering characteristics, and further the anti-reflection and anti-reflection effects of the film are ensured.

And further optimizing, wherein the seven-layer film layer structure is plated on the front side and the back side of the glass substrate.

For further optimization, the first tungsten-doped VO₂Thin film layer and second tungsten-doped VO₂Thin film layer, third doped tungsten VO₂The thickness of the thin film layer is 45-55 nm.

Preferably, the first tungsten-doped VO₂The tungsten content of the thin film layer is 1.5-2.1 at%; the second tungsten-doped VO₂The tungsten content of the thin film layer is 2.2-2.8 at%; the third tungsten-doped VO₂The tungsten content of the thin film layer is between 2.9 and 3.5 at.%.

For further optimization, the Si₃N₄The thickness of the thin film layer is 100-120 nm.

For further optimization, the SiO₂The thickness of the thin film layer is 200-260 nm.

A preparation method of an anti-reflection and anti-reflection composite film for a glass substrate is characterized by comprising the following steps:

firstly, pretreating a glass substrate material, and bombarding a pretreated glass base surface for 8-12 min by using an ion beam; then, preparing a first tungsten-doped VO by sequentially carrying out a direct-current magnetron sputtering method by adopting an ion source assisted deposition method₂Preparation of Si by thin film layer and intermediate frequency magnetron sputtering method₃N₄Thin film layer and second tungsten-doped VO₂Thin film layer and Si₃N₄Thin film layer, third doped tungsten VO₂Thin film layer and Si₃N₄A thin film layer for forming W-doped VO on the glass base surface₂Thin film layer and Si₃N₄Six composite film layers with alternately superposed film layers; then adopting the radio frequency magnetron sputtering method of ion source auxiliary deposition to form Si on the outermost layer₃N₄Preparation of SiO on the surface of the thin film layer₂A thin film layer; finally, obtaining SiO by magnetron sputtering₂And (4) placing the glass sheet behind the thin film layer under an ultraviolet lamp, and baking at high temperature to obtain the anti-reflection and anti-reflection composite film.

Further optimization, the ion beam bombardment comprises the following specific steps: opening the gas valve, continuously introducing argon gas, wherein the flow of the argon gas is 90-110 sccm, opening the bias power supply, and applying a bias voltage of 180-220V.

Ion beams are adopted for bombardment before magnetron sputtering, and when water vapor and other pollutants adsorbed on the surface of the substrate material are removed, adsorption bonds among the surfaces of the substrate material are changed into other chemical bonds such as covalent bonds and ionic bonds, so that the surface activity of the matrix is improved, the crystal grains of the film layer are refined, the nucleation density is increased, and the adhesion between the film layer and the surface of the matrix and the density of the deposited film are improved by matching with the stress expression form of the coating. Meanwhile, the ion element assistance is carried out during the film coating, and the momentum transfer of the ions to the film increases the energy and the mobility of the particles of the film material, so that a possibly formed columnar structure in the film is damaged, gaps are filled, the concentration density is improved, the structural integrity is improved, the stress condition between the films is further improved, and the density of the film is increased.

And finally, ultraviolet high-temperature baking is assisted, so that the chemical stability and the physical binding property between the matrix material and the composite film are improved.

For further optimization, the glass substrate adopts a QK3 substrate.

Further optimization is carried out, and the pretreatment specifically comprises the following steps: scrubbing a base surface of a glass base material by using acetone and alcohol, and completely wiping off grease on the base surface of the glass; then soaking the substrate material in a hydrofluoric acid alcohol solution with the concentration of 10%, removing an oxide film on the surface of the substrate material, and soaking for 7-9 min; washing and soaking the cotton seeds for 8-12 min by using clean water, taking out the cotton seeds, dipping the cotton seeds in alcohol, and repeatedly scrubbing the cotton seeds for 3-6 times; finally, the adhesive on the surface of the substrate material is blown off by an ear washing ball and is placed in a vacuum environment for standby.

Further optimized, in the direct current magnetron sputtering method, the medium frequency magnetron sputtering method and the radio frequency magnetron sputtering method, the background vacuum degree of the coating chamber is less than 2.0 multiplied by 10^-4After Pa, argon gas with a flow rate of 20sccm was introduced to maintain the pressure in the vacuum chamber at 1.0X 10²Pa, the target base distance is 60 mm.

Further optimized, the direct current magnetron sputtering method is used for preparing the tungsten-doped VO₂The film layer is specifically as follows: introducing oxygen with the oxygen flow of 38-42 sccm by using a metal vanadium target (the purity is 99.99%) and a tungsten target (the purity is 99.99%); the deposition temperature is 440-460 ℃, and the deposition time is 42-48 min; wherein, the power of magnetron sputtering is controlled to control each layer of the VO doped with tungsten₂The content of tungsten in the thin film layer, the first tungsten-doped VO₂The sputtering power of the thin film layer is 210-220W, and the second tungsten-doped VO₂The sputtering power of the thin film layer is 225-235W, and the third tungsten-doped VO₂The sputtering power of the thin film layer is 240-250W.

Further optimized, the intermediate frequency magnetron sputtering method is used for preparing Si₃N₄The film layer is specifically as follows: introducing nitrogen into a silicon target with the purity of 99.99% at a flow rate of 58-62 sccm; the sputtering power is 200-220W, the deposition temperature is room temperature (namely 25 ℃), and the deposition time is 28-32 min.

Further optimized, the radio frequency magnetron sputtering method is used for preparing SiO₂The film layer is specifically as follows: introducing oxygen into a silicon target with the purity of 99.99%, wherein the oxygen flow is 55-65 sccm; the sputtering power is 170-190W, the deposition temperature is 360-400 ℃, and the deposition time is 45-55 min.

Further optimizing, wherein the high-temperature baking temperature is 590-610 ℃, and the time is 18-22 min; the high-temperature baking is carried out under normal pressure.

The invention has the following technical effects:

the invention provides an anti-reflection and anti-reflection composite film for a glass substrate and a preparation method thereof₂Thin film layer, Si₃N₄Thin film layer and SiO layer at outermost layer₂Obtaining tungsten-doped VO (vanadium oxide) through a thin film layer₂/Si₃N₄/ SiO₂The seven-layer composite film structure improves the adhesive force and compactness of the film layer by an ion source assisted deposition method; meanwhile, the combination strength between the film layers and the substrate is further improved by matching with the selection of the substances of the film layers and the stress expression form of the film layers, the stress between the film layers is reduced, and the integral stress value of the whole film is smaller than 300MPa, so that the phenomena of falling off, film cracking, micro-structure curling deformation and the like of the film layers are avoided. And ultraviolet high-temperature baking is assisted, so that the chemical stability and physical binding property between the matrix material and the whole composite film are improved.

The method effectively solves the problem that the low reflectivity and the high mechanical property can not be simultaneously considered in the prior art, and the prepared tungsten-doped VO₂/Si₃N₄/SiO₂The seven-layer composite film structure has good thermotropic phase change characteristics, is transparent in a visible light wave band, and has small absorption, scattering and reflection characteristics; the film has firm and stable structure and no obvious damage to the surface.

Drawings

FIG. 1 is a schematic structural diagram of an antireflection composite film according to an embodiment of the present invention.

FIG. 2 is a graph showing the transmittance before and after coating of the same glass substrate in example 1 of the present invention.

FIG. 3 is a graph showing the light reflectance before and after coating on the same glass substrate in example 1 of the present invention.

FIG. 4 is an electron micrograph of a load test performed after plating in example 3 of the present invention.

FIG. 5 is an SEM image of the film coated in example 3 of the present invention.

Wherein, 1, a glass substrate; 21. first doped tungsten VO₂A thin film layer; 22. second tungsten-doped VO₂A thin film layer; 23. third doped tungsten VO₂A thin film layer; 3. si₃N₄A thin film layer; 4. SiO 2₂A thin film layer.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.