CN110331366B - Preparation method of vanadium dioxide-based composite film - Google Patents
Preparation method of vanadium dioxide-based composite film Download PDFInfo
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- CN110331366B CN110331366B CN201910700292.2A CN201910700292A CN110331366B CN 110331366 B CN110331366 B CN 110331366B CN 201910700292 A CN201910700292 A CN 201910700292A CN 110331366 B CN110331366 B CN 110331366B
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- C—CHEMISTRY; METALLURGY
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
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- C—CHEMISTRY; METALLURGY
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- 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
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
Abstract
The invention discloses a preparation method of a vanadium dioxide-based composite film, which comprises the following steps: sputtering a target material by using a metal vanadium target and a zinc oxide ceramic target, and depositing on quartz glass by using argon as a reaction gas to obtain a vanadium film doped with zinc oxide; and putting the obtained vanadium film doped with the zinc oxide into an annealing furnace for annealing treatment to obtain the vanadium dioxide-based composite film. According to the invention, the substrate table is not required to be heated in the magnetron sputtering process, the sputtering process is simple, the processes of preparing the zinc oxide-doped vanadium film and preparing the vanadium dioxide-based composite film are separately processed, the preparation process is easier to control, the subsequent annealing process is simple to operate, other gases are not required to be introduced, and the requirements of large-scale production are met. Meanwhile, zinc vanadate is generated on the basis of ensuring a certain amount of vanadium dioxide, so that the visible light transmittance of the film is greatly increased, the sunlight modulation efficiency is also slightly improved, and the film has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a vanadium dioxide-based composite film.
Background
With the rapid development of economy in China, the energy consumption is more and more, and therefore, the problems of air pollution and the like are caused, and how to save energy and reduce emission becomes the current hot topic. According to statistics, the unit area energy consumption of the building in China is far higher than that of developed countries, and the specific energy consumption of the building is mainly reflected in the aspects of lighting, heating, refrigerating and the like. In order to solve the problems, low-E glass is already put forward in the market and is characterized in that a layer of film is plated on the glass to enable infrared light to be reflected greatly, so that the indoor temperature is reduced, and the effect of saving energy in summer is achieved. However, the low-E glass cannot meet the requirement of bidirectional adjustment of winter cooling and summer heating in China, and the intelligent glass can adjust indoor light and heat according to the temperature change in different seasons, so that the effects of being warm in winter and cool in summer are achieved. 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.
Vanadium dioxide as a thermochromic material is widely researched in recent years, the material can generate reversible phase change at a certain temperature, the vanadium dioxide can be converted from a monoclinic phase to a tetragonal rutile phase in a short time when the temperature is increased, the infrared light transmittance of the vanadium dioxide is greatly changed before and after the phase change, the vanadium dioxide is converted from high transmittance to low transmittance, but the visible light transmittance is basically unchanged, the phase change temperature of the vanadium dioxide is lower than that of other thermochromic materials, and the phase change temperature of the massive 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, on the premise of meeting certain sunlight modulation efficiency, the vanadium dioxide film prepared by a magnetron sputtering method has generally low visible light transmittance and higher phase transition temperature, and is far from the application requirements.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium dioxide-based composite film with good solar light modulation efficiency and high visible light transmittance.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a vanadium dioxide-based composite film comprises the following steps:
1) sputtering a target material by using a metal vanadium target and a zinc oxide ceramic target, and depositing on quartz glass by using argon as a reaction gas to obtain a vanadium film doped with zinc oxide;
2) and putting the obtained vanadium film doped with the zinc oxide into an annealing furnace for annealing treatment to obtain the vanadium dioxide-based composite film.
According to the scheme, the purity of the metal vanadium target used in the step 1 is 99.99wt%, and the purity of the zinc oxide ceramic target used is 99.99 wt%.
According to the above scheme, the purity of the argon used in step 1 was 99.9 wt%.
According to the scheme, the vacuum of the back bottom is controlled to be 1 multiplied by 10 in the step 1-3-3×10-3Pa, the sputtering power is 65-85W, the sputtering time of the metal vanadium target is 15-18min, and the sputtering time of the zinc oxide ceramic target is 2-6 min.
According to the scheme, the deposition temperature in the step 1 is normal temperature, and the working pressure of the deposition is 0.1-1.0 Pa.
According to the scheme, the annealing process in the step 2 is divided into three stages of temperature rise, heat preservation and temperature reduction; during annealing, the annealing furnace is vacuumized to 1000-1500Pa, the annealing temperature is set to 400-500 ℃, the annealing temperature rise speed is 5-10 ℃/min, the heat preservation time is 30-90min, and after the heat preservation is finished, the furnace chamber is slowly cooled to the normal temperature under the action of cooling water.
According to the preparation method of the vanadium dioxide-based composite film, provided by the invention, metal vanadium can react with zinc oxide at a certain temperature to generate zinc vanadate, and the zinc vanadate is a substance with good stability and high visible light transmittance. In the process of preparing the vanadium dioxide film, the vanadium dioxide-based composite film with high visible light transmittance can be generated by doping part of zinc oxide, and the film has high sunlight modulation efficiency and meets certain use requirements.
The requirement of the substrate is not particularly limited, the vanadium dioxide thermochromic thin film is generally used on glass, the glass is preferably used as the substrate, and the quartz glass is better attached to the thin film and does not introduce other impurities into the thin film in the subsequent annealing process, so the quartz glass is used as the substrate in the invention.
The invention has the beneficial effects that:
(1) according to the invention, the substrate table is not required to be heated in the magnetron sputtering process, the sputtering process is simple, the processes of preparing the zinc oxide-doped vanadium film and preparing the vanadium dioxide-based composite film are separately processed, the preparation process is easier to control, the subsequent annealing process is simple to operate, other gases are not required to be introduced, and the requirements of large-scale production are met.
(2) The vanadium dioxide-based composite film prepared by the invention has the advantages that zinc vanadate is generated on the basis of ensuring a certain amount of vanadium dioxide, the visible light transmittance of the film is greatly increased, the sunlight modulation efficiency is also slightly improved, and the application prospect is wide.
Drawings
FIG. 1: XRD diffractogram of vanadium dioxide-based composite film prepared in example 1.
FIG. 2: the transmission spectra at room temperature and at high temperature of the vanadium dioxide-based composite film prepared in example 1.
FIG. 3: XRD diffractogram of vanadium dioxide-based composite film prepared in example 2.
FIG. 4: the transmission spectra at room temperature and at high temperature of the vanadium dioxide-based composite film prepared in example 2.
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.
The process for preparing the vanadium dioxide-based composite film by adopting the double-target magnetron sputtering comprises the following steps:
(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 zinc oxide doped vanadium film
Putting the cleaned quartz glass substrate into a magnetron sputtering vacuum chamber, adopting vanadium and zinc oxide with the mass purity of 99.99 percent as target materials, argon with the mass purity of 99.9 percent as working gas, and the background vacuum degree of 1 multiplied by 10-3-3×10-3Pa, the substrate is at normal temperature in the sputtering process, the flux of argon gas is 100-200sccm, the sputtering working pressure is 0.1-1.0Pa, the sputtering power of the vanadium target and the zinc oxide target is the same, the sputtering time of the vanadium target in the sputtering process is 15-18min and is uninterrupted, and the zinc oxide target adopts interrupted sputtering.
(3) Preparation of vanadium dioxide-based composite film
The vanadium film doped with zinc oxide is put into an annealing furnace for annealing treatment, and the temperature change rule in the annealing furnace is divided into three stages of temperature rise, heat preservation and temperature reduction. During annealing, the annealing furnace is vacuumized to 1000-1500Pa, the annealing temperature is set to 400-500 ℃, the annealing temperature rise speed is 5-10 ℃/min, the annealing heat preservation time is 30-90min, and after the heat preservation is finished, the furnace chamber is slowly cooled to the normal temperature under the action of cooling water.
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 rotates slowly in the sputtering process; the vanadium target adopts direct current magnetron sputtering, and the zinc oxide target adopts radio frequency magnetron sputtering.
Example 1
The method for preparing the vanadium dioxide-based composite film on the quartz glass substrate comprises the following specific steps:
(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 20min, finally placing the glass into absolute ethyl alcohol for ultrasonic cleaning for 20min, and then placing the cleaned glass sheet into the absolute ethyl alcohol for sealing for later use.
(2) Preparing a vanadium film doped with zinc oxide on the substrate by adopting direct current and radio frequency magnetron sputtering, drying a 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 (with the purity of 99.99%) and a zinc oxide target (with the purity of 99.99%), pumping the substrate table to be in low vacuum by using a mechanical pump, and then finely pumping the substrate table to 3.0 multiplied by 10 by using a molecular pump-3Pa, introducing reaction gas argon (the purity is 99.9 percent) until the pressure in the cavity is stabilized at 0.5Pa, and keeping the pressure stable. The metal vanadium target adopts direct current magnetron sputtering, and the zinc oxide target adopts radio frequency 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 65W. The sputtering time of the vanadium target in the sputtering process is 16min and is uninterrupted, the zinc oxide target is sputtered for 2min discontinuously, the sputtering is started simultaneously when the vanadium target is sputtered for 1.75min, 5.75min, 9.75min and 13.75min respectively, and the sputtering is stopped after 0.5min of each sputtering.
(3) And (3) placing the zinc oxide-doped vanadium film obtained by sputtering into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 1000Pa, setting the annealing temperature to 450 ℃, setting the annealing temperature-rising speed to 10 ℃/min, setting the annealing heat-preservation time to 50min, and after the heat preservation is finished, slowly cooling the furnace chamber to below 70 ℃ under the action of cooling water, and taking out a sample in the furnace.
(4) The XRD pattern in figure 1 shows that the composition of the film is mainly a composite of vanadium dioxide and zinc vanadate. And the infrared light transmittance of the vanadium dioxide-based composite film is higher at room temperature, and when the temperature is increased to be higher than the phase transition temperature of the film, the infrared light transmittance of the vanadium dioxide-based composite film is reduced. The visible light transmittance of the vanadium dioxide-based composite film is 38.9%, the solar light modulation efficiency is 11.8%, and the high and low temperature transmittance spectrum is shown in fig. 2.
Example 2
The method for preparing the vanadium dioxide-based composite film on the quartz glass substrate comprises the following specific steps:
(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 20min, finally placing the glass into absolute ethyl alcohol for ultrasonic cleaning for 20min, and then placing the cleaned glass sheet into the absolute ethyl alcohol for sealing for later use.
(2) Preparing a vanadium film doped with zinc oxide on the substrate by adopting direct current and radio frequency magnetron sputtering, drying a 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 (with the purity of 99.99%) and a zinc oxide target (with the purity of 99.99%), pumping the substrate table to be in low vacuum by using a mechanical pump, and then finely pumping the substrate table to 1.0 multiplied by 10 by using a molecular pump-3Pa, introducing reaction gas argon (the purity is 99.9 percent) until the pressure in the cavity is stabilized at 0.1Pa, and keeping the pressure stable. The metal vanadium target adopts direct current magnetron sputtering, and the zinc oxide target adopts radio frequency 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 75W. The sputtering time of the vanadium target in the sputtering process is 16min and is uninterrupted, the zinc oxide target is sputtered for 4min discontinuously, the sputtering is started simultaneously when the vanadium target is sputtered for 1.5min, 5.5min, 9.5min and 13.5min respectively, and the sputtering is stopped after 1min of each sputtering.
(3) And (3) placing the zinc oxide-doped vanadium film obtained by sputtering into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 1500Pa, setting the annealing temperature to 400 ℃, setting the annealing temperature-rising speed to 10 ℃/min, setting the annealing heat-preservation time to 70min, and after the heat preservation is finished, slowly cooling the furnace chamber to below 70 ℃ under the action of cooling water, and taking out a sample in the furnace.
(4) The XRD pattern in FIG. 3 shows that the composition of the film is mainly a composite of vanadium dioxide and zinc vanadate. And the infrared light transmittance of the vanadium dioxide-based composite film is higher at room temperature, and when the temperature is increased to be higher than the phase transition temperature of the film, the infrared light transmittance of the vanadium dioxide-based composite film is reduced. Wherein the visible light transmittance of the vanadium dioxide-based composite film is 48.7%, the solar light modulation efficiency is 12.2%, and the high and low temperature transmittance spectrum is shown in figure 4.
Claims (3)
1. A preparation method of a vanadium dioxide-based composite film is characterized by comprising the following steps:
1) sputtering a target material by using a metal vanadium target and a zinc oxide ceramic target, and depositing on quartz glass by using argon as a reaction gas to obtain a vanadium film doped with zinc oxide; specifically, the backing vacuum was controlled to 1X 10-3-3×10-3Pa, the sputtering power is 65-85W, the sputtering time of the metal vanadium target is 15-18min, and the sputtering time of the zinc oxide ceramic target is 2-6 min; the deposition temperature is normal temperature, and the deposition working pressure is 0.1-1.0 Pa;
2) putting the obtained vanadium film doped with the zinc oxide into an annealing furnace for annealing treatment to obtain a compound with the main components of vanadium dioxide and zinc vanadate; specifically, the annealing process is divided into three stages of temperature rise, heat preservation and temperature reduction; during annealing, the annealing furnace is vacuumized to 1000-1500Pa, the annealing temperature is set to 400-500 ℃, the annealing temperature rise speed is 5-10 ℃/min, the heat preservation time is 30-90min, and after the heat preservation is finished, the furnace chamber is slowly cooled to the normal temperature under the action of cooling water.
2. The method for preparing a vanadium dioxide-based composite film according to claim 1, wherein the purity of the metal vanadium target used in step 1 is 99.99wt%, and the purity of the zinc oxide ceramic target used is 99.99 wt%.
3. The method for preparing a vanadium dioxide-based composite film according to claim 1, wherein the purity of argon used in the step 1 is 99.9 wt%.
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| CN110791740B (en) * | 2019-12-02 | 2021-08-24 | 武汉理工大学 | Preparation method of high-performance ZIF-L/vanadium dioxide composite film |
| CN111334771B (en) * | 2020-04-24 | 2021-04-27 | 中国科学院兰州化学物理研究所 | Electrochromic film and preparation method and application thereof |
| CN112981347B (en) * | 2021-02-10 | 2022-08-05 | 武汉理工大学 | Preparation method of acid-treated vanadium dioxide film |
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| CN1807321A (en) * | 2005-12-31 | 2006-07-26 | 中国科学院广州能源研究所 | Highly energy-saving coating glass automatically adjusting light according to environment temperature and multi-layed assembled glass body |
| CN103823310A (en) * | 2014-03-18 | 2014-05-28 | 上海理工大学 | Manufacturing method for high-efficiency infrared heat light modulator |
| CN104961354A (en) * | 2015-06-10 | 2015-10-07 | 武汉理工大学 | Production method of high visible light transmittance vanadium dioxide-based film |
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| US20150362374A1 (en) * | 2014-06-16 | 2015-12-17 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Atomic Layer Deposition of Vanadium Oxide for Microbolometer and Imager |
| AU2017210601B2 (en) * | 2017-08-04 | 2024-03-28 | Royal Melbourne Institute Of Technology | Vanadium oxide films and methods of fabricating the same |
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|---|---|---|---|---|
| CN1807321A (en) * | 2005-12-31 | 2006-07-26 | 中国科学院广州能源研究所 | Highly energy-saving coating glass automatically adjusting light according to environment temperature and multi-layed assembled glass body |
| CN103823310A (en) * | 2014-03-18 | 2014-05-28 | 上海理工大学 | Manufacturing method for high-efficiency infrared heat light modulator |
| CN104961354A (en) * | 2015-06-10 | 2015-10-07 | 武汉理工大学 | Production method of high visible light transmittance vanadium dioxide-based film |
| CN108179394A (en) * | 2018-02-07 | 2018-06-19 | 天津大学 | A kind of method for improving vanadium dioxide phase time-varying amplitude by regulating and controlling sputtering power |
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