CN111116050A - Tungsten-doped vanadium dioxide thin film and preparation method and application thereof - Google Patents
Tungsten-doped vanadium dioxide thin film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a tungsten-doped vanadium dioxide thin film and a preparation method and application thereof, wherein the film thickness of the tungsten-doped vanadium dioxide thin film is 20-40 nm, the phase transition temperature is 25-45 ℃, and the visible light transmittance is 50-60%. The tungsten-doped vanadium dioxide thin film has low phase transition temperature, can generate phase transition at the most suitable temperature for human life, and meets the requirements of intelligent glass windows; the preparation method of the invention adopts the metal vanadium target and the tungsten target to be simultaneously mixed and sputtered, has short sputtering time, is simple and easy to operate, does not need to add other gases during subsequent annealing, and is convenient for large-scale production.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a tungsten-doped vanadium dioxide film and a preparation method and application thereof.
Background
As human society develops, we will face many difficulties and challenges, and climate change will be one of the major challenges we will overcome in the near future. The global average air temperature has risen rapidly over the past 40 years, leading to increased concerns about energy efficiency. In order to reduce energy consumption, the energy utilization efficiency of the building can be improved by using the intelligent window. The intelligent window is a window which is additionally plated with a film material with the thermochromic performance on the surface of glass, and the film material with the thermochromic performance can regulate and control indoor light and heat according to the change of temperatures in different seasons, so that the effects of being warm in winter and cool in summer are achieved, the energy consumption is reduced, the operation is simple, and the cost is relatively low.
In recent years, vanadium dioxide has been widely studied as a thermochromic material, the mechanism of which is that vanadium dioxide undergoes a phase change to change its optical properties. Specifically, when the temperature is increased to exceed the transition temperature, the monoclinic structure is changed into a tetragonal rutile structure, the forbidden band is changed into a conduction band with a metal characteristic, and the near-mid infrared band (400-4000 cm)-1) The transmittance is obviously changed, the absorption and reflection of electromagnetic waves in visible and infrared wave bands are enhanced, and the transmittance is reduced; when the temperature is lower than the transition temperature, the monoclinic structure has a forbidden band with the width of 0.7eV, so that the optical fiber has very high transmittance for visible light and infrared bands. Therefore, the vanadium dioxide thin film coating can play a role in adjusting the solar light transmittance.
Research institutions of various countries still struggle in the direction of industrialization of vanadium dioxide intelligent windows with inexhaustible cumin, but the effect is very little, and the main reason is that the phase transition temperature of a pure vanadium dioxide film is too high (68 ℃), the phase transition temperature of the film needs to be reduced to be close to the most suitable temperature (25 ℃) for human life, and the vanadium dioxide film applied to automobiles, glass and building materials can be ensured to have phase transition and effectively adjust solar radiation when the environmental temperature is higher than the temperature.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a tungsten-doped vanadium dioxide film and a preparation method and application thereof, and solves the technical problem that the pure vanadium dioxide film in the prior art has overhigh phase transition temperature and is not beneficial to phase transition at the optimum temperature for human life.
In order to achieve the technical purpose, the first aspect of the invention provides a tungsten-doped vanadium dioxide thin film, wherein the thickness of the tungsten-doped vanadium dioxide thin film is 20-40 nm, the phase transition temperature is 25-45 ℃, and the visible light transmittance is 50-60%.
The second aspect of the invention provides a preparation method of a tungsten-doped vanadium dioxide film, which comprises the following steps:
forming a tungsten-doped vanadium film on the surface of the substrate by adopting double-target magnetron sputtering;
and annealing the tungsten-doped vanadium dioxide film to obtain the tungsten-doped vanadium dioxide film.
The preparation method of the tungsten-doped vanadium dioxide film provided by the second solution of the invention is used for preparing the tungsten-doped vanadium dioxide film provided by the first aspect of the invention.
A third aspect of the invention provides the use of a tungsten doped vanadium dioxide film in a smart glazing, using the tungsten doped vanadium dioxide film provided in the first solution of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the tungsten-doped vanadium dioxide thin film has low phase transition temperature, can generate phase transition at the most suitable temperature for human life, and meets the requirements of intelligent glass windows;
the preparation method of the invention adopts the metal vanadium target and the tungsten target to be simultaneously mixed and sputtered, has short sputtering time, is simple and easy to operate, does not need to add other gases during subsequent annealing, and is convenient for large-scale production.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a tungsten-doped vanadium dioxide thin film according to the present invention;
FIG. 2 is an XRD pattern of a tungsten doped vanadium dioxide thin film obtained in example 1;
FIG. 3 is an XPS plot of a tungsten doped vanadium dioxide film obtained in example 1;
FIG. 4 is a SEM image of a cross-section of a tungsten-doped vanadium dioxide thin film obtained in example 1;
FIG. 5 is a graph showing the hysteresis curve of the tungsten-doped vanadium dioxide thin film obtained in example 1;
FIG. 6 is a transmission spectrum of the tungsten-doped vanadium dioxide thin film obtained in example 1 at room temperature and high temperature;
FIG. 7 is a SEM image of a cross-section of a tungsten-doped vanadium dioxide thin film obtained in example 2.
FIG. 8 is a graph showing the hysteresis curve of the tungsten-doped vanadium dioxide thin film obtained in example 2;
FIG. 9 is a graph of the room temperature and high temperature transmission spectra of the tungsten doped vanadium dioxide thin film obtained in example 2;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of the invention provides a tungsten-doped vanadium dioxide thin film, wherein the thickness of the tungsten-doped vanadium dioxide thin film is 20-40 nm, the phase transition temperature is 25-45 ℃, and the visible light transmittance is 50-60%.
Preferably, the thickness of the tungsten-doped vanadium dioxide film is 20-30 nm, and the phase transition temperature is 25-35 ℃.
More preferably, the phase transition temperature of the tungsten-doped vanadium dioxide thin film is 25-30 ℃.
Research shows that extra electrons can be generated by doping high-valence cations into the vanadium dioxide thin film to destroy the symmetric structure of the crystal lattice, thereby reducing the phase transition temperature. In the present invention, W is+6The valence form exists, and the phenomenon of breaking the symmetrical structure of the crystal lattice is most obvious, so that the phase transition temperature is obviously reduced.
The invention provides a preparation method of a tungsten-doped vanadium dioxide film, which comprises the following steps:
s1, forming a tungsten-doped vanadium film on the surface of the substrate by adopting double-target magnetron sputtering;
and S2, annealing the tungsten-doped vanadium film to obtain the tungsten-doped vanadium dioxide film.
In the invention, double-target magnetron sputtering is adopted, compared with the conventional single-target magnetron sputtering, tungsten atoms and vanadium atoms can be uniformly mixed before sputtering, and the component uniformity of the obtained tungsten-doped vanadium dioxide film is improved, so that the tungsten after annealing treatment can be better doped in the room-temperature crystal lattice of the vanadium dioxide, and the phase change temperature is finally greatly reduced.
Preferably, the substrate is one of FTO glass, quartz glass, sapphire or mica sheet.
Preferably, the process of the dual-target magnetron sputtering specifically comprises the following steps: and placing the substrate in a magnetron sputtering vacuum chamber, introducing argon gas by taking a vanadium target and a tungsten target as target materials, and carrying out pre-sputtering and co-sputtering on the vanadium target and the tungsten target.
Further, the mass purity of the argon gas is 99.95-99.99%, and the vanadium isTargetAnd said tungstenTargetThe mass purity of (A) was 99.99%.
Further, during the pre-sputtering process, the vacuum degree of the vacuum chamber is 1.5 × 10-3～3.2×10-3Pa, the flux of argon is 180-250 sccm, the pre-sputtering working pressure is 0.1-1.0 Pa, the direct-current magnetron sputtering power of the vanadium target is 65-105W, the radio-frequency magnetron sputtering power of the tungsten target is 8-15W, and the pre-sputtering time is 10-30 min, so that nitrides, oxides and the like on the surface of the target material are removed, and the sputtering rate of the target material is improved.
Further, in the co-sputtering process, the flux of argon is 180-210 sccm, and the deposition working pressure is 0.05-0.2 pa; the direct-current magnetron sputtering power of the vanadium target is 105-135W, the radio-frequency magnetron sputtering power of the tungsten target is 3-10W, and the co-sputtering time is 1-6 min, so that the sputtering efficiency is improved, the tungsten content in the tungsten-doped vanadium film is reduced, and finally the uniform tungsten-doped vanadium film is formed on the surface of the substrate.
Further, in the process of the double-target magnetron sputtering, the substrate temperature is 60-120 ℃.
Furthermore, in the process of the double-target magnetron sputtering, the substrate temperature is 70-100 ℃. Within the range, the obtained tungsten-doped vanadium film has better thickness and compactness. Specifically, the density of the film is affected by too low temperature, and the temperature of the cavity is affected by too high temperature, so that the thickness of the film is affected.
Preferably, during the double-target magnetron sputtering process, the substrate is slowly rotated, so as to further improve the uniformity of the obtained tungsten-doped vanadium film.
Preferably, in the annealing treatment process, the temperature is increased to 350-450 ℃ at the temperature increase speed of 5-15 ℃/min, the temperature is kept for 45-100 min, and then the tungsten-doped vanadium dioxide film is obtained after the temperature is slowly cooled to 50-70 ℃.
Further, in the annealing process, the annealing pressure is 800-1200 Pa.
Preferably, the substrate is placed in front of the magnetron sputtering vacuum chamber, and the substrate is further required to be cleaned and dried, and the method specifically comprises the following steps: cleaning a substrate by using a cleaning agent, putting the substrate into distilled water for ultrasonic cleaning, then putting the substrate into absolute ethyl alcohol for ultrasonic cleaning, finally putting the substrate into the absolute ethyl alcohol for sealing, taking out the substrate for drying when in use, thereby cleaning the insoluble lipid substances on the glass surface and ensuring the surface to be clean.
A third aspect of the invention provides the use of a tungsten doped vanadium dioxide film in a smart glazing, using the tungsten doped vanadium dioxide film provided in the first solution of the invention.
Example 1
(1) Cleaning quartz glass to be plated with a cleaning agent, putting the cleaned quartz glass into distilled water for ultrasonic cleaning for 20min, then putting the cleaned quartz glass into absolute ethyl alcohol for ultrasonic cleaning for 35min, finally putting the cleaned quartz glass into the absolute ethyl alcohol for sealing, and taking out the cleaned quartz glass for drying when in use;
(2) placing the dried quartz glass substrate in a magnetron sputtering vacuum chamber, taking vanadium and tungsten with the mass purity of 99.99 percent as target materials, and pumping the vacuum degree of the vacuum chamber to 2.9 multiplied by 10-3After Pa, raising the temperature of the substrate to 80 ℃, controlling the flux of argon gas to be 200sccm and the pre-sputtering working pressure to be 0.5Pa, and pre-sputtering a vanadium target and a tungsten target by using argon gas with the mass purity of 99.99% as the working gas, wherein the power of the vanadium target is 75W, the power of the tungsten target is 10W, and the pre-sputtering time is 15 min; then controlling the flux of argon gas to be 200sccm, the deposition working pressure to be 0.1pa, the direct-current magnetron sputtering power of a vanadium target to be 105W, the radio-frequency magnetron sputtering power of a tungsten target to be 5W, and carrying out co-sputtering for 2min to obtain a tungsten-doped vanadium film;
(3) putting the tungsten-doped vanadium film into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 1000Pa, setting the annealing temperature to 400 ℃, setting the annealing temperature rise speed to 5 ℃/min, setting the annealing heat preservation time to 60min, 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.
Example 2
(1) Cleaning the to-be-plated quartz glass with a cleaning agent, putting the to-be-plated quartz glass into distilled water, ultrasonically cleaning the quartz glass for 25min, then putting the quartz glass into absolute ethyl alcohol, ultrasonically cleaning the quartz glass for 40min, finally putting the quartz glass into the absolute ethyl alcohol, sealing the quartz glass, and taking the quartz glass out for blow-drying when in use.
(2) Placing the blow-dried quartz glass substrate in a magnetron sputtering vacuum chamber, adopting vanadium and tungsten with the mass purity of 99.99 percent as target materials, and pumping the vacuum degree of the vacuum chamber to 2.9 multiplied by 10-3After Pa, raising the temperature of the substrate to 80 ℃, controlling the flux of argon gas to be 200sccm and the pre-sputtering working pressure to be 0.5Pa, and pre-sputtering the vanadium target and the tungsten target by using argon gas with the mass purity of 99.99% as the working gas, wherein the power of the vanadium target is 75W, the power of the tungsten target is 10W, and the pre-sputtering time is 15 min; then controlling the flux of argon gas to be 200sccm, the deposition working pressure to be 0.1pa, the direct-current magnetron sputtering power of the vanadium target to be 125W, the radio-frequency magnetron sputtering power of the tungsten target to be 5W, and carrying out co-sputtering for 2min to obtain a tungsten-doped vanadium film;
(3) putting the tungsten-doped vanadium film into an annealing furnace, closing a furnace door, vacuumizing the annealing furnace to 1000Pa, setting the annealing temperature to 400 ℃, setting the annealing temperature rise speed to 5 ℃/min, setting the annealing heat preservation time to 60min, 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.
Performance testing
The performance test of the tungsten-doped vanadium dioxide thin films obtained in the above examples 1-2 is shown in fig. 2-9. As can be seen from fig. 2 and 3, the tungsten-doped vanadium dioxide thin film provided by the present invention has a main component of vanadium dioxide, and a small amount of tungsten is also doped therein.
As shown in FIG. 4, the thickness of the tungsten-doped vanadium dioxide thin film obtained in example 1 is 23.51 nm; as shown in fig. 5, the electrical property test result shows that the phase transition temperature of the tungsten-doped vanadium dioxide thin film obtained in example 1 is 27.5 ℃; as shown in fig. 6, the room temperature and high temperature spectrum results show that the infrared light transmittance of the tungsten-doped vanadium dioxide thin film is higher at room temperature, when the temperature rises to be higher than the phase transition temperature of the thin film, the infrared light transmittance of the vanadium dioxide-based composite thin film is reduced, the visible light transmittance of the tungsten-doped vanadium dioxide thin film obtained in example 1 is 59.81%, and the solar light modulation efficiency is 1.27%.
As shown in FIG. 7, the thickness of the tungsten-doped vanadium dioxide thin film obtained in example 2 is 28.125 nm; as shown in fig. 8, the electrical property test result shows that the phase transition temperature of the tungsten-doped vanadium dioxide thin film obtained in example 2 is 26 ℃; as shown in fig. 9, the room temperature and high temperature spectrum results show that the infrared light transmittance of the tungsten-doped vanadium dioxide thin film is higher at room temperature, when the temperature rises to be higher than the phase transition temperature of the thin film, the infrared light transmittance of the vanadium dioxide-based composite thin film is reduced, the visible light transmittance of the tungsten-doped vanadium dioxide thin film obtained in example 2 is 53.75%, and the solar light modulation efficiency is 1.43%.
In conclusion, the tungsten-doped vanadium dioxide film provided by the invention is prepared by simultaneously mixing and sputtering the metal vanadium target and the tungsten target, and has low phase change temperature which is close to room temperature.
Compared with the prior art, the invention has the beneficial effects that:
the tungsten-doped vanadium dioxide thin film provided by the invention has low phase transition temperature, and can generate phase transition at the most suitable temperature for human life;
the preparation method of the tungsten-doped vanadium dioxide film provided by the invention adopts the metal vanadium target and the tungsten target to be simultaneously mixed and sputtered, the sputtering time is short, the operation is simple and easy, other gases are not required to be added during the subsequent annealing, and the mass production is convenient;
the tungsten-doped vanadium dioxide film provided by the invention can meet the requirements of intelligent glass windows.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The tungsten-doped vanadium dioxide thin film is characterized in that the thickness of the tungsten-doped vanadium dioxide thin film is 20-40 nm, the phase change temperature is 25-45 ℃, and the visible light transmittance is 50-60%.
2. The tungsten-doped vanadium dioxide thin film according to claim 1, wherein the tungsten-doped vanadium dioxide thin film has a film thickness of 20 to 30nm and a phase transition temperature of 25 to 35 ℃.
3. A method for preparing a tungsten-doped vanadium dioxide film according to claim 1 or 2, characterized in that it comprises the following steps:
forming a tungsten-doped vanadium film on the surface of the substrate by adopting double-target magnetron sputtering;
and annealing the tungsten-doped vanadium oxide film to obtain the tungsten-doped vanadium dioxide film.
4. The method for preparing the tungsten-doped vanadium dioxide thin film according to claim 3, wherein the substrate is one of FTO glass, quartz glass, sapphire or mica sheet.
5. The method for preparing the tungsten-doped vanadium dioxide film according to claim 3, wherein the process of the double-target magnetron sputtering specifically comprises the following steps: and placing the substrate in a magnetron sputtering vacuum chamber, introducing argon gas by taking a vanadium target and a tungsten target as target materials, and performing pre-sputtering and co-sputtering on the vanadium target and the tungsten target.
6. The method for preparing the tungsten-doped vanadium dioxide film according to claim 5, wherein the degree of vacuum of the vacuum chamber during the pre-sputtering process is 1.5 x 10-3～3.2×10-3Pa, the flux of argon is 180-250 sccm, the pre-sputtering working pressure is 0.1-1.0 Pa, the direct-current magnetron sputtering power of the vanadium target is 65-105W, the radio-frequency magnetron sputtering power of the tungsten target is 8-15W, and the pre-sputtering time is 10-30 min.
7. The method for preparing the tungsten-doped vanadium dioxide thin film according to claim 5, wherein in the co-sputtering process, the flux of argon is 180-210 sccm, and the deposition working pressure is 0.05-0.2 pa; the direct-current magnetron sputtering power of the vanadium target is 105-135W, the radio-frequency magnetron sputtering power of the tungsten target is 3-10W, and the co-sputtering time is 1-6 min.
8. The method for preparing the tungsten-doped vanadium dioxide film according to claim 3, wherein the substrate temperature is 60-120 ℃ in the double-target magnetron sputtering process.
9. The method for preparing the tungsten-doped vanadium dioxide film according to claim 3, wherein in the annealing process, the temperature is raised to 350-450 ℃ at a temperature rise rate of 5-15 ℃/min, the temperature is kept for 45-100 min, and then the film is slowly cooled to 50-70 ℃.
10. Use of a tungsten doped vanadium dioxide film according to claim 1 or 2 in smart glazing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010017835.3A CN111116050A (en) | 2020-01-08 | 2020-01-08 | Tungsten-doped vanadium dioxide thin film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN112921291A (en) * | 2021-01-26 | 2021-06-08 | 上海交通大学 | Preparation method of tungsten-doped vanadium dioxide thin film with adjustable phase-change temperature |
| CN115322442A (en) * | 2022-08-23 | 2022-11-11 | 中国科学院深圳先进技术研究院 | Electromagnetic shielding composite material with temperature response characteristic and preparation method and application thereof |
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