CN110791740A - Preparation method of high-performance ZIF-L/vanadium dioxide composite film - Google Patents
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a high-performance ZIF-L/VO2A preparation method of a composite film. Depositing a vanadium film on a quartz glass substrate by taking a metal vanadium target as a sputtering target material and argon as a reaction gas; annealing to form a vanadium dioxide film; preparing ZIF-L sol by a chemical method; and spin-coating the chemically prepared ZIF-L sol on the vanadium dioxide film to obtain a double-layer film structure. ZIF-L/VO prepared by the invention2The composite film adopts the combination of a magnetron sputtering physical deposition method and a chemical method sol, so that the visible light transmittance and the sunlight regulation efficiency of the composite film are improved, and the prepared ZIF-L/VO2The visible light transmittance of the film is 35.3-46.4%, the solar light modulation efficiency is 9.8-14.89%, and the film has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a high-performance ZIF-L/VO2A preparation method of a composite film.
Background
The rapid development of economy usually brings huge consumption of energy and resource consumption, and then various pollution problems of the environment, including water pollution, atmospheric pollution and soil pollution, so that energy conservation and emission reduction become very important problems in the current era. According to statistics, the energy consumption per unit area of a building in China is much higher than that of a developed country, and the energy consumption of the building is mainly reflected in the aspects of heating, lighting, refrigerating and the like. In view of these problems, the heating and cooling equipment for buildings has been changed to energy saving type, and in the aspect of building glass for lighting, low-E glass has been introduced in the market, and the low-E glass is characterized in that a layer of film is mainly plated on the lighting glass, and the film can reflect a large amount of infrared rays to reduce the indoor temperature, thereby reducing the energy consumption. However, the low-E glass on the market only reflects infrared rays to reduce the room temperature at present, but cannot intelligently and bidirectionally adjust the room temperature according to cold and hot alternation in four seasons. To this problem, intelligent window glass has just aroused people's attention, and it can be according to the cold and hot alternation that the four seasons changes and intelligent carries out the light and heat regulation and control to indoor temperature, realizes the effect that warm in winter and cool in summer. The intelligent glass is prepared by plating a film material with thermochromic performance on the glass, and has the advantages of simple operation, relatively low cost and wide application prospect in the field of energy-saving glass.
The M-phase vanadium dioxide has attracted much attention since 1953, and the characteristics of the M-phase vanadium dioxide, namely the phase transition temperature point closest to room temperature, huge physical property changes before and after phase transition, and high and reversible phase transition speed are very prominent in the aspect of preparing intelligent window materials. The M-phase vanadium dioxide has reversible phase change at a certain temperature, a low-temperature semiconductor phase is converted into a high-temperature rutile phase, and a crystal form before and after the phase change is converted into the rutile phase from a monoclinic phase. In addition, the infrared transmittance of the R-phase vanadium dioxide after the phase transformation is significantly reduced, thereby achieving the effect of reflecting infrared light, but the visible light transmittance thereof is almost unchanged. The phase transition temperature of the bulk M-phase vanadium dioxide material is 68 ℃. By combining the performance characteristics, the vanadium dioxide has obvious advantages in the application of the intelligent glass.
The methods for preparing vanadium dioxide films are various, and mainly comprise a magnetron sputtering method, a sol-gel method, a pulse laser deposition method, an ion beam sputtering method and the like.
At present, the sunlight regulation efficiency of the M-phase vanadium dioxide film prepared by a simple magnetron sputtering method is not high, the transmittance of visible light is low, and the phase change temperature is higher than room temperature, so how to solve the problems becomes the important factor of the practical application of the vanadium dioxide film on an intelligent window.
Disclosure of Invention
The invention aims to provide a ZIF-L/VO with good solar light modulation efficiency and high visible light transmittance2A preparation method of a composite film. In order to achieve the purpose, the technical scheme is as follows:
high-performance ZIF-L/VO2The preparation method of the composite film comprises the following steps:
1) depositing a vanadium film on a quartz glass substrate by taking a metal vanadium target as a sputtering target material and argon as a reaction gas; annealing to form a vanadium dioxide film;
2) preparing ZIF-L sol by a chemical method;
3) and spin-coating the chemically prepared ZIF-L sol on the vanadium dioxide film to obtain a double-layer film structure.
According to the scheme, the background vacuum degree of the preparation process of the vanadium film in the step 1 is controlled to be 1.0-3.0 multiplied by 10-3Pa, the substrate is 40-80 ℃ in the sputtering process, the flux of argon gas is 100-200sccm (standard milliliter/minute), the sputtering working pressure is 0.1-1.0Pa, the sputtering power of the vanadium target is 60-80W, and the sputtering time of the vanadium target is 8-16min without interruption.
According to the scheme, the vanadium film obtained in the step 1 is placed in a vacuum annealing furnace for annealing treatment, and the annealing treatment comprises three stages of temperature rise, heat preservation and temperature reduction; the air pressure is adjusted to 650-1000Pa, the annealing temperature is set to 370-470 ℃, the temperature rising speed is 2-10 ℃/min, the heat preservation time is 30-90min, and the furnace is cooled to the room temperature by the circulating water in the furnace cavity after the heat preservation is finished.
According to the scheme, in the step 2, zinc acetate dihydrate and dimethyl imidazole are added into a methanol solvent, and are mixed and stirred for 2-6 hours at room temperature to obtain transparent ZIF-L sol.
According to the scheme, the concentration of the ZIF-L sol in the step 3 is 1-5mol/L, the steps of spin-coating the ZIF-L film are 1-2 steps, the rotating speed is 1500-4500r/min, the spin-coating time is 10-30s, and the curing temperature is 80-140 ℃.
The invention provides a high-performance ZIF-L/VO2The preparation method of the composite film utilizes the organic combination of the high light transmittance of the ZIF-L film and the pure vanadium dioxide film to improve the overall performance of the composite film. A layer of ZIF-L film is coated on the basis of the pure vanadium dioxide film in a spin mode, so that the overall sunlight regulation efficiency and the visible light transmittance are improved to a certain degree, and certain use requirements are met.
The requirement of the invention on the substrate is not very high, because the vanadium dioxide thermochromic thin film is generally applied to common glass, the invention takes the glass as the thin film substrate, and because the adhesiveness of the thin film on the quartz glass is better, and other impurities which influence the performance of the thin film can not be generated in the subsequent annealing treatment, the invention takes the quartz glass as the substrate.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the ZIF-L sol is simple, and the preparation process of the M-phase vanadium dioxide and the ZIF-L sol by magnetron sputtering is separated, so that the preparation process is easier to operate and regulate.
The method comprises the steps of obtaining a metal vanadium film by sputtering a direct-current metal vanadium target, then carrying out annealing treatment, carrying out spin coating treatment on ZIF-L sol prepared by a chemical method on the basis of obtaining a pure vanadium dioxide film obtained by a physical method, and then carrying out heating and curing to obtain the composite double-layer structure film with high solar light regulation efficiency and high stability of visible light transmittance.
ZIF-L/VO prepared by the invention2The composite film adopts the combination of a magnetron sputtering physical deposition method and a chemical method sol, so that the visible light transmittance and the sunlight regulation efficiency of the composite film are improved, and the prepared ZIF-L/VO2The visible light transmittance of the film is 35.3-46.4%, the solar light modulation efficiency is 9.8-14.89%, and the film has wide application prospect.
Drawings
FIG. 1: vanadium dioxide thin film obtained in example 1 and ZIF-L/VO2XRD diffraction pattern of the composite film;
FIG. 2: ZIF-L/VO obtained in example 12A cross-sectional SEM image of the composite film;
FIG. 3: ZIF-L/VO obtained in example 12A transmission spectrum of the composite film at room temperature and high temperature;
FIG. 4: ZIF-L/VO obtained in example 22Transmission spectra of the composite film at room temperature and elevated temperature.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
ZIF-L/VO of the invention2The detailed preparation process of the composite film is as follows:
(1) cleaning of quartz glass substrates
Cleaning quartz glass with a detergent, sequentially carrying out ultrasonic cleaning with distilled water and absolute ethyl alcohol, and finally placing the quartz glass into the absolute ethyl alcohol for sealing for later use.
(2) Preparation of pure M-phase vanadium dioxide film
Putting the cleaned quartz glass substrate into a magnetron sputtering vacuum chamber, adopting metal vanadium with the mass purity of 99.99 percent as a target material, adopting argon with the mass purity of 99.9 percent as a working gas, wherein the background vacuum degree is 1.0-3.0 multiplied by 10 < -3 > Pa, the substrate is 40-80 ℃ in the sputtering process, the flux of the argon gas is 100 plus 200sccm (standard milliliter per minute), the sputtering working gas pressure is 0.1-1.0Pa, the sputtering power of a vanadium target is 60-80W, and the sputtering time of the vanadium target in the sputtering process is 8-16min and is uninterrupted. And (3) putting the sputtered metal vanadium film into a vacuum annealing furnace for annealing treatment, wherein the temperature in the annealing furnace is set to be three stages of temperature rise, heat preservation and temperature reduction. During annealing, the annealing pressure is adjusted to 650-1000Pa, the annealing temperature is set to 370-470 ℃, the annealing temperature rise speed is 2-10 ℃/min, the annealing heat preservation time is 30-90min, and after the heat preservation is finished, the annealing furnace is cooled to the room temperature by circulating water in the furnace cavity.
(3) Preparation of ZIF-L Sol
2.7439g-5.4878g of zinc acetate dihydrate and 1.0263g-2.0525g of dimethyl imidazole are respectively weighed by an electronic analytical balance and placed in a 30mL transparent glass bottle filled with magnetons, then 5mL-25mL of methanol solvent is added, and the mixture is placed on a magnetic stirrer at room temperature and stirred for 2-6h, so that transparent ZIF-L sol is obtained.
(4)ZIF-L/VO2Preparation of composite films
And (3) cleaning the surface of the pure M-phase vanadium dioxide film prepared in the step (2), placing the film in a spin coater, uniformly coating the ZIF-L sol prepared in the step (3) on the vanadium dioxide film for spin coating treatment, wherein the number of steps of the spin coater is set to be 1-2, the spin coating speed is 1500r/min-4500r/min, and the spin coating time is 10-30 s. The ZIF-L/VO which is spin-coated is finished2And (3) placing the composite film on a digital display heating table for heating and curing, wherein the curing temperature of the digital display heating table is 80-140 ℃.
The ultrasonic cleaning time of the distilled water and the absolute ethyl alcohol in the step 1 is the same. In the step 2, in order to make the sputtered film more uniform, the glass substrate table slowly rotates in the sputtering process; the vanadium target adopts direct current magnetron sputtering. The zinc acetate dihydrate and the dimethyl imidazole in the step 3 are analytical pure reagents, and the purity of the reagents is 99%.
Example 1
(1) The glass substrate is cleaned by the following process: firstly, cleaning the surface of glass by using a detergent, then adding distilled water for ultrasonic cleaning for 30min, finally placing the glass into absolute ethyl alcohol for ultrasonic cleaning for 30min, and then placing the cleaned glass sheet into the absolute ethyl alcohol for sealing for later use.
(2) Preparing a pure metal vanadium film on the substrate by adopting direct current magnetron sputtering, drying the quartz glass substrate, fixing the quartz glass substrate on a substrate table by using a high-temperature resistant adhesive tape, putting the substrate table into a magnetron sputtering working chamber, putting a metal vanadium target (the purity is 99.99%), controlling the substrate to be 40 ℃ in the sputtering process, firstly pumping the substrate to be 15Pa by using a mechanical pump, then finely pumping the substrate to be 3.0 x 10 < -3 > Pa by using a molecular pump, introducing reaction gas argon (the purity is 99.9%), controlling the flux of the argon gas to be 100sccm (standard milliliter per minute), and keeping the pressure in the chamber to be 0.5Pa stably. The metal vanadium target adopts direct current magnetron sputtering, the sputtering power of the direct current magnetron sputtering and the sputtering power of the radio frequency magnetron sputtering are both set to be 80W, and the sputtering time of the vanadium target is 10min and is uninterrupted. Placing the pure metal vanadium film obtained by sputtering into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 650Pa, setting the annealing heat preservation temperature to 370 ℃, setting the annealing temperature rise speed to 2 ℃/min, setting the annealing heat preservation time to 90min, and after the heat preservation is finished, slowly cooling the furnace chamber to below 50 ℃ under the action of cooling water, and taking out a sample in the furnace.
(3) 5.4878g of zinc acetate dihydrate and 2.0525g of dimethyl imidazole are respectively weighed by an electronic analytical balance and placed in a 30mL transparent glass bottle filled with magnetons, 5mL of methanol solvent is added, the glass bottle is placed on a magnetic stirrer to be mixed and stirred for 3 hours, and transparent ZIF-L sol is obtained, wherein the concentration of the sol is 5 mol/L.
(4) And (4) spin-coating the ZIF-L sol obtained in the step (3) on the pure vanadium dioxide obtained in the step (2) by using a spin coater. The number of steps of spin coating is set as 2 steps, the rotating speed of the first step is 1000r/min, the rotating time is 10s, the rotating speed of the second step is 3500r/min, and the rotating time is 15 s. And (3) placing the spin-coated composite film on a digital display heating plate at the temperature of 80 ℃ for curing treatment until the curing is complete.
FIG. 1 shows a pure vanadium dioxide thin film and ZIF-L/VO fabricated on a quartz glass substrate by sputter deposition in this example2XRD diffraction pattern of the composite film, it can be seen that the first layer of the film is pure M-phase vanadium dioxide film, and ZIF-L and VO are used2The XRD after recombination also shows VO2A peak and an amorphous peak, wherein the amorphous peak is amorphous ZIF-L. FIG. 2 is ZIF-L/VO prepared in this example2SEM image of the cross section of the composite film, from which it can be seen that the film has two layers of filmsConsists of the following components: thinner VO2Membranes and thicker ZIF-L membranes. FIG. 3 is ZIF-L/VO prepared in this example2The transmission spectrum of the composite film at room temperature and high temperature is shown as ZIF-L/VO2The film has high infrared light transmittance at room temperature, and ZIF-L/VO is obtained when the temperature reaches 90 DEG C2The infrared transmittance of the film is significantly reduced. The low-temperature visible light transmittance of the composite film is 46.43% and the sunlight regulation efficiency is 9.8% through calculation.
Example 2
(1) The glass substrate is cleaned by the following process: firstly, cleaning the surface of glass by using a detergent, then adding distilled water for ultrasonic cleaning for 50min, finally placing the glass into absolute ethyl alcohol for ultrasonic cleaning for 50min, and then placing the cleaned glass sheet into the absolute ethyl alcohol for sealing for later use.
(2) Preparing a pure metal vanadium film on the substrate by adopting direct current magnetron sputtering, drying the quartz glass substrate, fixing the quartz glass substrate on a substrate table by using a high-temperature resistant adhesive tape, putting the substrate table into a magnetron sputtering working chamber, putting a metal vanadium target (the purity is 99.99%), wherein the substrate is 80 ℃ in the sputtering process, firstly pumping the vacuum to 15Pa by using a mechanical pump, then finely pumping the substrate to 1.0 x 10 < -3 > Pa by using a molecular pump, introducing reaction gas argon (the purity is 99.9%), ensuring the flux of the argon gas to be 200sccm (standard milliliter per minute), and keeping the pressure in the chamber to be stable at 1.0Pa and keeping the stability. The metal vanadium target adopts direct current magnetron sputtering, the sputtering power of the direct current magnetron sputtering and the sputtering power of the radio frequency magnetron sputtering are both set to be 60W, and the sputtering time of the vanadium target is 15min and is uninterrupted. Placing the pure metal vanadium film obtained by sputtering into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 1000Pa, setting the annealing heat preservation temperature to 470 ℃, setting the annealing temperature rise speed to 10 ℃/min, setting the annealing heat preservation time to 30min, and taking out a sample in the furnace when the furnace chamber is slowly cooled to below 50 ℃ under the action of cooling water after the heat preservation is finished.
(3) 2.7439g of zinc acetate dihydrate and 1.0263g of dimethyl imidazole are respectively weighed by an electronic analytical balance and placed in a 30mL transparent glass bottle filled with magnetons, then 25mL of methanol solvent is added, the glass bottle is placed on a magnetic stirrer to be mixed and stirred for 3 hours, and transparent ZIF-L sol is obtained, wherein the concentration of the sol is 1.0 mol/L.
(4) And (4) spin-coating the ZIF-L sol obtained in the step (3) on the pure vanadium dioxide obtained in the step (2) by using a spin coater. The number of steps of spin coating is set as 2 steps, the rotating speed of the first step is 1000r/min, the rotating time is 10s, the rotating speed of the second step is 4500r/min, and the rotating time is 10 s. And (3) placing the spin-coated composite film on a digital display heating plate at 140 ℃ for curing treatment until the curing is complete.
FIG. 4 shows ZIF-L/VO of the present embodiment2The transmission spectrum of the composite film at room temperature and high temperature is shown as ZIF-L/VO2The film has high infrared light transmittance at room temperature, and ZIF-L/VO is obtained when the temperature reaches 90 DEG C2The infrared transmittance of the film is significantly reduced. The low-temperature visible light transmittance of the composite film is 36.13% and the sunlight regulation efficiency is 14.89%.
Claims (5)
1. High-performance ZIF-L/VO2The preparation method of the composite film is characterized by comprising the following steps:
1) depositing a vanadium film on a quartz glass substrate by taking a metal vanadium target as a sputtering target material and argon as a reaction gas; annealing to form a vanadium dioxide film;
2) preparing ZIF-L sol by a chemical method;
3) and spin-coating the chemically prepared ZIF-L sol on the vanadium dioxide film to obtain a double-layer film structure.
2. The high performance ZIF-L/VO of claim 12The preparation method of the composite film is characterized in that the background vacuum degree of the preparation process of the vanadium film in the step 1 is controlled to be 1.0-3.0 multiplied by 10-3Pa, the substrate is 40-80 ℃ in the sputtering process, the flux of argon gas is 100-200sccm (standard milliliter/minute), the sputtering working pressure is 0.1-1.0Pa, the sputtering power of the vanadium target is 60-80W, and the sputtering time of the vanadium target is 8-16min without interruption.
3. The high performance ZIF-L/VO of claim 12The preparation method of the composite film is characterized in that the vanadium obtained in the step 1The film is put into a vacuum annealing furnace for annealing treatment, and the annealing treatment comprises three stages of temperature rise, heat preservation and temperature reduction; the air pressure is adjusted to 650-1000Pa, the annealing temperature is set to 370-470 ℃, the temperature rising speed is 2-10 ℃/min, the heat preservation time is 30-90min, and the furnace is cooled to the room temperature by the circulating water in the furnace cavity after the heat preservation is finished.
4. The high performance ZIF-L/VO of claim 12The preparation method of the composite film is characterized in that in the step 2, zinc acetate dihydrate and dimethyl imidazole are added into a methanol solvent, and are mixed and stirred for 2-6 hours at room temperature to obtain transparent ZIF-L sol.
5. The high performance ZIF-L/VO of claim 12The preparation method of the composite film is characterized in that the concentration of the ZIF-L sol in the step 3 is 1-5mol/L, the step number of the ZIF-L film spin coating is 1-2 steps, the rotating speed is 1500-4500r/min, the spin coating time is 10-30s, and the curing temperature is 80-140 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286697A (en) * | 2020-03-13 | 2020-06-16 | 武汉理工大学 | High-performance reticular vanadium dioxide-based composite film and preparation method thereof |
| CN111334771A (en) * | 2020-04-24 | 2020-06-26 | 中国科学院兰州化学物理研究所 | Electrochromic film and preparation method and application thereof |
| CN112981347A (en) * | 2021-02-10 | 2021-06-18 | 武汉理工大学 | Preparation method of acid-treated vanadium dioxide film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009134211A1 (en) * | 2008-04-29 | 2009-11-05 | Agency For Science, Technology And Research | Inorganic graded barrier film and methods for their manufacture |
| CN102061112A (en) * | 2010-11-12 | 2011-05-18 | 华东师范大学 | Preparation method of composite metal organic framework material colloidal solution and application thereof in optical coatings |
| CN102212782A (en) * | 2011-05-24 | 2011-10-12 | 天津大学 | Quick thermal treatment method for preparing vanadium dioxide film |
| CN104099563A (en) * | 2013-04-03 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Method for preparing vanadium dioxide film by using magnetron sputtering process |
| CN106868451A (en) * | 2017-03-28 | 2017-06-20 | 泉州市中知信息科技有限公司 | One kind has VO2The coating process of the intelligent power saving glass of plated film |
| CN109989002A (en) * | 2019-05-13 | 2019-07-09 | 河南理工大学 | HfO2/VO2/HfO2Sandwich structure smart window film and preparation method thereof |
| CN110331366A (en) * | 2019-07-31 | 2019-10-15 | 武汉理工大学 | A kind of preparation method of hypovanadic oxide-based composite film |
-
2019
- 2019-12-02 CN CN201911212754.2A patent/CN110791740B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009134211A1 (en) * | 2008-04-29 | 2009-11-05 | Agency For Science, Technology And Research | Inorganic graded barrier film and methods for their manufacture |
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