CN114059032A - Preparation method of vanadium dioxide film - Google Patents
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- CN114059032A CN114059032A CN202111370877.6A CN202111370877A CN114059032A CN 114059032 A CN114059032 A CN 114059032A CN 202111370877 A CN202111370877 A CN 202111370877A CN 114059032 A CN114059032 A CN 114059032A
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
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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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Abstract
The invention relates to the technical field of phase-change materials, in particular to a preparation method of a vanadium dioxide film. The preparation method provided by the invention comprises the steps of sputtering vanadium dioxide on the surface of a substrate in a vacuum reaction chamber by adopting a radio frequency magnetron sputtering method, and then raising the temperature of the substrate for in-situ annealing to obtain a vanadium dioxide film; a buffer layer is not arranged between the substrate and the vanadium dioxide film; the conditions of the radio frequency magnetron sputtering are as follows: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min; the sputtering power is 95W; the temperature of in-situ annealing is 460-520 ℃, and the heat preservation time is 200 s; the time for heating to the in-situ annealing temperature is less than or equal to 7 s. The preparation method can also obtain the vanadium dioxide film with good optical performance on the premise of not arranging the buffer layer.
Description
Technical Field
The invention relates to the technical field of phase-change materials, in particular to a preparation method of a vanadium dioxide film.
Background
In 1959, first, MIT (metal-semiconductor) phase transition characteristics of vanadium dioxide, a phase transition material, were discovered and studied in F.J.Morin (Morin F.J.oxidates while having a short-term-to-insulator transition at the New temporal [ J ]. Physical Review Letters,1959,3(1): 34.). In the next decades, vanadium dioxide, a metal oxide with phase transition characteristics, generally with a phase transition temperature of about 68 ℃, has been studied intensively by a large number of researchers as a typical phase transition material. And the vanadium dioxide in the film state can realize the phase change from a low-temperature monoclinic rutile structure to a high-temperature tetragonal rutile structure before and after the phase change temperature, the process is reversible, if the quality of the vanadium dioxide film is high, the optical and electrical properties of the vanadium dioxide film can also generate great mutation along with the phase change, the phase change time is femtosecond level, and the phase change is almost completed instantly. Meanwhile, the phase change of the vanadium dioxide film can be triggered by various factors such as an electric field, an optical field, temperature, pressure and the like, and based on the characteristics, the vanadium dioxide film has a very wide application prospect.
The preparation conditions of the single-crystal vanadium dioxide film are very harsh, for example, the preparation process is highly sensitive to oxygen, and vanadium and oxygen can form a very complex vanadium oxide system. Generally, dozens of different vanadium molybdenum oxides exist in a narrow vanadium-to-oxygen ratio range, so that parameters need to be controlled very accurately, the current preparation methods of vanadium dioxide films mainly include a hydrothermal method, a sol-gel method or a pulse laser deposition method, and the like, but the methods hardly achieve the consideration of cost and quality, either the cost is too high, the film forming quality cannot be guaranteed, and if a good optical performance is achieved, the design of composite films such as buffer layers, anti-reflection layers and the like is often needed, and common substrates generally need to be selected such as Si3N4、ZnO、TiO2Or sapphire substrate, etc., e.g., "The effect of TiO" in The prior art2 buffer layer thickness on the thermochromic properties of VO2 thin-film fabricated by high density plasma source[Japanese Journal of Applied Physics 60,SAAB04(2021)]"it is reported that the optical performance of vanadium dioxide thin film is improved by introducing titanium dioxide buffer layer, although the optical performance of the thin film deposited under the same condition is improved by about 10% in infrared band. However, in the method, the buffer layer is arranged, so that the preparation cost is greatly increased to a certain extent, and the preparation process is complicated.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium dioxide film, which can obtain the vanadium dioxide film with good optical performance on the premise of not arranging a buffer layer.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a vanadium dioxide film, which comprises the following steps:
in a vacuum reaction chamber, a radio frequency magnetron sputtering method is adopted, after vanadium dioxide is sputtered on the surface of a substrate, the temperature of the substrate is raised for in-situ annealing, and a vanadium dioxide film is obtained; a buffer layer is not arranged between the substrate and the vanadium dioxide film;
the radio frequency magnetron sputtering conditions are as follows: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min; the sputtering power is 95W;
the temperature of the in-situ annealing is 460-520 ℃, and the heat preservation time is 200 s;
the time for heating to the in-situ annealing temperature is less than or equal to 7 s.
Preferably, the substrate is cleaned before the sputtering;
the cleaning comprises sequentially cleaning with acetone, anhydrous ethanol and water under ultrasonic condition.
Preferably, the target material used for sputtering is a vanadium target with the purity of 99.9%.
Preferably, the target is pre-sputtered before the sputtering.
Preferably, the pre-sputtering conditions include: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 10-15 min.
Preferably, the distance between the substrate and the target is 80mm, and the rotation speed of the substrate is 25 rad/s.
The invention provides a preparation method of a vanadium dioxide film, which comprises the following steps: in a vacuum reaction chamber, a radio frequency magnetron sputtering method is adopted, after vanadium dioxide is sputtered on the surface of a substrate, the temperature of the substrate is raised for in-situ annealing, and a vanadium dioxide film is obtained; a buffer layer is not arranged between the substrate and the vanadium dioxide film; the radio frequency magnetron sputtering conditions are as follows: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min; the sputtering power is 95W; the temperature of the in-situ annealing is 460-520 ℃, and the heat preservation time is 200 s; the time for heating to the in-situ annealing temperature is less than or equal to 7 s.
Compared with the prior art, the method has the following beneficial effects:
1) the lower substrate temperature is adopted, the sputtering time is shorter, and the annealing operation in a tube furnace in the prior art is not needed;
2) the method accurately regulates and controls the parameters of magnetron sputtering, and ensures the crystallinity of the film to the maximum extent by matching the parameters of proper substrate temperature, in-situ annealing operation under vacuum, proper annealing temperature and heat preservation time, sputtering pressure and sputtering power, and proper oxygen and argon flow to ensure the content of tetravalent vanadium in the film;
3) the vanadium dioxide film prepared by the method has higher infrared mutation amplitude and also gives consideration to the performance of visible light wave bands;
4) the design of the element-free doping and composite film, the subsequent annealing process does not need to change instruments and equipment, and the operation is simple and convenient.
Drawings
FIG. 1 is an SEM photograph of a vanadium dioxide thin film prepared in example 1;
FIG. 2 is a SEM image of a cross-section of a vanadium dioxide thin film prepared in example 1;
FIG. 3 is an XRD pattern of a vanadium dioxide thin film prepared in example 1;
FIG. 4 is a graph showing the visible-infrared transmittance curves of the vanadium dioxide thin film prepared in example 1 at room temperature and 80 deg.C, respectively;
FIG. 5 is an SEM image of a vanadium dioxide thin film prepared in comparative example 1;
FIG. 6 is an XRD pattern of a vanadium dioxide thin film prepared in comparative example 1;
FIG. 7 is a graph showing the visible-infrared transmittance of the vanadium dioxide film prepared in comparative example 1 at room temperature (25 ℃ C.) and 80 ℃ C, respectively;
FIG. 8 is an XRD pattern of a vanadium dioxide thin film prepared in comparative example 2;
FIG. 9 is an SEM image of a vanadium dioxide thin film prepared in comparative example 2;
FIG. 10 is a graph showing the visible-infrared transmittance of the vanadium dioxide thin film prepared in comparative example 2 at room temperature and 80 ℃.
Detailed Description
The invention provides a preparation method of a vanadium dioxide film, which comprises the following steps:
in a vacuum reaction chamber, a radio frequency magnetron sputtering method is adopted, after vanadium dioxide is sputtered on the surface of a substrate, the temperature of the substrate is raised for in-situ annealing, and a vanadium dioxide film is obtained; a buffer layer is not arranged between the substrate and the vanadium dioxide film;
the radio frequency magnetron sputtering conditions are as follows: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min; the sputtering power is 95W;
the temperature of the in-situ annealing is 460-520 ℃, and the heat preservation time is 200 s;
the time for heating to the in-situ annealing temperature is less than or equal to 7 s.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In a vacuum reaction chamber, after sputtering vanadium dioxide on the surface of a substrate by adopting a radio frequency magnetron sputtering method, raising the temperature of the substrate for in-situ annealing to obtain a vanadium dioxide film; and a buffer layer is not arranged between the substrate and the vanadium dioxide film.
In the present invention, the material of the substrate is preferably quartz glass, more preferably sapphire; the thickness of the substrate is preferably 1 mm.
The invention also preferably includes cleaning the substrate prior to the sputtering. In the invention, the cleaning is preferably performed by sequentially using acetone, absolute ethyl alcohol and deionized water under an ultrasonic condition. In the present invention, the time of the sonication is preferably 15 min. The frequency of the ultrasound is not limited in any way in the present invention, and may be any frequency known to those skilled in the art.
In the invention, the purpose of cleaning is to remove dirt and impurities on the surface, ensure the surface of the substrate to be clean and dry, and further ensure the quality of the film and the adhesion of the film on the substrate.
After the cleaning is completed, the present invention also preferably includes drying; the drying is preferably carried out by drying with a nitrogen gun or drying with a dryer; the specific condition parameters of the drying and drying are not limited in any way, and the condition parameters known to those skilled in the art can be adopted.
After the drying is finished, the pretreated substrate is preferably placed into a glass dish and a preservative film is laid on the pretreated substrate for later use.
In the present invention, the degree of vacuum of the vacuum reaction chamber is preferably 8X 10-4Pa. The vacuum degree of the vacuum reaction chamber is preferably achieved by mechanical pumping or molecular pumping.
In the present invention, the target material used for the sputtering is preferably a vanadium target with a purity of 99.9%.
Before the sputtering, the target is preferably subjected to pre-sputtering; the conditions of the pre-sputtering are preferably as follows: the temperature of the substrate is preferably 250-300 ℃, more preferably 260-290 ℃, and most preferably 270-280 ℃; the flow rate of argon introduced into the reaction chamber is preferably 0.8 sccm; the flow rate of oxygen into the reaction chamber is preferably 40 sccm; the pressure in the reaction chamber is preferably 0.8 Pa; the sputtering time is preferably 10 to 15min, and more preferably 12 to 13 min.
In the present invention, the pre-sputtering process is preferably: the pressure in the sputtering chamber is evacuated to 8X 10 by a mechanical or molecular pump-4Pa, raising the temperature of the substrate to 250-300 ℃; oxygen and argon are respectively controlled to be introduced into the reaction cavity through a gas flow meter, sputtering pressure is controlled to be 0.8Pa through a gate valve, and the target is blocked by a baffle plate for pre-sputtering.
In the invention, the pre-sputtering is used for removing impurities on the surface of the vanadium target.
In the invention, the radio frequency magnetron sputtering conditions are as follows: the temperature of the substrate is 250-300 ℃, preferably 260-290 ℃, and more preferably 270-280 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min, preferably 16-19 min, and more preferably 17-18 min; the sputtering power was 95W.
In the present invention, the distance between the substrate and the target is preferably 80mm, and the rotation speed of the substrate is preferably 25 rad/s.
In the present invention, the sputtering process is preferably: and after the pre-sputtering is finished, moving away the baffle, controlling the distance between the target and the substrate to be 80mm, and controlling the rotating speed of the substrate to be 25rad/s, and carrying out radio frequency sputtering.
After the sputtering is complete, the invention also preferably includes gas flow meters that shut off the oxygen and argon.
In the invention, the temperature of the in-situ annealing is preferably 460-520 ℃, and more preferably 480-500 ℃; the incubation time is preferably 200 s. The time for raising the temperature to the temperature of the in-situ annealing is preferably less than or equal to 7 s.
After the in-situ annealing is completed, the method also preferably comprises cooling; the cooling process is not particularly limited in the present invention, and the cooling process may be performed to room temperature by a process well known to those skilled in the art.
In the invention, the thickness of the vanadium dioxide film prepared by the preparation method in the technical scheme is preferably 80-120 nm; the vanadium dioxide in the vanadium dioxide film is in a monoclinic rutile phase; growing on the substrate in the form of island growth single-layer or multi-layer compact particles.
The following will explain the preparation method of the vanadium dioxide thin film provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Ultrasonically cleaning a sapphire substrate for 15min by using acetone, absolute ethyl alcohol and high-purity deionized water in sequence, blow-drying by using a nitrogen gun, and placing in a sputtering chamber;
the pressure in the sputtering chamber was pumped by mechanical pumping to 8X 10-4Pa, raising the temperature of the substrate to 270 ℃, respectively controlling oxygen and argon to be introduced into the reaction chamber cavity at the flow rates of 0.8sccm and 40sccm through a gas flowmeter, and controlling the sputtering pressure to be 0.8Pa through a gate valve; blocking the target material by using a baffle plate, starting a sputtering power supply to perform pre-sputtering (the sputtering power is 95W) so as to remove impurities on the surface of the target material; removing the baffle, setting the distance between the target and the substrate to be 80mm, the rotating speed of the substrate to be 25rad/s, the radio frequency power to be 95W, closing the gas flowmeter after depositing for 16min, heating the substrate to 490 ℃ within 7s, preserving the temperature for 200s, and naturally cooling to room temperature to obtain the vanadium dioxide film (light yellow);
the vanadium dioxide thin film is subjected to SEM test, the test result is shown in figure 1, and as can be seen from figure 1, the vanadium dioxide thin film presents a crystalline form and a compact microstructure, the surface roughness of the thin film is large, the thin film is composed of obvious particles, and meanwhile, the particle boundary is clear, which shows that the vanadium dioxide thin film has good crystallinity;
FIG. 2 is a SEM (scanning Electron microscope) cross-sectional view of the vanadium dioxide thin film, wherein the thickness of the vanadium dioxide thin film is 120nm as shown in FIG. 2;
the dioxygenXRD test is carried out on the vanadium film, the test result is shown in figure 3, and as can be seen from figure 3, corresponding VO appears at about 28 DEG2The strong peak intensity and the small half height width of the (monoclinic phase, m) phase (101) plane further illustrate the good crystallinity;
the vanadium dioxide film is subjected to visible-infrared transmittance tests at room temperature and 80 ℃, and the test results are shown in fig. 4. fig. 4 shows that the vanadium dioxide film has good optical performance in both visible and infrared bands, and has an obvious infrared mutation rate at 2500nm, which reaches 65.1%.
Comparative example 1
Referring to example 1, except that the in-situ annealing temperature was 530 ℃, the color of the resulting vanadium dioxide film was lighter than that of example 1;
the vanadium dioxide thin film is subjected to SEM test, and the test result is shown in fig. 5, as can be seen from fig. 5, the vanadium dioxide thin film still has certain roughness and crystal type, but certain cracks appear on the surface of the sample, which is caused by the excessively high annealing temperature, which causes stronger stress to be generated in the interior of the thin film during the cooling process, thereby causing cracks to be generated on the surface of the thin film and deteriorating the quality of the thin film;
XRD (X-ray diffraction) test is carried out on the vanadium dioxide film, the test result is shown in figure 6, and as can be seen from figure 6, the vanadium dioxide film still generates corresponding VO at the position of about 28 DEG2The peak of the (monoclinic phase, m) phase (101) plane, but the full width at half maximum is wider and weaker than that of the vanadium dioxide film described in example 1, further illustrating that the crystalline phase is worse than that of example 1;
the vanadium dioxide thin film is subjected to visible-infrared transmittance tests at room temperature and 80 ℃, and the test results are shown in fig. 7, and as can be seen from fig. 7, the vanadium dioxide thin film also has certain optical properties in visible and infrared bands, and has an obvious infrared mutation rate at 2500nm, but only 56%.
Comparative example 2
With reference to example 1, except that the temperature of the substrate was 200 ℃, the resulting vanadium dioxide film was light gray in color;
the vanadium dioxide thin film is subjected to XRD test, the test result is shown in figure 8, and as can be seen from figure 8, the vanadium dioxide thin film has no obvious diffraction peak, which indicates that the crystallinity is very poor, even the surface has no crystallization, and the reason for generating the phenomenon is that the subsequent growth of the thin film is influenced because the temperature of the substrate is not enough and the nucleation is not enough in the island-shaped growth process, and the bonding force between the thin film and the substrate is poor due to the insufficient temperature of the substrate, so that the film explosion phenomenon is generated during annealing;
the vanadium dioxide thin film is subjected to SEM test, the test result is shown in figure 9, and as can be seen from figure 9, any crystal grains can hardly be seen on the surface of the vanadium dioxide thin film;
the vanadium dioxide film is subjected to visible-infrared transmittance tests at room temperature and 80 ℃, and the test result is shown in fig. 10, wherein the vanadium dioxide film has an obvious infrared mutation rate of 17.8% at 2500 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The preparation method of the vanadium dioxide film is characterized by comprising the following steps:
in a vacuum reaction chamber, a radio frequency magnetron sputtering method is adopted, after vanadium dioxide is sputtered on the surface of a substrate, the temperature of the substrate is raised for in-situ annealing, and a vanadium dioxide film is obtained; a buffer layer is not arranged between the substrate and the vanadium dioxide film;
the radio frequency magnetron sputtering conditions are as follows: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 15-20 min; the sputtering power is 95W;
the temperature of the in-situ annealing is 460-520 ℃, and the heat preservation time is 200 s;
the time for heating to the in-situ annealing temperature is less than or equal to 7 s.
2. The method according to claim 1, wherein the substrate is cleaned before the sputtering;
the cleaning comprises sequentially cleaning with acetone, anhydrous ethanol and water under ultrasonic condition.
3. The production method according to claim 1 or 2, wherein a target material used for the sputtering is a vanadium target having a purity of 99.9%.
4. The method according to claim 3, wherein the target is pre-sputtered before the sputtering.
5. The method of claim 4, wherein the pre-sputtering conditions include: the temperature of the substrate is 250-300 ℃; the flow rate of argon introduced into the reaction chamber is 0.8 sccm; the flow rate of oxygen introduced into the reaction chamber is 40 sccm; the air pressure of the reaction chamber is 0.8 Pa; the sputtering time is 10-15 min.
6. The method according to claim 4, wherein the sputtering is performed at a substrate-target distance of 80mm and a substrate rotation speed of 25 rad/s.
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| CN115125488A (en) * | 2022-07-08 | 2022-09-30 | 成都市精鹰光电技术有限责任公司 | Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering |
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Cited By (2)
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| CN115125488A (en) * | 2022-07-08 | 2022-09-30 | 成都市精鹰光电技术有限责任公司 | Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering |
| CN115125488B (en) * | 2022-07-08 | 2023-11-03 | 成都市精鹰光电技术有限责任公司 | Thermosensitive film prepared based on mixed pulse reaction magnetron sputtering |
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