CN107043223B - A kind of ordered straight groove microstructure multilayer film glass and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of special glass material processing and production, and relates to ordered linear groove microstructure multilayer film glass and a preparation method thereofPreparing a method; ZrO alternately distributed on surface of glass plate with linear groove microstructure film ₂ Step and trench bottom corresponding thereto, ZrO ₂ Metal layers Al and Cu are sequentially and continuously prepared on the upper surfaces of the bottoms of the steps and the grooves ₂ The O layer and the ZnO layer are three thin films; the preparation method comprises the following steps: 1. preparation of ZrO ₂ The step and the bottom of the groove; 2. preparing a metal Al layer; 3. preparation of Cu ₂ An O layer; 4. preparing a ZnO layer; the invention has the effects of heat insulation, energy conservation, photocatalysis, decoration and the like. For example, the heat insulation and energy saving of the solar cell are realized in that the multilayer film and the microgrooves can block infrared heat radiation and allow visible light to penetrate; the organic matter adsorbed on the surface can be decomposed into water and carbon dioxide under the photocatalysis effect, and the degraded residues are effectively washed clean by the linear micro-groove structure along with natural rainwater, gravity and wind.

Description

A kind of ordered straight groove microstructure multilayer film glass and preparation method thereof

technical field

The invention belongs to the technical field of processing and production of special glass materials, and relates to an ordered linear groove microstructure multilayer film glass and a preparation method thereof.

Background technique

With the reduction of global petroleum energy and the aggravation of environmental pollution, the effective use of solar energy to control indoor heat and cold, photocatalysis to rapidly decompose organic pollutants into inorganic substances to enter the ecological cycle, and to achieve self-cleaning of architectural glass has become a sustainable development. one of the ways out. However, at present, most architectural window glass uses ordinary glass, colored glass or insulating glass (a frame is sandwiched between two pieces of glass and sealed), which has a certain effect on building energy saving and comfort, but cannot meet people's needs. In addition, there is a more popular technical method - that is, filming or coating on ordinary single glass, which can also achieve a certain purpose of heat insulation in summer and winter. In recent years, the popular products in the world include low-emissivity coated monolithic glass (LowE glass for short) and a new type of future glass product - electrochromic glass. They are insufficient in terms of energy-saving efficiency and cost-effectiveness. Chinese Utility Model Patent Application No. 200420083199.0 discloses a low-emissivity coated glass, which is compounded with five film layers: metal oxide film layer, metal or alloy barrier layer, metal silver, metal or alloy barrier layer, metal oxide film layer . The composite glass structure uses too many precious metals and alloys, and the cost is high.

The above-mentioned patents and other products do not have the function of making the energy-saving and light radiation transmission characteristics of the glass to be automatically adjusted in small amounts with the external environment, that is, they do not have the ability to make the glass window realize day/night, sunny/cloudy alternate conditions. They also do not have the more important function of window glass—glass self-cleaning. Regarding the basic principle of self-cleaning and its photocatalysis, the photoelectric/photocatalytic properties of TiO ₂ , which is a wide-bandgap semiconductor material, have always been a hot topic. Journal "J.Phys.D:Appl.Phys." 2010 No. 43 (P.035301) reported that the use of TiO ₂ nanocrystalline porous film as an electrode was applied to photoelectrochemical solar cells and the photoelectric conversion efficiency was improved from 1% to 7.9% or more. The journal "Applied Surface Science" 2011, Vol. 257, No. 20 (P.8451) reported research on the photocatalytic degradation of _TiO2 , which described the use of light-induced effects to study the self-cleaning and antibacterial properties of _TiO2 . The metal oxides with similar properties to the typical photocatalytic material TiO ₂ are also ZnO. The journal "Thin SolidFilms", 2006 No. 496 (P.89-94) reported the doping and multi-layering of ZnO and In ₂ O ₃ . Some in-depth and careful work on phase diagram theory and other aspects, especially the research on electrical conductivity/photoelectricity/photocatalysis of ZnO, has attracted much attention. This is mainly because ZnO not only has the basic properties of the above-mentioned excellent materials, but also has abundant resources, It is cheap and non-toxic, and there is a lot of room for further research and development.

In terms of low-cost optoelectronics and photocatalysis, many metal oxides are good candidate materials. Titanium oxide (ZnO) and cuprous oxide (Cu ₂ O) are used in the present invention because they not only have optoelectronic, photocatalytic and other materials Moreover, they are rich in resources, cheap and non-toxic, and there is a lot of room for further research and development.

At present, there is no decorative effect of rich and precious golden color in the market and literature, with photoelectric, photocatalytic self-cleaning and other functions, with low emissivity and energy saving effect, with no additional electronic control sensing system can automatically follow the outside world. "Linear grooved microstructured film glass", which slightly changes the light radiation transmission characteristics of the glass with light intensity, its structure, preparation method and performance are different from the traditional products and production methods in the past.

SUMMARY OF THE INVENTION

The present invention solves and overcomes the above-mentioned existing problems, and provides an ordered straight groove microstructure multilayer film glass and a preparation method thereof by using the preparation method of physical and chemical compounding.

The present invention is realized by adopting the following technical solutions, and is described as follows in conjunction with the accompanying drawings:

An orderly straight groove microstructure multilayer film glass, comprising a straight groove microstructure film glass plate 1, and the surface of the straight groove microstructure film glass plate 1 is alternately arranged with ZrO ₂ steps 2 and corresponding groove bottoms 3. Three thin films of metal layer Al, Cu ₂ O layer 5 and ZnO layer 6 are successively prepared on the upper surfaces of the ZrO ₂ step 2 and the trench bottom 3 .

The straight groove microstructure film glass plate 1 is a flat plate, and the area of the straight groove microstructure film glass plate 1 is between 1-58000 square centimeters; the period of the vertical projection plane of the ZrO ₂ step 2 and the groove bottom 3 between 700-3000 nm.

The method for preparing an ordered linear groove microstructure multilayer film glass is characterized in that it comprises the following steps:

Step 1. Prepare the ZrO ₂ step and the bottom of the trench;

Step 2, preparing metal layer Al;

Step 3, preparing a Cu ₂ O layer;

Step 4, preparing a ZnO layer.

The specific steps for preparing the ZrO ₂ step 2 and the trench bottom 3 described in the technical solution step 1 are as follows:

1) Equipped with a precursor liquid of ZrO ₂ ; the ratio of the precursor liquid of ZrO ₂ is zirconium tetrabutoxide: benzoylacetone: absolute ethanol=1:0.8:28;

2) using the vertical pulling method to prepare the ZrO ₂ thin film on a clean glass plate;

3) The ZrO ₂ film on the top of the glass plate is obtained by using laser double beam interference to obtain the ZrO ₂ step 2 and the groove bottom 3 , and the glass plate with the ZrO 2 step 2 and the groove bottom 3 is obtained.

The specific steps of preparing the metal layer Al in the technical solution step 2 are as follows:

1) A metal layer Al is deposited by dc physical magnetron sputtering method on the glass plate with ZrO2 steps and the bottom of the groove;

2) In the dc physical magnetron sputtering process, the target material (source material) of the deposited metal layer Al is selected from high-purity Al metal, the sputtering power density is selected as 31W/cm ² , and the sputtering gas pressure of Ar gas is selected. is 1.2Pa, the vacuum degree of the back of the vacuum chamber is selected as 10 ^-3 Pa, and the heating temperature of the substrate table is selected as 200 degrees;

The thickness of the metal layer Al film is between 20 and 200 nanometers.

The specific steps for preparing the Cu ₂ O layer described in step 3 of the technical solution are as follows:

1) Use copper ion solution I and sodium citrate solution II to carry out colloidal chemical reaction in the reaction tank;

2) During the reaction, place the "glass/ZrO ₂ /Al" {ZrO ₂ [with ZrO2 steps 2 and trench bottom 3], Al layer} substrate to be deposited from the glass surface to be deposited after the completion of step 2. into the chemical solution in the reaction tank; at the same time, ultrasonic energy is provided to control the chemical reaction to prepare Cu ₂ O film, the ultrasonic frequency is selected as 15-75 kHz and the output power is 45-250 watts, and the reaction temperature is controlled at 40-75 ℃ scope;

The thickness of the Cu ₂ O layer is between 20 and 500 nanometers.

In the technical scheme, the copper ion-containing solution I is prepared as follows: copper sulfate 0.7-1.3 mol/L, sodium ascorbate 0.3-0.8 mol/L; copper sulfate is preferably 1 mol/L, and sodium ascorbate is preferably 0.5 mol/L;

The sodium citrate solution II is formulated as follows: sodium citrate, 0.03-0.08mol/L; sodium citrate is preferably 0.05mol/L;

The specific steps of preparing the ZnO layer 6 described in the technical solution step 4 are as follows:

1) Using the rf physical magnetron sputtering method on the "glass/ZrO ₂ /Al/Cu ₂ O" (ZrO ₂ , Al layer, Cu ₂ O layer in order from the glass surface) substrate obtained by completing step 3 Preparation of oxide layer ZnO;

2) In the rf physical magnetron sputtering process, the target material (source material) of the deposited oxide layer ZnO is selected from high-purity ZnO ceramics, the sputtering power density is selected as 56W/cm ² , and the sputtering of Ar and O ₂ gases The gas pressure of the ejector is selected as ^2.0Pa , the vacuum degree of the back of the vacuum chamber is selected as 10-3Pa, and the heating temperature of the substrate table is selected as 300 degrees; the thickness of the ZnO layer 6 is between 20-900 nanometers. Finally, "glass/ZrO ₂ /Al/Cu ₂ O/ZnO" is obtained (ZrO ₂ , Al layer, Cu ₂ O layer, ZnO layer in order from the glass surface).

The present invention mainly utilizes a variety of physical and chemical principles—(i) semiconductor photoelectric effect and photocatalytic effect; (ii) material composite principle; (iii) linear groove microstructure design; (iv) low surface emissivity material.

(i) Semiconductor photoelectric effect and photocatalytic effect

The absorption band gap Eg of ZnO is a 3.30eV semiconductor material, which can well match the visible light region of the solar spectrum and has a very good transmittance to visible light. It is well known that a similar oxide semiconductor is Cu ₂ O, which has a forbidden band width Eg of 2.20 eV, and also has almost all of the above-mentioned good physical and chemical properties, as well as optoelectronic properties and photocatalytic properties. The good photoelectric conversion properties of the above two materials are mainly manifested in that when sensitive sunlight irradiates the surface, the carriers in the film material increase; thus, the conductive properties of the ZnO and Cu ₂ O film glass vary with the intensity of the incident light. And change, which will produce the effect of preventing infrared heat radiation and achieve the effect of heat insulation; the photocatalytic properties can enable the film glass to be used for photocatalytic degradation of organic dirt to achieve self-cleaning effect.

(ii) Composite principle of materials

According to the knowledge of energy band theory and crystallography, the forbidden band width of general semiconductors is narrow, and the electrons in the full band are easily excited to enter the conduction band, while leaving holes in the full band. Under the action of the external electric field, the electrons in the conduction band Holes in both and full band can participate in conduction. This explains why the above-mentioned Cu ₂ O/ZnO bilayer film material has good physical and chemical properties and composite effect. In the case of the two metal oxide composite materials of the present invention, because the Cu ₂ O/ZnO double-layer interface has different band gap Eg sizes and carrier potentials, under photon hν irradiation, the oxide semiconductor Cu ₂ The excited photogenerated electrons in O can migrate to the conduction band of another oxide semiconductor, ZnO; the excited holes generated in ZnO can migrate to the valence band of CdS. All of these will enable the effective separation of the respective photogenerated electrons and holes, improve the semiconductor photoelectric effect of both, and ultimately lead to a good photocatalytic self-cleaning effect.

Similar analysis and situation, at the "metal/metal oxide" layer interface of "Al/Cu ₂ O", the Cu ₂ O oxide with the lowest conduction band energy level E _c and the forbidden band width E _g and the Al metal conductor layer The composite band structure can explain its enhanced photocatalytic activity. During the illumination process, the excited photogenerated electrons from the interior of ZnO and Cu ₂ O migrate from the conduction band to the metal, which ultimately reduces the recombination rate of holes and electrons, and improves the properties of optoelectronic and photocatalysts .

Generally, Cu ₂ O with a small band gap can in principle absorb light with a wavelength of 400-800 nm, which can absorb visible light well and make full use of it, but Cu ₂ O cannot make good use of ultraviolet light , because a large part of the energy of the excited electrons and holes is converted into the energy of phonon vibration and is not used for catalysis. We know that the wide band gap of ZnO corresponds to the absorption of the spectral band in the "violet-ultraviolet" region, so A wider spectral range of incident light response can be achieved by combining Cu ₂ O with ZnO.

(iii) Microstructure design of straight grooves

The orderly and densely arranged linear groove microstructure in "Linear Groove Microstructure Film Glass" increases the surface area of the glass sheet and improves the reflection characteristics of sunlight and various thermal radiations. Under the influence of the size effect of the microstructures, they will transmit, reflect and scatter light in different spectral bands differently according to their design; thus, the microstructures of smaller size can improve the blocking of the radiant light in the infrared band to a certain extent, ensuring that The characteristic of visible light transmission is realized.

As we all know, in our environment, solar energy and various thermal radiation sources, light sources, etc. are generally incident light rays to window glass; and the small size of the microstructure makes the thermal radiation light incident on the glass surface produce a certain amount of light. It can be reflected at multiple angles and attenuated by multiple reflections in the linear groove microstructure; this avoids the reflection glare and light pollution caused by the specular reflection (i.e., regular reflection) of ordinary window glass and coated glass. .

(iv) Low surface emissivity materials.

Since the "ZrO ₂ /Al/Cu ₂ O/ZnO" coated on the surface of the straight groove and its steps is a multilayer film of photoelectric and low-emissivity materials, this infrared photothermal radiation reflection layer makes the "straight groove microstructure film""glass" has a very low surface emissivity and a high reflectivity for infrared thermal radiation; while visible light can still pass through the film and glass sheet. The overall effect can keep the indoor light soft, save lighting energy, feel comfortable and beneficial to health.

Through the comprehensive design and utilization of the above four physical principles, the "straight groove microstructure film glass" realizes the following scenario applications. In summer, it can prevent some of the heat radiation from the outdoor sun from entering the room, but the indoor air-conditioning cannot be convected to the outside, saving the cost of air-conditioning; at the same time, it has good transmission characteristics to the visible light diffused in the sky, saving energy lighting costs. In winter, it will effectively reflect the far-infrared rays emitted by indoor heat sinks and indoor objects back into the room to ensure that the indoor heat does not dissipate to the outdoors. At the same time, it can also allow part of the visible light of the sun to enter the room, thereby saving the cost of air conditioning, heating and lighting.

Compared with the prior art, the present invention has beneficial technical effects:

1) A linear groove microstructure film with an orderly and dense arrangement of the multi-layer films "ZrO ₂ /Al/Cu ₂ O/ZnO" and "Al/Cu ₂ O/ZnO" with alternating peaks and valleys, respectively, is realized. Glass and its manufacturing method, the invention "straight groove microstructure film glass" has the effects of sunshade, energy saving and decoration.

2) Its energy saving and low carbon are reflected in the heat insulation and heat preservation, and it can also allow sunlight in the spectral range of the visible region to pass through, so as to achieve the effect of saving electricity for lighting and achieving the effect of glass.

3) Its thermal insulation is reflected in the fact that the multilayer film and micro-grooves can block infrared radiation.

4) The "straight groove microstructure film glass" can automatically change the light radiation transmission characteristics of the glass according to the external light intensity without using an additional electronically controlled sensing system.

5) The photocatalytic effect of the "linear groove microstructure film glass" can also decompose the organic matter adsorbed on the surface into water and carbon dioxide. It is cleaned by the wind; that is, the composite film will make the surface of the object have the function of self-cleaning.

6) The "straight groove microstructure film glass" also has a certain curtain effect, that is, it can realize that people and objects in the room cannot be seen outside in the daytime, but the scene outside can be easily seen indoors.

7) The "straight groove microstructure film glass" can be selectively designed to have various colors such as light yellow, silver and rich golden yellow; it has the characteristics of making the human eye comfortable and certain light transmission; it can be selectively multi-colored Light splitting can selectively reduce the reflection of light (avoid reflection glare and light pollution) and achieve slow reflection, and can selectively have the decorative effect of semi-reflection or full-reflection mirror.

Description of drawings

Below in conjunction with accompanying drawing, the present invention is further described:

Fig. 1 is the front view of the overall structure of the first embodiment of the present invention;

Fig. 2 is A-A sectional view in Fig. 1;

In the figure: 1. Microstructure film glass plate with straight groove; 2. ZrO ₂ step; 3. Bottom of groove; 4. Metal layer Al; 5. Cu ₂ O layer; 6. ZnO layer.

Detailed ways

The present invention is described in detail below:

Example 1

This embodiment is a multi-layer film "ZrO ₂ /Al/Cu ₂ O/ZnO" and "Al/Cu ₂ O/ZnO", which are straight line groove microstructure film glass with alternating peaks and valleys, and the straight line The groove microstructured film glass plate 1 is a 1 cm2 flat plate shape with peaks and valleys alternately wavy-shaped surface ZrO ₂ The period of the vertical projection plane of the step 2 and the groove bottom 3 is 700 nm; the thickness of the metal layer Al is 20 nanometers; the thickness of the Cu ₂ O layer is 20 nanometers; the thickness of the ZnO layer is 20 nanometers.

The manufacturing method of ordered linear groove microstructure multilayer film glass comprises the following steps:

Step 1. Prepare ZrO ₂ step 2 and trench bottom 3:

The ratio of the used ZrO ₂ precursor solution is zirconium tetrabutoxide: benzoylacetone: anhydrous ethanol=1:0.8:28, and ZrO ₂ was prepared on a clean glass plate by vertical pulling method; laser double beam interference was used Acting on the ZrO ₂ above the glass plate, a ZrO ₂ step 2 and a trench bottom 3 are obtained, and the period of the vertical projection plane of the ZrO ₂ step 2 and the trench bottom 3 is 700 nm.

Step 2, prepare metal layer Al:

The metal layer Al was prepared on the surface of the ZrO ₂ step 2 and the trench bottom 3 by the physical magnetron sputtering method; the thickness of the metal layer Al was controlled at 20 nm, the target material was high-purity Al metal, and the DC sputtering power density was 31W /cm ² , the sputtering pressure of Ar gas is 1.2 Pa, the vacuum degree of the back of the vacuum chamber is 10 ^-3 Pa, and the heating temperature of the substrate table is 200 degrees.

Step 3. Preparation of Cu ₂ O layer:

Use copper ion solution I and sodium citrate solution II to carry out colloidal chemical reaction in the reaction tank. During the reaction process, the "glass/ZrO ₂ /Al" substrate to be deposited is put into the chemical solution in the reaction tank. Provide ultrasonic energy to control chemical reaction to prepare Cu ₂ O film; oxide Cu ₂ O layer film thickness is controlled at 20 nanometers; copper ion-containing solution I is: copper sulfate 0.7mol/L, sodium ascorbate 0.3mol/L; The sodium citrate solution II is: sodium citrate, 0.03mol/L. The temperature of solution I and solution II were controlled at 40°C when the Cu ₂ O film was prepared by the chemical method, and the ultrasonic wave was selected as a frequency of 15 kHz and an energy field with an output power of 45 watts was applied to the reaction solution.

Step 4. Preparation of ZnO layer:

A ZnO layer was prepared on the upper surface of the "glass/ZrO ₂ /Al/Cu ₂ O" substrate by means of physical magnetron sputtering. The thickness of the ZnO layer is controlled at 20 nanometers, the target material is high-purity ZnO ceramics, the radio frequency power density is 56W/cm ² , the sputtering gas pressure of Ar and O ₂ gas is 2.0Pa, and the vacuum degree of the back of the vacuum chamber is 10 ^{- 3} Pa, and the substrate table heating temperature is 300 degrees.

Embodiment 2

This embodiment is a multi-layer film "ZrO ₂ /Al/Cu ₂ O/ZnO" and "Al/Cu ₂ O/ZnO", which are straight line groove microstructure film glass with alternating peaks and valleys, and the straight line The grooved microstructured film glass plate is a 1 cm square plate shape with alternating peaks and valleys of the wavy shape of the surface of the ZrO2 step ₂ and the period of the vertical projection plane of the groove bottom 3 is 1800 nm; the thickness of the metal layer Al is 100 nm ; the thickness of the Cu ₂ O layer is 100 nm; the thickness of the ZnO layer is 500 nm.

The manufacturing method of ordered linear groove microstructure multilayer film glass comprises the following steps:

Step 1. Prepare ZrO ₂ step 2 and trench bottom 3:

The ratio of the used ZrO ₂ precursor solution is zirconium tetrabutoxide: benzoylacetone: anhydrous ethanol=1:0.8:28, and ZrO ₂ was prepared on a clean glass plate by vertical pulling method; laser double beam interference was used Acting on the ZrO ₂ above the glass plate, a ZrO ₂ step 2 and a trench bottom 3 are obtained, and the period of the vertical projection plane of the ZrO ₂ step 2 and the trench bottom 3 is 1800 nm.

Step 2, prepare metal layer Al:

A metal layer Al4 was prepared on the surface of the ZrO ₂ step 2 and the trench bottom 3 by physical magnetron sputtering; the thickness of the metal layer Al was controlled at 100 nm, the target material was high-purity Al metal, and the DC sputtering power density was 31W /cm ² , the sputtering pressure of Ar gas is 1.2 Pa, the vacuum degree of the back of the vacuum chamber is 10 ^-3 Pa, and the heating temperature of the substrate table is 200 degrees.

Step 3. Preparation of Cu ₂ O layer:

Use copper ion solution I and sodium citrate solution II to carry out colloidal chemical reaction in the reaction tank. During the reaction process, the "glass/ZrO ₂ /Al" substrate to be deposited is put into the chemical solution in the reaction tank. Provide ultrasonic energy to control chemical reaction to prepare Cu ₂ O film; oxide layer Cu ₂ O film thickness is controlled at 100 nanometers; copper ion-containing solution I is: copper sulfate 1mol/L, sodium ascorbate 0.5mol/L; the lemon Sodium solution II is: sodium citrate, 0.05mol/L. The temperature of solution I and solution II were controlled at 55°C when the Cu ₂ O film was prepared by the chemical method, and an ultrasonic wave with a frequency of 45 kHz and an energy field with an output power of 150 watts was applied to the reaction solution.

Step 4. Preparation of ZnO layer:

A ZnO layer 6 is prepared on the upper surface of the "glass/ZrO ₂ /Al/Cu ₂ O" substrate by means of physical magnetron sputtering. The thickness of the ZnO layer 6 is controlled at 500 nanometers, the target material is high-purity ZnO ceramics, the radio frequency power density is 56W/cm ² , the sputtering gas pressure of Ar and O ₂ gas is 2.0Pa, and the vacuum degree of the back of the vacuum chamber is 10 ^-3 Pa, the substrate table heating temperature is 300 degrees.

Embodiment 3

This embodiment is a multi-layer film "ZrO ₂ /Al/Cu ₂ O/ZnO" and "Al/Cu ₂ O/ZnO", which are straight line groove microstructure film glass with alternating peaks and valleys, and the straight line The grooved microstructured film glass plate 1 is a 1 cm square plate shape with peaks and valleys alternately wavy-shaped surface ZrO ₂ The period of the vertical projection plane of the step 2 and the groove bottom 3 is 3000 nm; the thickness of the metal layer Al is 200 nm nanometers; the thickness of the Cu ₂ O layer is 500 nanometers; the thickness of the ZnO layer is 900 nanometers.

The manufacturing method of ordered linear groove microstructure multilayer film glass comprises the following steps:

Step 1. Prepare ZrO ₂ step 2 and trench bottom 3:

The ratio of the used ZrO ₂ precursor solution is zirconium tetrabutoxide: benzoylacetone: anhydrous ethanol=1:0.8:28, and ZrO ₂ was prepared on a clean glass plate by vertical pulling method; laser double beam interference was used Acting on the ZrO ₂ above the glass plate, a ZrO ₂ step 2 and a trench bottom 3 are obtained, and the period of the vertical projection plane of the ZrO ₂ step 2 and the trench bottom 3 is 3000 nm.

Step 2, prepare metal layer Al:

A metal layer Al4 was prepared on the surface of the ZrO ₂ step 2 and the trench bottom 3 by the physical magnetron sputtering method; the thickness of the metal layer Al was controlled at 200 nm, the target material was high-purity Al metal, and the DC sputtering power density was 31W /cm ² , the sputtering pressure of Ar gas is 1.2 Pa, the vacuum degree of the back of the vacuum chamber is 10 ^-3 Pa, and the heating temperature of the substrate table is 200 degrees.

Step 3. Preparation of Cu ₂ O layer:

Use copper ion solution I and sodium citrate solution II to carry out colloidal chemical reaction in the reaction tank. During the reaction process, the "glass/ZrO ₂ /Al" substrate to be deposited is put into the chemical solution in the reaction tank. Provide ultrasonic energy to control chemical reaction to prepare Cu ₂ O film; oxide layer Cu ₂ O film thickness is controlled at 500 nanometers; copper ion-containing solution I is: copper sulfate 1.3mol/L, sodium ascorbate 0.8mol/L; Sodium citrate solution II is: sodium citrate, 0.08mol/L. The temperature of solution I and solution II were controlled at 75°C when the Cu ₂ O film was prepared by the chemical method, and an ultrasonic wave with a frequency of 75 kHz and an energy field with an output power of 250 watts was applied to the reaction solution.

Step 4. Preparation of ZnO layer:

A ZnO layer 6 is prepared on the upper surface of the "glass/ZrO ₂ /Al/Cu ₂ O" substrate by means of physical magnetron sputtering. The thickness of the ZnO layer 6 is controlled at 900 nanometers, the target material is high-purity ZnO ceramics, the radio frequency power density is 56W/cm ² , the sputtering gas pressure of Ar and O ₂ gas is 2.0Pa, and the vacuum degree of the back of the vacuum chamber is 10 ^-3 Pa, the substrate table heating temperature is 300 degrees.

Claims (10)

1. a preparation method of ordered linear groove microstructure multilayer film glass, is characterized in that, comprises the following steps: Step 1. Prepare ZrO ₂ steps (2) and trench bottoms (3); Step 2, preparing metal layer Al; Step 3, preparing a Cu ₂ O layer; Step 4, preparing a ZnO layer. 2. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 1, is characterized in that: The specific steps for preparing the ZrO ₂ step (2) and the trench bottom (3) described in step 1 are as follows: 1) Equipped with a precursor liquid of ZrO ₂ ; the ratio of the precursor liquid of ZrO ₂ is zirconium tetrabutoxide: benzoylacetone: absolute ethanol=1:0.8:28; 2) using the vertical pulling method to prepare the ZrO ₂ thin film on a clean glass plate; 3) Using laser double beam interference on the ZrO ₂ film above the glass plate to obtain ZrO ₂ steps (2) and groove bottoms (3), and obtain a glass with ZrO ₂ steps (2) and groove bottoms (3) plate. 3. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 2, is characterized in that: The specific steps of preparing the metal layer Al in step 2 are as follows: 1) depositing a metal layer Al (4) on top of the glass plate with ZrO ₂ steps (2) and trench bottoms (3) using a dc physical magnetron sputtering method; 2) In the dc physical magnetron sputtering process, the target material of the deposited metal layer Al(4) is selected as high-purity Al metal, the sputtering power density is selected as 31W/cm ² , and the sputtering gas pressure of Ar gas is selected as 1.2Pa, the vacuum degree of the back of the vacuum chamber is selected as 10 ^-3 Pa, and the heating temperature of the substrate table is selected as 200 degrees. 4. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 3, is characterized in that: The Al(4) film thickness of the metal layer is between 20-200 nanometers. 5. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 4, is characterized in that: The specific steps for preparing the Cu ₂ O layer described in step 3 are as follows: 1) Use copper ion solution I and sodium citrate solution II to carry out colloidal chemical reaction in the reaction tank; 2) put the to-be-deposited "glass/ZrO ₂ /Al" substrate obtained in step 2 into the chemical solution in the reaction tank during the reaction; simultaneously provide ultrasonic energy to control the chemical reaction to prepare the Cu ₂ O film, Ultrasonic waves are selected at a frequency of 15-75 kHz and an output power of 45-250 watts, and the reaction temperature is controlled in the range of 40-75°C. 6. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 5, is characterized in that: The thickness of the Cu ₂ O layer is between 20-500 nanometers; The copper ion-containing solution I is prepared as follows: copper sulfate 0.7-1.3 mol/L, and sodium ascorbate 0.3-0.8 mol/L; the sodium citrate solution II is prepared as: sodium citrate, 0.03-0.08 mol/L. 7. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 6, is characterized in that: The specific steps of preparing the ZnO layer described in step 4 are as follows: 1) using the rf physical magnetron sputtering method to prepare the oxide ZnO layer (6) on the "glass/ZrO ₂ /Al/Cu ₂ O" substrate obtained by completing step 3; 2) In the rf physical magnetron sputtering process, the target material of the deposited oxide ZnO layer (6) is high-purity ZnO ceramics, the sputtering power density is selected as 56W/cm ² , and the sputtering of Ar and O ₂ gases The gas pressure was selected as 2.0 Pa, the vacuum degree of the back of the vacuum chamber was selected as 10 ^-3 Pa, and the heating temperature of the substrate table was selected as 300 degrees. 8. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 7, is characterized in that: The thickness of the ZnO layer (6) is between 20 and 900 nanometers. 9. The method for preparing an ordered straight groove microstructure multilayer film glass according to claim 8, wherein the ordered straight groove microstructure multilayer film glass comprises a straight groove microstructure film glass plate (1), ZrO ₂ steps (2) and corresponding groove bottoms (3) are alternately arranged on the surface of the straight groove microstructure film glass plate (1), and ZrO ₂ steps (2) and the upper surface of the groove bottom (3) Three-layer thin films of metal layer Al (4), Cu ₂ O layer (5) and ZnO layer (6) are successively prepared. 10. the preparation method of a kind of ordered straight groove microstructure multilayer film glass according to claim 9, is characterized in that: The linear groove microstructure film glass plate (1) is a flat plate, and the area of the linear groove microstructure film glass plate (1) is between 1-58000 square centimeters; The period of the vertical projection plane of the ZrO ₂ step (2) and the trench bottom (3) is between 700-3000 nanometers.

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