CN105132877B - A kind of vanadium dioxide film low temperature deposition method - Google Patents
A kind of vanadium dioxide film low temperature deposition method Download PDFInfo
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- CN105132877B CN105132877B CN201510590007.8A CN201510590007A CN105132877B CN 105132877 B CN105132877 B CN 105132877B CN 201510590007 A CN201510590007 A CN 201510590007A CN 105132877 B CN105132877 B CN 105132877B
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- film
- oxygen
- vanadium
- low temperature
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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
-
- 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
Abstract
The invention discloses a kind of methods of low temperature depositing vanadium dioxide film, and using magnetron sputtering technique, using vanadium metal or vanadium alloy as target, using oxygen as reaction gas, argon gas is sputter gas；Before preparing film, first vacuum chamber is evacuated to less than 1 × 10‑3Pa base vacuums then pass to oxygen and argon gas mixed gas, and partial pressure of oxygen remains 0.01-0.06Pa, and during deposition film, control depositing temperature is 240~260 DEG C, and add back bias voltage in substrate, and target surface Sputtering power density is 2 3W/cm2, high performance VO is obtained in substrate surface2Film.The low temperature deposition method of the present invention is by VO2The depositing temperature of film is low, and coordinates appropriate back bias voltage and film even compact that other technological parameters are prepared, phase transition temperature of vanadium dioxide are low, has the high-performance VO of good phase transition performance2Film；Greatly reduce production cost.
Description
Technical field
The invention belongs to function film preparing technical fields, are related to a kind of preparation process of vanadium dioxide film, especially relate to
And a kind of vanadium dioxide film low temperature deposition method.
Technical background
VO2It is a kind of thermotropic phase-change material of solid-state, monocrystalline VO2In phase transition temperature（Tc）It can be from the tetragonal of high temperature at 68 DEG C
It is the monoclinic system distortion rutile-type that rutile-type is converted to low temperature, with the variation of temperature, its crystalline structure is correspondingly sent out
The raw level-one displacement phase transition from metallic state to semiconductor form.VO2Phase-change characteristic be thermal induced phase transition, the variation of temperature can lead to it
Reversible variation occurs for resistivity, light transmission rate.There are 98 % to be at infrared light and visible ray in the gross energy of solar radiation
Wave band all concentrates on infrared band wherein most of, and VO2When semiconductor-metal phase transformation occurs just to infrared band
Light transmission rate and reflectivity mutate, and this characteristic of vanadium dioxide becomes the first choice of intelligent power saving window material.Summer temperature
When spending high, VO2In high-temperature metal state, it is very low to infrared light transmittance at this time, can inhibit the incidence of infrared light, reach drop
The purpose of low room temperature；In contrast, when ambient temperature is less than VO2During the phase transition temperature of film, infrared light can be with higher saturating
Rate is crossed through smart window, indoor temperature is made to increase.Window is installed and is coated with VO2The glass of film then can be achieved cool in summer and warm in winter
Purpose.
VO2The common depositing temperature of film is generally 450 ~ 500 DEG C or by room temperature depositing high temperature annealing (450 ~ 500
DEG C) mode obtains, and glass pane is typically tempered glass, i.e., glass will pass through about 600 DEG C of toughening process after being made.This gives
VO is prepared on glazing2Film brings difficulty：If VO is deposited with glass after tempering2Film, then due to depositing temperature compared with
Height, the original tempering effect of glass will weaken significantly；If simple glass deposits VO2Tempering is carried out after film again, at this moment tempering
Temperature is too high, the VO being originally coated with2Film will lose phase transition performance.Preparation technology in low temperature can then solve this problem, i.e.,
By reducing depositing temperature, depositing operation is allow to be carried out directly on tempered glass, there is major application value.
Invention describes a kind of low temperature preparing methods of vanadium dioxide glass, using vanadium as target, are splashed by reacting magnetic control
The technology penetrated, the method that negative substrate bias is added in deposition process, realizes vanadium dioxide film low temperature depositing purpose, has
Huge value.
Invention content
The purpose of the present invention is to provide a kind of high quality vanadium dioxide film low temperature preparing methods simple for process, prepare
Technique uses reaction magnetocontrol sputtering technology, and magnetron sputtering is by introducing magnetic field in target cathode surface, using magnetic field to electronics
Constraint improves plasma density to increase the method for sputtering raste, reaction magnetocontrol sputtering be in magnetron sputtering process using metal as
Target reacts the method for prepare compound film by the metallic atom for being passed through active gases and sputtering.
To achieve these goals, technical scheme of the present invention is specially：
A kind of vanadium dioxide film low temperature deposition method, using magnetron sputtering technique, using vanadium metal or vanadium alloy as target,
Using oxygen as reaction gas, argon gas is sputter gas；Before preparing film, first vacuum chamber is evacuated to less than 1 × 10-3Pa backgrounds are true
Sky then passes to oxygen and argon gas mixed gas, and partial pressure of oxygen remains 0.01-0.06Pa, during deposition film, control
Depositing temperature is 240~260 DEG C, and adds back bias voltage in substrate, and target surface Sputtering power density is 2-3W/cm2, in substrate
Surface obtains high performance VO2Film.This method does not need to the last handling processes such as annealing, directly prepares VO2Film.
Further, during the deposition film, substrate add back bias voltage, bias size be -100V ~ -
250V。
Further, the substrate is simple glass, quartz glass, tempered glass, sapphire, glass steel or stainless steel.
Preferably, the substrate is tempered glass.
Preferably, during the deposition film, control depositing temperature is 240 DEG C.
Preferably, target surface Sputtering power density is 2W/cm2。
A kind of vanadium dioxide film low temperature deposition method, the vanadium dioxide being mainly used for when using tempered glass as substrate are thin
Film deposits.Reaction magnetocontrol sputtering technology is specifically used, using vanadium metal or vanadium alloy as target, using oxygen as reaction gas, argon gas
For sputter gas；Before preparing film, first vacuum chamber is evacuated to less than 1 × 10-3Pa base vacuums, then pass to oxygen and argon gas
Mixed gas, partial pressure of oxygen remain 0.01-0.06Pa, and during deposition film, control depositing temperature is 240 DEG C, and in base
Back bias voltage is added at bottom, and bias size is -100V ~ -250V；Target surface Sputtering power density is 2-3W/cm2, prepare high property
The VO of energy2Film.
The present invention has following technique effect：
1. the low temperature deposition method of the present invention is by VO2The depositing temperature of film is by common 400-500 DEG C, minimum reduction
About 240 DEG C have been arrived, and appropriate back bias voltage and other technological parameters is coordinated to prepare the high-performance VO with good phase transition performance2
Film；Greatly reduce production cost；And especially under the premise of the tempering effect of tempered glass is not changed, in tempering glass
Glass surface can form high-performance VO2Film so that its processing compatibility with existing tempered glass greatly improves, has
Very big application value.
2. the VO of the present invention2The low temperature depositing of film avoids high temperature post-deposition annealing process, simplifies production technology,
Manufacture cost is saved, is not related to the raw material for having pollution to environment in preparation process.Aftertreatment technology is not needed to, once low
Vanadium dioxide film is prepared under temperature.
3. the present invention has wide application prospects in multiple fields such as smart windows.
Description of the drawings
Fig. 1 is witch culture VO under -150V back bias voltages in the embodiment of the present invention 12Transmission spectrum under film different temperatures；
Fig. 2 is witch culture VO under -200V back bias voltages in the embodiment of the present invention 22Transmission spectrum under film different temperatures；
Fig. 3 is pure VO under -185V back bias voltages in the embodiment of the present invention 22Transmission spectrum under film different temperatures.
Specific embodiment
Embodiment 1
VO in the present embodiment2The preparation of film is using direct current reaction magnetron sputtering, with vanadium tungsten alloy target（W at.%=
0.81%) for target, substrate is K9 glass, is cleaned by ultrasonic respectively 10 minutes by alcohol and deionized water, sheet during film preparation
Bottom vacuum is 6 × 10-4Pa, using oxygen and argon gas as reaction gas and sputter gas, before preparing film, first to target pre-sputtering 10
Depositing temperature remained 245 DEG C, deposited to remove surface contaminant, working vacuum 0.5Pa, partial pressure of oxygen 0.02Pa minute
In thin-film process, back bias voltage is added in substrate, bias size is -150V, sputtering power 80W, and sedimentation time obtains for 30min
The VO of even compact2Film.Wherein, the present embodiment uses vanadium tungsten alloy target, can easily be adjusted by adjusting W content in target
Save VO2The phase transition temperature of film.Prepared vanadium dioxide film sample before phase change with wavelength change curve be shown in by rear sample transmitance
Fig. 1, as seen from the figure, prepared thin film silicon oxide vanadium phase transition temperature are low, have good phase transformation and infrared regulation performance.
Embodiment 2
The preparation of vanadium dioxide film is using direct current reaction magnetron sputtering, to mix the vanadium tungsten alloy target of tungsten（W.at.%=
0.81%) for target, substrate is tempered glass, is cleaned by ultrasonic respectively 10 minutes by alcohol and deionized water, during film preparation
Base vacuum is 6 × 10-4Pa, using oxygen and argon gas as reaction gas and sputter gas, before preparing film, first target pre-sputtering
To remove surface contaminants, working vacuum 0.5Pa, partial pressure of oxygen 0.02Pa, depositing temperature remains 240 DEG C, is depositing 10min
In thin-film process, in substrate addition -200V back bias voltages, sputtering power 80W, sedimentation time 30min, then in tempered glass base
The vanadium dioxide film of even compact is obtained on bottom.Sample transmitance is with wave after gained prepares vanadium dioxide film sample before phase change
Long change curve is shown in Fig. 2, and as seen from the figure, prepared film has good phase transition performance.And the substrate employed in the present embodiment
It is the tempering effect for not influencing tempered glass, by VO for tempered glass2The depositing temperature of film is maintained at 240 DEG C, and with suitable
When back bias voltage and other technological parameters, tempered glass surface formed with good phase transition performance high-performance VO2Film；Greatly
Reduce production cost greatly.Compared with Example 1, the present embodiment main purpose is to form VO on tempered glass surface2Film,
To realize the purpose, depositing temperature is maintained at 240 DEG C by the present embodiment, appropriate back bias voltage size is added to substrate, and coordinate
Other technological parameters, to obtain the high-performance VO with good phase transition performance on tempered glass surface2Film.In addition gained VO2It is thin
The phase transition performances such as the phase transition temperature of film and embodiment 1 are also different.
Embodiment 3
The preparation of vanadium dioxide film is using direct current reaction magnetron sputtering, and using pure vanadium as target, substrate is K9 glass, is passed through
It crosses alcohol and deionized water to be respectively cleaned by ultrasonic 10 minutes, base vacuum during film preparation is 6 × 10-4Pa, with oxygen and argon
Gas is reaction gas and sputter gas, before preparing film, first target pre-sputtering 10min to remove surface contaminants, working vacuum
For 0.5Pa, partial pressure of oxygen 0.02Pa, depositing temperature remains 250 DEG C, during deposition film, is born in substrate addition -185V
Bias, sputtering power 80W, sedimentation time obtain the VO of even compact for 30min2Film.Gained prepares vanadium dioxide film
Rear sample transmitance is shown in Fig. 3 to sample with wavelength change curve before phase change, and as seen from the figure, prepared film has good interconvertibility
Energy.
The above embodiment and following embodiment that the present invention is described in detail are merely to illustrate the present invention rather than limit this hair
Bright range, some nonessential modifications and adaptations that those skilled in the art's the above according to the present invention is made belong to
In protection scope of the present invention.
Claims (3)
1. a kind of vanadium dioxide film low temperature deposition method, which is characterized in that the vanadium dioxide film low temperature deposition method is adopted
With magnetron sputtering technique, using vanadium metal or vanadium alloy as target, using oxygen as reaction gas, argon gas is sputter gas；It prepares thin
Before film, first vacuum chamber is evacuated to less than 1 × 10-3Pa base vacuums, then pass to oxygen and argon gas mixed gas, and partial pressure of oxygen is kept
For 0.01 ~ 0.06Pa, during deposition film, control depositing temperature is 240~245 DEG C, and adds back bias voltage in substrate,
Target surface Sputtering power density is 2-3W/cm2, prepare and obtain high performance VO in substrate surface2Film, the substrate are tempering
Glass；
During the deposition film, back bias voltage is added in substrate, bias size is -150V ~ -250V.
2. vanadium dioxide film low temperature deposition method according to claim 1, which is characterized in that in the deposition film mistake
Cheng Zhong, control depositing temperature are 240 DEG C；
Target surface Sputtering power density is 2W/cm2；
The low temperature deposition method does not need to annealing last handling process, directly prepares VO2Film.
3. vanadium dioxide film low temperature deposition method according to claim 1, which is characterized in that the vanadium dioxide film
Low temperature deposition method uses reaction magnetocontrol sputtering technology, using vanadium metal or vanadium alloy as target, selects tempered glass as substrate,
Using oxygen as reaction gas, argon gas is sputter gas；Before preparing film, first vacuum chamber is evacuated to less than 1 × 10-3Pa backgrounds are true
Sky then passes to oxygen and argon gas mixed gas, and partial pressure of oxygen remains 0.01 ~ 0.06Pa, during deposition film, control
Depositing temperature is 240 DEG C, and adds back bias voltage in substrate, and bias size is -150V ~ ~ -250V；Target surface Sputtering power density
For 2 ~ 3W/cm2, high performance VO is prepared2Film.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510590007.8A CN105132877B (en) | 2015-09-16 | 2015-09-16 | A kind of vanadium dioxide film low temperature deposition method |
| PCT/CN2016/079322 WO2017045398A1 (en) | 2015-09-16 | 2016-04-14 | Low-temperature deposition method for vanadium dioxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510590007.8A CN105132877B (en) | 2015-09-16 | 2015-09-16 | A kind of vanadium dioxide film low temperature deposition method |
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| CN105132877A CN105132877A (en) | 2015-12-09 |
| CN105132877B true CN105132877B (en) | 2018-06-08 |
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| WO (1) | WO2017045398A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105132877B (en) * | 2015-09-16 | 2018-06-08 | 深圳大学 | A kind of vanadium dioxide film low temperature deposition method |
| CN108220897B (en) * | 2016-12-14 | 2019-11-19 | 中国科学院上海硅酸盐研究所 | The method of magnetron sputtering low temperature preparation vanadium dioxide film |
| US11072855B2 (en) | 2017-08-04 | 2021-07-27 | Royal Melbourne Institute Of Technology | Vanadium oxide films and methods of fabricating the same |
| CN108588661B (en) * | 2018-06-12 | 2020-06-23 | 电子科技大学 | Method for optimizing performance of vanadium oxide film by adopting low-valence vanadium seed layer |
| CN111386252A (en) * | 2019-12-11 | 2020-07-07 | 深圳大学 | Preparation method of vanadium dioxide film |
| CN112126895A (en) * | 2020-09-22 | 2020-12-25 | 北京航空航天大学合肥创新研究院 | Preparation method of vanadium dioxide single crystal film |
| CN114561617A (en) * | 2022-03-03 | 2022-05-31 | 季华实验室 | Preparation method of metal oxide film and metal oxide film |
| CN117026193A (en) * | 2023-09-07 | 2023-11-10 | 无锡尚积半导体科技有限公司 | High-phase-change-performance vanadium dioxide film and preparation method thereof |
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| CN101174671A (en) * | 2007-10-18 | 2008-05-07 | 天津大学 | Production method for vanadium dioxide nano thin film with phase-change characteristic |
| CN101280413A (en) * | 2008-04-07 | 2008-10-08 | 中国科学院广州能源研究所 | Low temperature deposition method of hypovanadic oxide thin film on glass |
| CN102061073A (en) * | 2010-11-17 | 2011-05-18 | 苏州奥美材料科技有限公司 | Intelligent temperature control ageing-resisting transparent polycarbonate sheet and manufacture method thereof |
| CN102912308B (en) * | 2012-10-25 | 2014-07-09 | 深圳大学 | Process for manufacturing vanadium dioxide thin film with low phase-transition temperature |
| CN104099563A (en) * | 2013-04-03 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Method for preparing vanadium dioxide film by using magnetron sputtering process |
| CN104195552B (en) * | 2014-07-16 | 2016-09-07 | 电子科技大学 | A kind of method preparing high resistance rate of change vanadium dioxide film on a silicon substrate |
| CN105132877B (en) * | 2015-09-16 | 2018-06-08 | 深圳大学 | A kind of vanadium dioxide film low temperature deposition method |
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2016
- 2016-04-14 WO PCT/CN2016/079322 patent/WO2017045398A1/en active Application Filing
Non-Patent Citations (1)
| Title |
|---|
| "Formation and Thermochromism of VO2 Films Deposited by RF Magnetron Sputtering at Low Substrate Temperature";Ping JIN等;《Japanese Journal of Applied Physics Part 1》;19940331;第33卷(第3A期);第1478-1483页 * |
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| CN105132877A (en) | 2015-12-09 |
| WO2017045398A1 (en) | 2017-03-23 |
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