CN116200712A - High-switching-ratio vanadium dioxide film and preparation method thereof - Google Patents
High-switching-ratio vanadium dioxide film and preparation method thereof Download PDFInfo
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 89
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 238000000151 deposition Methods 0.000 claims abstract description 28
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000005137 deposition process Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 88
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 239000001301 oxygen Substances 0.000 claims description 39
- 229910052760 oxygen Inorganic materials 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000004544 sputter deposition Methods 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000005546 reactive sputtering Methods 0.000 claims description 6
- 229910004205 SiNX Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims 1
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 42
- 230000008859 change Effects 0.000 description 11
- 230000000087 stabilizing effect Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000427 thin-film deposition Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
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- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0042—Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
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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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- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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Abstract
The invention provides a vanadium dioxide film with high on-off ratio and a preparation method thereof, comprising the following steps: (1) Firstly, depositing a 10-30nm vanadium dioxide seed layer on a substrate through a high-temperature film deposition process; (2) Then reducing the temperature, and continuously depositing a vanadium oxide film with a required thickness on the vanadium dioxide seed layer obtained in the step (1) to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film; (3) And (3) carrying out heat treatment on the double-layer film obtained by the deposition in the step (2) through atmosphere in-situ annealing to prepare the vanadium dioxide film with high on-off ratio. The U-I characteristic curve obtained by continuous scanning of the voltage of 0V-2.2V-0V proves that the vanadium dioxide film material prepared according to the invention has a switching ratio of 200-300, which is higher than that of a conventional magnetron sputtering polycrystalline vanadium dioxide film and an electroformed vanadium dioxide film.
Description
Technical Field
The invention belongs to the field of compatibility of high-performance vanadium dioxide film preparation and semiconductor technology, and particularly relates to a high-on-off ratio vanadium dioxide film and a preparation method thereof.
Background
Vanadium dioxide (VO) 2 ) Is a material which can reversibly change phase between an insulating state and a metal state, wherein the insulating state is in a monoclinic (M) phase, and the metal state is in a rutile (R) phase. VO (VO) 2 The phase transition temperature is about 68 ℃, which is closest to room temperature among various vanadium oxides having phase transition characteristics. Thus, among various vanadium oxides, VO 2 The most studied and most widely used are obtained.
VO 2 Below the phase transition temperature, the M phase has a band gap of 0.6 eV. When the temperature exceeds the phase transition temperature, this band gap in the R phase disappears. This change takes time on the order of femtoseconds, with a concomitant change in the photoelectric properties. Electrically, VO 2 The phase change of (2) will produce a change in resistivity of up to 5 orders of magnitude. Optically, VO 2 The autogenous light transmittance is changed during phase change, and visible light and infrared wave bands are obviously changed.
VO 2 The change in resistivity and optical transmittance before and after phase change has achieved a variety of applications. Typical examples are uncooled infrared detectors, laser protection equipment, high sensitivity photoelectric threshold switches, thermochromic smart windows, etc. In addition, the neuromorphic device in the corner of the brand-new head can also find VO 2 Is a figure of the figure. VO (VO) 2 The temperature brings nonlinear resistance change, and the Mort memristor can be prepared. Compared with other types of memristors, the Moire memristor has the advantages of low energy consumption, high speed and the like, and becomes one of schemes with the most potential for nerve morphology calculation in the post CMOS era.
Vanadium is a transition element, the common valence states are +2, +3, +4, +5, and the corresponding oxides are VO and V 2 O 3 、VO 2 、V 2 O 5 . In addition to this, there are a wide variety of vanadium oxides. The magnetron sputtering preparation of the vanadium dioxide film is a comprehensive consideration of film performance and preparation cost speed, but the thickness of the finished film is basically hundred nanometers due to the complexity of a vanadium-oxygen system. So that the vanadium dioxide film prepared by the magnetron sputtering method is multipleThe crystal grain size of the vanadium dioxide in the film is not large, and the grain boundary is more. The above phenomenon directly causes that the on-off ratio of the vanadium dioxide film is not high, the on-off ratio of the conventional vanadium dioxide film is about 50, and the electroformed vanadium dioxide film is about 100. These products are increasingly difficult to meet the performance requirements of vanadium dioxide in threshold switches, while making the development of vanadium dioxide memristors in neuromorphic devices slow. The method for preparing the vanadium dioxide film with high on-off ratio by using the laser pulse deposition and the molecular beam epitaxy has the advantages of high cost, low efficiency and complete inapplicability to industrial production. In addition, single crystal substrates such as titanium dioxide are commonly used for preparing the vanadium dioxide film with high on-off ratio, and the substrates are expensive and have compatibility problems with monolithic integration. In the invention, the substrate with the amorphous surface is used, so that the production cost is effectively reduced, and the substrate is compatible with a monolithic integration process. Firstly, directly depositing a monocrystalline vanadium dioxide seed layer on a high-temperature substrate, then, reducing the substrate to a safe temperature of a silicon-based process to sputter a vanadium dioxide functional layer, and finally, carrying out conventional in-situ annealing on a sample. The deposition and annealing of the seed layer and the functional layer are compatible with silicon-based processes without damaging the integrated devices on the substrate. The seed layer enables the subsequent vanadium dioxide functional layer to have good crystallinity, and high on-off ratio of the film is realized.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method is low in process equipment dependence, simple to operate, suitable for industrial mass production, and free from damaging the integrated silicon-based process devices on the substrate in the preparation process.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a vanadium dioxide film with high switching ratio comprises the following steps:
(1) Firstly, depositing a 10-30nm vanadium dioxide seed layer on a substrate through a high-temperature film deposition process;
(2) Then reducing the temperature, and continuously depositing a vanadium oxide film with a required thickness on the vanadium dioxide seed layer obtained in the step (1) to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film;
(3) And (3) carrying out heat treatment on the double-layer film obtained by the deposition in the step (2) through atmosphere in-situ annealing to prepare the vanadium dioxide film with high on-off ratio.
Preferably, the substrate comprises one of Si/SiOx substrate, si/SiNx substrate, quartz glass and common glass.
Preferably, the high temperature thin film deposition process in the step (1) is a reactive sputtering process; wherein the temperature of the substrate is 350-450 ℃, and the film deposition time is 1-3min.
Preferably, the step (1) specifically includes the following steps:
(1) placing the substrate at 2.3X10 -3 Pa-3.0×10 -3 In a vacuum environment of Pa, the temperature is increased to 350-450 ℃ and stabilized for 3-5min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and adopting a reactive sputtering process to deposit a 10-30nm vanadium dioxide seed layer on the surface of the preheated substrate in the step (1).
Preferably, the step (2) specifically includes the following steps:
(1) in the same process equipment of the step (1), the temperature of the substrate is reduced to 100-300 ℃ and stabilized for 30-60min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and continuously depositing a vanadium oxide film with a required thickness on the surface of the vanadium dioxide seed layer prepared in the step (1) so as to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film.
Preferably, the step (3) specifically includes the following steps:
(1) in the same process equipment used in the step (2), raising the temperature of the substrate to a set annealing temperature at a heating rate of 8-10 ℃/min, and then carrying out in-situ annealing on the double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film prepared in the step (2) in an oxygen atmosphere to obtain a vanadium dioxide film;
(2) after annealing, at a gas pressure of less than 5 x 10 -3 And naturally cooling the vanadium dioxide film sample to below 120 ℃ in a vacuum environment of Pa.
Preferably, the annealing temperature is 400-420 ℃.
Preferably, the oxygen partial pressure at the time of annealing is 1.2Pa to 2.0Pa.
The invention also provides a vanadium dioxide film with high on-off ratio obtained by the preparation method.
Preferably, the high-on-off ratio vanadium dioxide film comprises from bottom to top: a substrate layer, a vanadium dioxide seed layer and a vanadium oxide layer.
The metal vanadium target and the hafnium target are made of high-purity vanadium powder and hafnium powder which are formed into blanks and sintered in vacuum.
The invention has the following beneficial effects:
the U-I characteristic curve obtained by continuous scanning of the voltage of 0V-2.2V-0V proves that the vanadium dioxide film material prepared according to the invention has a switching ratio of 200-300, which is higher than that of a conventional magnetron sputtering polycrystalline vanadium dioxide film and an electroformed vanadium dioxide film.
The high-vacuum magnetron sputtering deposition method related to the preparation method of the vanadium dioxide film with high on-off ratio is easy to realize by the existing sputtering equipment, has low requirements on equipment process and has high film deposition rate.
The substrate surface involved in the preparation method of the high-on-off ratio vanadium dioxide film is amorphous, and the material is low in cost and suitable for monolithic integrated circuits.
The sputtering vanadium dioxide seed layer involved in the preparation method of the high-on-off ratio vanadium dioxide film provided by the invention is compatible with a silicon-based process and does not damage an integrated CMOS device. The seed layer enables the vanadium dioxide functional layer prepared by the subsequent conventional sputtering process to have good crystallinity.
Drawings
FIG. 1 is a general flow chart of the method for preparing a high-on-off-ratio vanadium dioxide film according to the invention.
FIG. 2 is a graph showing the U-I characteristics of the film sample prepared in example 1.
FIG. 3 is a graph showing the U-I characteristics of the film sample prepared in example 2.
FIG. 4 is a graph showing the U-I characteristics of the film sample prepared in example 3.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The invention provides a preparation method of a vanadium dioxide film with high on-off ratio, which comprises the following steps:
(1) Firstly, depositing a 10-30nm vanadium dioxide seed layer on a substrate through a high-temperature film deposition process;
(2) Then reducing the temperature, and continuously depositing a vanadium oxide film with a required thickness on the vanadium dioxide seed layer obtained in the step (1) to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film;
(3) And (3) carrying out heat treatment on the double-layer film obtained by the deposition in the step (2) through atmosphere in-situ annealing to prepare the vanadium dioxide film with high on-off ratio.
In some embodiments, the substrate is selected from one of a Si/SiOx substrate, a Si/SiNx substrate, quartz glass, and plain glass.
In some embodiments, the high temperature thin film deposition process of step (1) is a reactive sputtering process; wherein the temperature of the substrate is 350-450 ℃, and the film deposition time is 1-3min.
In some embodiments, step (1) specifically comprises the steps of:
(1) placing the substrate at 2.3X10 -3 Pa-3.0×10 -3 In a vacuum environment of Pa, the temperature is increased to 350-450 ℃ and stabilized for 3-5min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and adopting a reactive sputtering process to deposit a 10-30nm vanadium dioxide seed layer on the surface of the preheated substrate in the step (1).
In some embodiments, step (2) specifically comprises the steps of:
(1) in the same process equipment of the step (1), the temperature of the substrate is reduced to 100-300 ℃ and stabilized for 30-60min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and continuously depositing a vanadium oxide film with a required thickness on the surface of the vanadium dioxide seed layer prepared in the step (1) so as to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film.
In some embodiments, step (3) specifically comprises the steps of:
(1) in the same process equipment used in the step (2), raising the temperature of the substrate to a set annealing temperature at a heating rate of 8-10 ℃/min, and then carrying out in-situ annealing on the double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film prepared in the step (2) in an oxygen atmosphere to obtain a vanadium dioxide film;
(2) after annealing, at a gas pressure of less than 5 x 10 -3 And naturally cooling the vanadium dioxide film sample to below 120 ℃ in a vacuum environment of Pa.
In some embodiments, the annealing temperature is 400-420 ℃.
In some embodiments, the partial pressure of oxygen at the time of annealing is 1.2Pa to 2.0Pa.
The obtained high-switching-ratio vanadium dioxide film comprises the following components from bottom to top: a substrate layer, a vanadium dioxide seed layer and a vanadium oxide layer.
Example 1:
(1) Placing cleaned substrate in substrate frame, wherein the substrate is Si/SiOx substrate, and vacuum chamber of sputtering system is pumped to 2.5X10 -3 Pa, raising the temperature of the substrate to 400 ℃ and stabilizing for 3min; introducing high-purity argon into the vacuum chamber, ensuring the pressure of the vacuum chamber to be 6.9Pa, and pre-sputtering the high-purity metal vanadium target for 10 minutes at room temperature to remove surface oxides; and (3) introducing high-purity oxygen, ensuring the atmosphere with the oxygen/argon flow ratio of 1:50, keeping the working air pressure of a vacuum chamber at 0.85Pa, depositing a vanadium dioxide seed layer on the surface of the substrate for not more than 3min, and ensuring the film thickness to be 15nm.
(2) Cutting off the supply of argon and oxygen to recover the vacuum chamber pressure to 2.5X10 -3 Pa, reducing the temperature of the substrate to 100 ℃ and stabilizing for 30min; introducing high-purity argon with purity of more than 99.99% into the vacuum chamber, ensuring the pressure of the vacuum chamber to be 6.9Pa, and pre-sputtering the high-purity metal vanadium target for 10 minutes at room temperature to remove surface oxides; high-purity oxygen is introduced, the atmosphere with the oxygen/argon flow ratio of 1:45 is ensured, the working pressure of a vacuum chamber is kept at 0.85Pa, and a layer of vanadium oxide film with the thickness of 200 nanometers is sputtered on the vanadium dioxide seed layer.
(3) Stopping argon supply, reducing oxygen supply, and heating the substrate to 400 ℃ at a heating rate of 8 ℃/min, wherein the pressure of the vacuum chamber is ensured to be 1.3Pa; keeping the temperature of the substrate constant for 60min, and introducing oxygen to the substrate under the low-oxygen atmosphere with the constant working air pressure of 1.2 Pa; then stopping heating and oxygen supply to ensure that the working air pressure is lower than 3×10 -3 Under Pa, the substrate is naturally cooled to below 120 ℃. Finally, the sample is taken out.
(4) And (3) carrying out continuous voltage V scanning of 0V-2.2V-0V on the sample, and recording the value of the current I to obtain a U-I characteristic curve. By calculating the phase change of the sample at 0V and the insulation state into the metal state voltage U IMT The maximum slope of the U-I characteristic curve is taken as the resistance value R of the insulating state of the sample I . Calculating the voltage U of the sample from 2.2V to the insulation state after the phase change of the metal state MIT The testing instrument exits 5ma current limiting protection, and the maximum slope of the U-I characteristic curve is used as the resistance value R of the sample metal state M . Sample light opening ratio is R I And R is M Ratio of (2)Values.
The on-off ratio of the sample was 203.
Example 2
(1) Placing cleaned substrate in a substrate frame, wherein the substrate is Si/SiNx substrate, and vacuum chamber of sputtering system is pumped to 2.3X10 -3 Pa, heating the substrate to 450 ℃ and stabilizing for 5min; introducing high-purity argon into the vacuum chamber, ensuring the pressure of the vacuum chamber to be 6.9Pa, and pre-sputtering the high-purity metal vanadium target for 10 minutes at room temperature to remove surface oxides; and (3) introducing high-purity oxygen, ensuring the atmosphere with the oxygen/argon flow ratio of 1:45, keeping the working air pressure of a vacuum chamber at 0.85Pa, depositing a vanadium dioxide seed layer on the surface of the substrate, wherein the deposition time is not more than 3min, and the film thickness is 10nm.
(2) Cutting off the supply of argon and oxygen to recover the vacuum chamber pressure to 2.3X10 -3 Pa, reducing the temperature of the substrate to 300 ℃ and stabilizing for 60min; introducing high-purity argon into the vacuum chamber, ensuring the pressure of the vacuum chamber to be 6.9Pa, and pre-sputtering the high-purity metal vanadium target for 5 minutes at room temperature to remove surface oxides; high-purity oxygen is introduced, the atmosphere with the oxygen/argon flow ratio of 1:50 is ensured, the working pressure of a vacuum chamber is kept at 0.85Pa, and a layer of 300-nanometer vanadium oxide film is sputtered on the vanadium dioxide seed layer.
(3) Stopping argon supply, reducing oxygen supply, and heating the substrate to 410 ℃ at a heating rate of 9 ℃/min, wherein the pressure of the vacuum chamber is ensured to be 1.3Pa; keeping the temperature of the substrate constant for 60min, and introducing oxygen to the substrate under the low-oxygen atmosphere with the constant working air pressure of 2.0 Pa; then stopping heating and oxygen supply to ensure that the working air pressure is lower than 4×10 -3 Under Pa, the substrate is naturally cooled to below 120 ℃. Finally, the sample is taken out.
(4) The same test as in experimental example 1 was performed.
The on-off ratio of the sample was 279.
Example 3
(1) Placing cleaned substrate in a substrate frame, wherein the substrate is quartz glass, and vacuum chamber of sputtering system is pumped to 3.0X10 -3 Pa, raising the temperature of the substrate to 350 ℃ and stabilizing for 4min; high-purity argon is introduced into the vacuum chamber, the pressure of the vacuum chamber is ensured to be 6.9Pa, and the high-purity metal vanadium target is subjected toPre-sputtering for 10 minutes at room temperature to remove surface oxides; and (3) introducing high-purity oxygen, ensuring the atmosphere with the oxygen/argon flow ratio of 1:60, keeping the working air pressure of a vacuum chamber at 0.85Pa, depositing a vanadium dioxide seed layer on the surface of the substrate, wherein the deposition time is not more than 3min, and the film thickness is 30nm.
(2) Cutting off the supply of argon and oxygen to recover the vacuum chamber pressure to 2.3X10 -3 Pa, reducing the temperature of the substrate to 200 ℃ and stabilizing for 45min; introducing high-purity argon into the vacuum chamber, ensuring the pressure of the vacuum chamber to be 6.9Pa, and pre-sputtering the high-purity metal vanadium target for 15 minutes at room temperature to remove surface oxides; high-purity oxygen is introduced, the atmosphere with the oxygen/argon flow ratio of 1:60 is ensured, the working pressure of a vacuum chamber is kept at 0.85Pa, and a layer of 300-nanometer vanadium oxide film is sputtered on the vanadium dioxide seed layer.
(3) Stopping argon supply, reducing oxygen supply, and heating the substrate to 420 ℃ at a heating rate of 10 ℃/min, wherein the pressure of the vacuum chamber is ensured to be 1.3Pa; keeping the temperature of the substrate constant for 60min, and introducing oxygen to the substrate under the low-oxygen atmosphere with the constant working air pressure of 1.8 Pa; then stopping heating and oxygen supply to ensure that the working air pressure is lower than 2 x 10 -3 Under Pa, the substrate is naturally cooled to below 120 ℃. Finally, the sample is taken out.
(4) The same test as in experimental example 1 was performed.
The on-off ratio of the sample was 264.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.
Claims (10)
1. The preparation method of the vanadium dioxide film with high switching ratio is characterized by comprising the following steps:
(1) Firstly, depositing a 10-30nm vanadium dioxide seed layer on a substrate through a high-temperature film deposition process;
(2) Then reducing the temperature, and continuously depositing a vanadium oxide film with a required thickness on the vanadium dioxide seed layer obtained in the step (1) to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film;
(3) And (3) carrying out heat treatment on the double-layer film obtained by the deposition in the step (2) through atmosphere in-situ annealing to prepare the vanadium dioxide film with high on-off ratio.
2. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 1, which is characterized in that: the substrate is selected from one of Si/SiOx substrate, si/SiNx substrate, quartz glass and common glass.
3. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 1, which is characterized in that: the high-temperature film deposition process in the step (1) is a reactive sputtering process; wherein the temperature of the substrate is 350-450 ℃, and the film deposition time is 1-3min.
4. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 1, which is characterized in that: the step (1) specifically comprises the following steps:
(1) placing the substrate at 2.3X10 -3 Pa-3.0×10 -3 In a vacuum environment of Pa, the temperature is increased to 350-450 ℃ and stabilized for 3-5min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and adopting a reactive sputtering process to deposit a 10-30nm vanadium dioxide seed layer on the surface of the preheated substrate in the step (1).
5. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 1, which is characterized in that: the step (2) specifically comprises the following steps:
(1) in the same process equipment of the step (1), the temperature of the substrate is reduced to 100-300 ℃ and stabilized for 30-60min;
(2) pre-sputtering a high-purity metal vanadium target with purity of more than 99.99% for 5-15min at room temperature under pure argon atmosphere;
(3) and (3) adopting an atmosphere with an oxygen/argon flow ratio of 1:45-1:60, and continuously depositing a vanadium oxide film with a required thickness on the surface of the vanadium dioxide seed layer prepared in the step (1) so as to obtain a double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film.
6. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 1, which is characterized in that: the step (3) specifically comprises the following steps:
(1) in the same process equipment used in the step (2), raising the temperature of the substrate to a set annealing temperature at a heating rate of 8-10 ℃/min, and then carrying out in-situ annealing on the double-layer film consisting of the vanadium dioxide seed layer and the vanadium oxide film prepared in the step (2) in an oxygen atmosphere to obtain a vanadium dioxide film;
(2) after annealing, at a gas pressure of less than 5 x 10 -3 And naturally cooling the vanadium dioxide film sample to below 120 ℃ in a vacuum environment of Pa.
7. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 6, which is characterized in that: the annealing temperature is 400-420 ℃.
8. The method for preparing the vanadium dioxide film with high on-off ratio according to claim 6, which is characterized in that: the oxygen partial pressure during annealing is 1.2Pa-2.0Pa.
9. A high on-off ratio vanadium dioxide film obtained by the production method according to any one of claims 1 to 8.
10. The high on-off ratio vanadium dioxide thin film according to claim 9, comprising, from bottom to top: a substrate layer, a vanadium dioxide seed layer and a vanadium oxide layer.
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