CN107794497B - Preparation method of A-phase or B-phase vanadium dioxide film - Google Patents
Preparation method of A-phase or B-phase vanadium dioxide film Download PDFInfo
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- CN107794497B CN107794497B CN201610792641.4A CN201610792641A CN107794497B CN 107794497 B CN107794497 B CN 107794497B CN 201610792641 A CN201610792641 A CN 201610792641A CN 107794497 B CN107794497 B CN 107794497B
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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
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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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
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Abstract
The invention relates to a method for preparing an A-phase or B-phase vanadium dioxide film by magnetron sputtering, which takes an A-phase vanadium dioxide ceramic target or a B-phase vanadium dioxide ceramic target as a target material, and takes argon as sputtering gas to sputter the target material so as to form the A-phase or B-phase vanadium dioxide film on a substrate, wherein the deposition temperature is 350-500 ℃, and the deposition total pressure is 0.5-5.0 Pa. The invention directly takes the A-phase or B-phase vanadium dioxide ceramic target as a target material, and directly prepares the A-phase or B-phase vanadium dioxide film by controlling the deposition temperature, the deposition total pressure and the like.
Description
Technical Field
The invention belongs to the field of novel inorganic functional materials, and particularly relates to a method for preparing an A-phase or B-phase vanadium dioxide film by utilizing magnetron sputtering.
Background
Vanadium dioxide, a tetravalent oxide of vanadium, has a wide variety of structures, and known structures include a rutile phase structure (R phase), a monoclinic phase structure (M phase), a triclinic phase structure (T phase), and mesophases a and B phases. The M-phase vanadium dioxide and the R-phase vanadium dioxide can be mutually converted, and the phase transition temperature is close to room temperature, so that the method is widely concerned, and has application prospects in the aspects of intelligent energy-saving windows and the like. While the mesophases phase a and phase B of vanadium dioxide are relatively less studied.
A-phase vanadium dioxide VO2(A) Is first discovered by Theobald, then Oka discovers VO for the first time2(A) Has a phase transition temperature of about 165 ℃ and gives VO2(A) Specific crystal structure and lattice parameters before and after phase change. However VO2(A) The preparation is difficult, only a hydrothermal synthesis method is adopted in the literature reported at present, and VO2(A) Unstable, making the preparation of purer VO2(A) It is more difficult.
B-phase vanadium dioxide VO2(B) Structurally composed of two different kinds of [ VO6]Octahedron structure to form continuous three-dimensional lithium ion diffusion channel, and VO due to stable interlayer structure to facilitate rapid diffusion of lithium ion2(B) Should be used widelyA positive electrode material for a lithium ion battery. About VO2(B) Is reported to be more VO than VO2(A) However, the preparation method is limited to hydrothermal wet chemical methods.
The research on the preparation method of the vanadium dioxide film is convenient to appear in large quantities like bamboo shoots in spring after raining since the last 70 th century, and in a plurality of synthetic methods, the physical magnetron sputtering method is concerned due to the large-scale industrialization prospect, uniform and stable products, strong repeatability and high automation degree. However, the research of preparing A-phase or B-phase vanadium dioxide by a sputtering method is still blank at present.
Disclosure of Invention
The invention relates to a method for preparing A-phase or B-phase vanadium dioxide film by utilizing A-phase or B-phase vanadium dioxide ceramic target magnetron sputtering, aiming at making up the blank of preparing A-phase or B-phase vanadium dioxide film by physical sputtering method and enriching the preparation method of functional compounds.
The invention provides a method for preparing an A-phase or B-phase vanadium dioxide film by magnetron sputtering, which comprises the steps of taking an A-phase vanadium dioxide ceramic target or a B-phase vanadium dioxide ceramic target as a target material, and sputtering the target material by taking argon as sputtering gas to form the A-phase or B-phase vanadium dioxide film on a substrate, wherein the deposition temperature is 350-500 ℃, and the deposition total pressure is 0.5-5.0 Pa.
The invention directly takes the A-phase or B-phase vanadium dioxide ceramic target as a target material, and directly prepares the A-phase or B-phase vanadium dioxide film by controlling the deposition temperature, the deposition total pressure and the like.
Preferably, the target is sputtered to directly form an A-phase or B-phase vanadium dioxide film on the substrate without annealing.
Preferably, the purity of the oxygen is 99.99% or more, and the purity of the argon is 99.99%.
Preferably, the substrate is strontium titanate STO, lanthanum aluminate LAO, lead magnesium niobate-lead titanate PMN-PT, strontium tantalum lanthanum aluminate LAST, strontium tantalum neodymium aluminate NSAT, neodymium gallate NdGaO3Yttrium scandate YScO3Holmium scandium acid HoScO3Terbium scandate TbScO3DySco of scandium acid3And gadolinium scandate GdScO3At least one of (1). It is composed ofThe substrate required for preparing the A-phase vanadium dioxide film can be (110) surface strontium titanate STO, (110) surface lanthanum aluminate LAO, (110) surface lead magnesium niobate-lead titanate PMN-PT, (110) surface strontium tantalum lanthanum aluminate LAST, (110) surface strontium tantalum neodymium aluminate NSAT, (110) surface neodymium gallate NdGaO3Yttrium scandium acid (110) YScO3Holmium scandate HoScO on (110) plane3Terbium scandate TbScO of (110)3Dysprosium scandium acid (110) DyScO3Gadolinium scandate GdScO of (110)3And the like. The substrate required for preparing the B-phase vanadium dioxide film can be (100) surface strontium titanate STO, (100) surface lanthanum aluminate LAO, (100) surface lead magnesium niobate-lead titanate PMN-PT, (100) surface strontium tantalum lanthanum aluminate LAST, (100) surface strontium tantalum neodymium aluminate NSAT, (100) surface neodymium gallate NdGaO3Yttrium scandium acid (100) YScO3Holmium scandate HoScO on (100) plane3Terbium scandium acid (100) TbScO3Dysprosium scandium acid (100) DyScO3Gadolinium scandate GdScO of (100)3And the like. Among them, strontium titanate has a perovskite structure and a cubic system, and therefore has (100) plane, (010) plane, and (001) plane as equivalent. For the sake of uniformity, the strontium titanate crystal face is written uniformly as (100) strontium titanate.
Preferably, the vacuum of the back bottom is controlled to be 5-10 × 10-5Pa, sputtering power of 50-150W, and sputtering time of 5-300 minutes.
On the other hand, the invention also provides an A-phase or B-phase vanadium dioxide film with the thickness of 5-500 nm.
The method of the invention has simple operation and easy control, and the obtained film can be used in the aspects of batteries, hydrogen storage, photoelectric switches and the like.
Drawings
FIG. 1 is an XRD diffraction pattern of a phase B vanadium dioxide film prepared in example 1;
FIG. 2 is an XRD diffraction pattern of a phase A vanadium dioxide film prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The method directly takes an A-phase vanadium dioxide ceramic target or a B-phase vanadium dioxide ceramic target as a target material, takes argon as sputtering gas, and obtains the A-phase or B-phase vanadium dioxide film under the condition that the deposition temperature (substrate temperature) is 200-500 ℃ and the deposition total pressure is 0.5-5.0 Pa. The A-phase vanadium dioxide Ceramic target or the B-phase vanadium dioxide Ceramic target can be formed by respectively sintering A-phase vanadium dioxide powder and B-phase vanadium dioxide powder through hot pressing, the hot pressing temperature can be 550-640, the pressure can be 20-60 MPa, the preparation of the A-phase vanadium dioxide powder can refer to Shidong Ji et al Synthesis and phase transformation boiler of w-shaped VO2(A) nano-rod of journal of the Ceramic Society of Japan, No. 118 (No. 10), No. 867-phase 871 and B-phase vanadium dioxide powder are prepared by adopting a hydrothermal method, however, the technical route can be diversified, for example, the method described in the preparation method of the B-phase vanadium dioxide of the Chinese patent (publication No. CN101041464) can be adopted.
The substrate can be selected from strontium titanate STO, lanthanum aluminate LAO, lead magnesium niobate-lead titanate PMN-PT, strontium tantalum lanthanum aluminate LAST, strontium tantalum neodymium aluminate NSAT, neodymium gallate NdGaO3yttrium scandate YScO3Holmium scandium acid HoScO3Terbium scandate TbScO3DySco of scandium acid3Gadolinium scandate GdScO3One kind of (1).
The argon gas used as the sputtering gas is a high-purity gas, and for example, argon gas having a purity of 99.99% or more is used.
The invention directly forms the A-phase or B-phase vanadium dioxide film on the substrate by sputtering the target without annealing treatment. Wherein the back vacuum is controlled to be 5-10 × 10-5Pa, sputtering power can be 50-150W, and sputtering time can be 5-300 minutes. .
The thickness of the A-phase or B-phase vanadium dioxide film prepared by magnetron sputtering is 5-500 nm. The application of the material comprises the aspects of batteries, hydrogen storage, photoelectric switches and the like.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Using B-phase vanadium dioxide ceramic target, sputtering argon gas with purity of 99.99%, controlling vacuum of back substrate to be 1 × 10-4Pa, the deposition temperature is 350 ℃, the deposition total pressure is 3.0Pa, the sputtering power is 90W, and the vanadium dioxide film is sputtered on the strontium titanate substrate with the (100) surface for 80 minutes. And naturally cooling after sputtering is finished. The thickness of the vanadium dioxide film is 50nm by an optical interference method.
The obtained film was characterized by X-ray diffraction and the results are shown in FIG. 1. Parallel light incidence mode, theta-2 theta scan, using X-ray diffraction. As can be seen from the figure, the obtained sample is a B-phase vanadium dioxide thin film, and the epitaxial mode of the thin film is (001) orientation epitaxy. No other miscellaneous peak is left in the atlas except the substrate and the B-phase vanadium dioxide, which proves that the phase purity of the obtained sample is high.
Example 2
Using A-phase vanadium dioxide ceramic target, sputtering argon gas with the purity of 99.99 percent, and controlling the vacuum of the back substrate to be 8 multiplied by 10-5Pa, the deposition temperature is 450 ℃, the deposition total pressure is 4.0Pa, the sputtering power is 100W, and the vanadium dioxide film is sputtered on the strontium titanate substrate with the (110) surface for 100 minutes. And naturally cooling after sputtering is finished. The thickness of the vanadium dioxide film is 65nm by an optical interference method.
The obtained film was characterized by X-ray diffraction and the results are shown in FIG. 2. Parallel light incidence mode, theta-2 theta scan, using X-ray diffraction. As can be seen from the figure, the obtained sample was a phase A vanadium dioxide thin film. No other miscellaneous peak is left in the atlas except the substrate and the A-phase vanadium dioxide film, which proves that the phase purity of the obtained sample is high.
Example 3
Using A-phase vanadium dioxide ceramic target, sputtering argon gas with purity of 99.99%, controlling vacuum of back substrate at 5 × 10-5Pa, deposition temperature 500 ℃, deposition total pressure 3.0Pa, sputtering power 70W, and sputtering the vanadium dioxide film on the lanthanum aluminate substrate with the (110) surface for 120 minutesA clock. And naturally cooling after sputtering is finished. The sample obtained by the test is an A-phase vanadium dioxide film. The thickness of the vanadium dioxide film is 65nm by an optical interference method.
Example 4
Using B-phase vanadium dioxide ceramic target, sputtering argon gas with purity of 99.99%, controlling vacuum of back substrate at 10 × 10-5Pa, deposition temperature 200 ℃, deposition total pressure 1.0Pa, sputtering power 120W, dysprosium scandate (DyScO) on (100) surface3) The vanadium dioxide film is sputtered on the substrate for 200 minutes. And naturally cooling after sputtering is finished. The sample is characterized, and dysprosium scandate (DyScO) is proved3) (100) direction and VO2(B) And matching the phase lattices to obtain the B-phase vanadium dioxide film. The thickness of the vanadium dioxide film is 110nm through an optical interference method.
Example 5
Using B-phase vanadium dioxide ceramic target, sputtering argon gas with purity of 99.99%, controlling vacuum of back substrate at 8 × 10-5Pa, the deposition temperature is 300 ℃, the deposition total pressure is 5.0Pa, the sputtering power is 50W, and the vanadium dioxide film is sputtered on the lead magnesium niobate-lead titanate substrate with the (100) surface for 300 minutes. And naturally cooling after sputtering is finished. And (5) characterizing the sample to prove that the B-phase vanadium dioxide film is obtained.
The present invention has been described in detail with reference to the specific examples provided herein to facilitate the understanding and appreciation of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to these embodiments and apply the idea in the present invention to other embodiments without having to go through the inventive work. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.
Claims (3)
1. A method for preparing an A-phase or B-phase vanadium dioxide film by magnetron sputtering is characterized in that an A-phase vanadium dioxide ceramic target or a B-phase vanadium dioxide ceramic target is used as a target material, and argon is used as sputtering gas to sputter the target materialForming an A-phase or B-phase vanadium dioxide film on a substrate without annealing, wherein the back substrate vacuum is controlled to be 5-10 x 10-5 Pa, sputtering power of 50-150W, sputtering time of 5-300 minutes, deposition temperature of 350-500 ℃ and deposition total pressure of 0.5-5.0 Pa.
2. The method of claim 1, wherein the argon gas has a purity of 99.99%.
3. The method of claim 1 or 2, wherein the substrate is strontium titanate STO, lanthanum aluminate LAO, lead magnesium niobate-lead titanate PMN-PT, strontium tantalum lanthanum aluminate LAST, strontium tantalum neodymium aluminate NSAT, neodymium gallate NdGaO3Yttrium scandate YScO3Holmium scandium acid HoScO3Terbium scandate TbScO3DySco of scandium acid3And gadolinium scandate GdScO3At least one of (1).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016072549A (en) * | 2014-10-01 | 2016-05-09 | 株式会社アルバック | Functional element and method of manufacturing vanadium dioxide thin film |
| CN105624629A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | B-phase VO2 thermal-sensitive film prepared through doping of high-valence metal positive ions and preparation method thereof |
| CN105624630A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | Preparation method of VO2 by using VOx/M/VOx sandwich structure film and application of VO2 |
| CN105845771A (en) * | 2016-05-01 | 2016-08-10 | 上海大学 | High-performance VO2 thermal-sensitive film employing buffer layer for inducing growth and preparation method of high-performance VO2 thermal-sensitive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016072549A (en) * | 2014-10-01 | 2016-05-09 | 株式会社アルバック | Functional element and method of manufacturing vanadium dioxide thin film |
| CN105624629A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | B-phase VO2 thermal-sensitive film prepared through doping of high-valence metal positive ions and preparation method thereof |
| CN105624630A (en) * | 2016-03-26 | 2016-06-01 | 上海大学 | Preparation method of VO2 by using VOx/M/VOx sandwich structure film and application of VO2 |
| CN105845771A (en) * | 2016-05-01 | 2016-08-10 | 上海大学 | High-performance VO2 thermal-sensitive film employing buffer layer for inducing growth and preparation method of high-performance VO2 thermal-sensitive film |
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