CN102732847A - Phase change vanadium dioxide film prepared by rapid thermal oxidation method - Google Patents
Phase change vanadium dioxide film prepared by rapid thermal oxidation method Download PDFInfo
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- CN102732847A CN102732847A CN2012102015055A CN201210201505A CN102732847A CN 102732847 A CN102732847 A CN 102732847A CN 2012102015055 A CN2012102015055 A CN 2012102015055A CN 201210201505 A CN201210201505 A CN 201210201505A CN 102732847 A CN102732847 A CN 102732847A
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Abstract
The present invention discloses a phase change vanadium dioxide film prepared by a rapid thermal oxidation method. The purpose of the present invention is to overcome disadvantages of more regulation parameters, complex process, poor experiment controllability in the existing preparation method for a vanadium dioxide film with a phase change characteristic. With the present invention, a metal vanadium film with a sputtering time of 10-30 minutes is subjected to rapid thermal oxidation for 30-90 seconds (wherein the thermal insulation time is the rapid thermal oxidation time) at a temperature of 430-500 DEG C to obtain the material with the thermal induced phase transition characteristic, wherein the temperature increasing speed is 50 DEG C per second, the temperature decreasing time is less than 3 minutes, and the working gas is high purity oxygen or nitrogen-oxygen mixed gas during the rapid thermal oxidation process. The method of present invention has high repeatability, and is suitable for large scale production.
Description
Technical field
The invention relates to method for manufacturing thin film, relate in particular to the method that a kind of preparation has the phase-change characteristic vanadium oxide film.
Background technology
Vanadium dioxide has the reversibility phase-change characteristic from cryogenic semiconductor to the hot metal phase near Tc=68 ℃, its transformation temperature near room temperature makes by VO
2The film of preparation has in fields such as smart window, micro-metering bolometer, photoswitches widely to be used.
The preparation method of vanadium dioxide film is more, comprises that mainly sputtering method, vacuum vapor deposition method, pulsed laser deposition and colloidal sol coagulate-glue method etc.Wherein but sputtering method has sputtering yield height, film forming evenly large area deposition and characteristics such as pollution-free, is that the lot of domestic and foreign researchist prepares vanadium dioxide film method commonly used.This method is in sputter procedure, to add oxygen and argon gas; Argon gas is as working gas; Oxygen is as reactant gases, in sputter procedure through vanadium metal and oxygen combine to prepare vanadium oxide film, annealed then processing obtains to have the vanadium dioxide film of phase-change characteristic.This method regulation and control parameter is many, preparation process more complicated, and the repeatability of experiment is restricted.Oxidation style is direct metal refining vanadium film fast; The vanadium dioxide film that has phase-change characteristic then through quick oxidizing thermal treatment preparation; This method regulates and control not only that parameter is few, and technology is simple, and adopts fast heat treatment device; Make process cycle significantly reduce, prepared film has good thermal induced phase transition characteristic.
Summary of the invention
The objective of the invention is; Utmost point unstable to vanadium dioxide; And, complex process many to the general preparing method's of vanadium dioxide film the regulation and control parameter that has phase-change characteristic in preparation, the relatively poor shortcoming of experiment controllability, a kind of get everything ready novel method of vanadium dioxide film of phase-change characteristic of rapid thermal oxidation legal system that adopts is provided.
The present invention is achieved through following technical scheme.
A kind of phase transformation vanadium dioxide film of rapid thermal oxidation process preparation has following steps:
(1) silicon chip is cut into the specification chip, be soaked in the ethanol solution, adopt the silicon chip cleaning of standard, ultrasonic cleaning is used washed with de-ionized water again, oven dry;
(2) with the substrate of the chip after step (1) oven dry, put on the ultrahigh vacuum(HHV) facing-target magnetron sputtering system coating equipment substrate frame as the preparation film; It is 99.99% vanadium metal target that target is selected purity for use, and working gas is an argon gas, and the body vacuum with Vakuumkammer before the sputter is evacuated to 2.5 * 10
-4Pa, argon flow amount are 50sccm, and operating pressure is 2.0Pa; At first carry out preparatory sputter removing the dirt of target material surface, sputtering power 165w, splash-proofing sputtering metal vanadium film on substrate subsequently, sputtering time is 10-30 minute, film thickness is 100-300nm;
(3) adopt fast heat treatment device that the vanadium metal film of step (2) is carried out rapid thermal oxidation; The rapid thermal oxidation temperature is 430 ℃-500 ℃, and the rapid thermal oxidation time is 30s-90s, and soaking time is the rapid thermal oxidation time; In the rapid thermal oxidation process, heat-up rate is 50 ℃/s, and temperature fall time is in 3 minutes; Working gas is high purity oxygen gas or nitrogen oxygen mixed gas, and the gas flow when intensification and cooling is 10slpm, and gas flow is 3slpm during insulation;
(4) measure the resistance-temperature characteristics of goods in 20 ℃ of-80 ℃ of scopes.
The ultrasonic cleaning time of said step (1) is 15-20 minute.
The ultrahigh vacuum(HHV) of said step (2) is a DPS-III type to target magnetic control sputtering plating film machine.
The purity of argon of said step (2) is 99.999%.
The AG610 type fast heat treatment device that the fast heat treatment device that said step (3) adopts is produced for Allwin21corp.USA company.
The quality purity of the high purity oxygen gas of said step (3) is 99.999%, and the ratio of nitrogen oxygen mixed gas is 1:1.
The invention has the beneficial effects as follows the novel method of the vanadium dioxide film that provide a kind of and adopted that rapid thermal oxidation method, few, the technology of regulation and control parameter are simple, preparation time and cycle significantly reduces with phase-change characteristic.The present invention is the vanadium metal film of 10-30min for sputtering time, 430 ℃-500 ℃ of rapid thermal oxidation temperature, and rapid thermal oxidation time 30s-90s (soaking time) can obtain the thermal induced phase transition characteristic.The present invention is repeatable high, is applicable to big area production.
Description of drawings
Fig. 1 is resistance-thetagram of embodiment 1;
Fig. 2 is resistance-thetagram of embodiment 2;
Fig. 3 is resistance-thetagram of embodiment 3.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
(1) silicon chip is cut into the chip that is of a size of 2cm * 2cm, be soaked in the ethanol solution, adopt the silicon chip cleaning of standard, ultrasonic cleaning is used washed with de-ionized water again, oven dry;
(2) cleaned print in the step (1) is placed DPS-III type ultrahigh vacuum(HHV) facing-target magnetron sputtering system coating equipment Vakuumkammer, the body vacuum is taken out 2.5 * 10
-4Pa; Feeding purity is 99.999% argon gas, and argon flow amount is 50sccm, regulates operating pressure to 2.0Pa; At first carry out preparatory sputter to remove the dirt of target material surface, sputtering power 165w begins metal refining vanadium film in advance after the sputter, and sputtering time is 10min;
(3) the vanadium metal film of step (2) is put in the AG610 type fast heat treatment device of Allwin21corp.USA company production, the rapid thermal oxidation temperature is 430 ℃, and the rapid thermal oxidation time is 90s; Temperature rise rate is 50 ℃/s; Working gas is oxygen (quality purity is 99.999%), and intensification and cooling gas flow are 10slpm, and gas flow is 3slpm during insulation;
(4) vanadium dioxide film that makes of step (3) is under 20 ℃ of conditions in temperature; The film rectangular resistance of measuring is 139.4K Ω/; In temperature is under 80 ℃ of conditions, and the film rectangular resistance of measurement is 3.2K Ω/, and the temperature coefficient of resistance of vanadium dioxide film is-1.62 * 10
-2K
-1
Resistance-temperature curve of embodiment 1 is as shown in Figure 1, can be found out by Fig. 1, and prepared vanadium dioxide film has phase-change characteristic.
Embodiment 2
Operation steps is identical with embodiment 1, and the processing condition of step (2) are: sputtering time 10min; Working gas is an oxygen in the rapid thermal oxidation process of step (3), 470 ℃ of rapid thermal oxidation temperature, rapid thermal oxidation time 30s;
The vanadium dioxide film that embodiment 2 makes is under 20 ℃ the condition in temperature; The square resistance of measuring is 197.2K Ω/; Be that the film rectangular resistance of measurement is 3.4K Ω/ under 80 ℃ the condition in temperature, the temperature coefficient of resistance of vanadium dioxide film is-1.63 * 10
-2K
-1
Resistance-temperature curve of embodiment 2 is as shown in Figure 2, can be found out by Fig. 2, and prepared vanadium dioxide film has phase-change characteristic.
Embodiment 3
Operation steps is identical with embodiment 1, and the processing condition of step (2) are: sputtering time 30min; Working gas is an oxygen in the rapid thermal oxidation process of step (3), 500 ℃ of rapid thermal oxidation temperature, rapid thermal oxidation time 40s;
The vanadium dioxide film that embodiment 3 makes is under 20 ℃ the condition in temperature; The square resistance of measuring is for being 225.8K Ω/; Be that the film rectangular resistance of measurement is 0.53K Ω/ under 80 ℃ the condition in temperature, the temperature coefficient of resistance of vanadium dioxide film is-1.66 * 10
-2K
-1
Resistance-temperature curve of embodiment 3 is as shown in Figure 3, can be found out by Fig. 3, and prepared vanadium dioxide film has phase-change characteristic.
Embodiment 4
Operation steps is identical with embodiment 1, and the processing condition of step (2) are: sputtering time 15min; Working gas is an oxygen in the rapid thermal oxidation process of step (3), 480 ℃ of rapid thermal oxidation temperature, rapid thermal oxidation time 33s;
The vanadium dioxide film that embodiment 4 makes is under 20 ℃ the condition in temperature, and the square resistance of measurement is for being 170.2K Ω/, is that the film rectangular resistance of measurement is 1.5K Ω/ under 80 ℃ the condition in temperature, and the temperature coefficient of resistance of film is-1.65 * 10
-2K
-1
Embodiment 5
Operation steps is identical with embodiment 1, and the processing condition of step (2) are: sputtering time 10min; Working gas is a nitrogen oxygen mixed gas in the rapid thermal oxidation process of step (3), and ratio is 1:1, and the rapid thermal oxidation temperature is 470 ℃, and the rapid thermal oxidation time is 50s.
The vanadium oxide film that embodiment 5 makes is under 20 ℃ the condition in temperature; The square resistance of measuring is for being 218.8K Ω/; Be that the film rectangular resistance of measurement is 5.7K Ω/ under 80 ℃ the condition in temperature, the temperature coefficient of resistance of vanadium dioxide film is-1.62 * 10
-2K
-1
Claims (6)
1. the phase transformation vanadium dioxide film of rapid thermal oxidation process preparation has following steps:
(1) silicon chip is cut into the specification chip, be soaked in the ethanol solution, adopt the silicon chip cleaning of standard, ultrasonic cleaning is used washed with de-ionized water again, oven dry;
(2) with the substrate of the chip after step (1) oven dry, put on the ultrahigh vacuum(HHV) facing-target magnetron sputtering system coating equipment substrate frame as the preparation film; It is 99.99% vanadium metal target that target is selected purity for use, and working gas is an argon gas, and the body vacuum with Vakuumkammer before the sputter is evacuated to 2.5 * 10
-4Pa, argon flow amount are 50sccm, and operating pressure is 2.0Pa; At first carry out preparatory sputter removing the dirt of target material surface, sputtering power 165w, splash-proofing sputtering metal vanadium film on substrate subsequently, sputtering time is 10-30 minute, film thickness is 100-300nm;
(3) adopt fast heat treatment device that the vanadium metal film of step (2) is carried out rapid thermal oxidation; The rapid thermal oxidation temperature is 430 ℃-500 ℃, and the rapid thermal oxidation time is 30s-90s, and soaking time is the rapid thermal oxidation time; In the rapid thermal oxidation process, heat-up rate is 50 ℃/s, and temperature fall time is in 3 minutes; Working gas is high purity oxygen gas or nitrogen oxygen mixed gas, and the gas flow when intensification and cooling is 10slpm, and gas flow is 3slpm during insulation;
(4) measure the resistance-temperature characteristics of goods in 20 ℃ of-80 ℃ of scopes.
2. according to the phase transformation vanadium dioxide film of the rapid thermal oxidation process of claim 1 preparation, it is characterized in that the ultrasonic cleaning time of said step (1) is 15-20 minute.
3. according to the phase transformation vanadium dioxide film of the rapid thermal oxidation process of claim 1 preparation, it is characterized in that the ultrahigh vacuum(HHV) of said step (2) is a DPS-III type to target magnetic control sputtering plating film machine.
4. according to the phase transformation vanadium dioxide film of the rapid thermal oxidation process of claim 1 preparation, it is characterized in that the purity of argon of said step (2) is 99.999%.
5. according to the phase transformation vanadium dioxide film of the rapid thermal oxidation process of claim 1 preparation, it is characterized in that the fast heat treatment device that said step (3) adopts is the AG610 type fast heat treatment device that Allwin21corp.USA company produces.
6. according to the phase transformation vanadium dioxide film of the rapid thermal oxidation process of claim 1 preparation, it is characterized in that the quality purity of the high purity oxygen gas of said step (3) is 99.999%, the ratio of nitrogen oxygen mixed gas is 1:1.
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Cited By (6)
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|---|---|---|---|---|
| CN103361614A (en) * | 2013-06-29 | 2013-10-23 | 天津大学 | Method for preparing Terahertz modulator film material based on flexible substrate |
| CN103882399A (en) * | 2014-03-18 | 2014-06-25 | 天津大学 | Preparation method of flexible substrate based nano vanadium oxide functional film with phase transition characteristic |
| CN103981488A (en) * | 2014-05-23 | 2014-08-13 | 天津大学 | Method for preparing vanadium oxide nanoparticle array by rapid heat treatment |
| CN103981500A (en) * | 2014-05-23 | 2014-08-13 | 天津大学 | Surface microstructure for improving phase change amplitude of vanadium dioxide thin film |
| CN104775101A (en) * | 2015-04-22 | 2015-07-15 | 武汉理工大学 | Preparation method and application of porous vanadium dioxide thin film |
| CN105256280A (en) * | 2015-11-24 | 2016-01-20 | 天津大学 | Method for regulating and controlling phase transition temperature of vanadium dioxide through fast heat treatment |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361614A (en) * | 2013-06-29 | 2013-10-23 | 天津大学 | Method for preparing Terahertz modulator film material based on flexible substrate |
| CN103882399A (en) * | 2014-03-18 | 2014-06-25 | 天津大学 | Preparation method of flexible substrate based nano vanadium oxide functional film with phase transition characteristic |
| CN103981488A (en) * | 2014-05-23 | 2014-08-13 | 天津大学 | Method for preparing vanadium oxide nanoparticle array by rapid heat treatment |
| CN103981500A (en) * | 2014-05-23 | 2014-08-13 | 天津大学 | Surface microstructure for improving phase change amplitude of vanadium dioxide thin film |
| CN103981500B (en) * | 2014-05-23 | 2016-04-27 | 天津大学 | A kind of surface micro-structure improving vanadium dioxide film phase time-varying amplitude |
| CN104775101A (en) * | 2015-04-22 | 2015-07-15 | 武汉理工大学 | Preparation method and application of porous vanadium dioxide thin film |
| CN104775101B (en) * | 2015-04-22 | 2017-06-13 | 武汉理工大学 | A kind of preparation method and application of loose structure vanadium dioxide film |
| CN105256280A (en) * | 2015-11-24 | 2016-01-20 | 天津大学 | Method for regulating and controlling phase transition temperature of vanadium dioxide through fast heat treatment |
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Application publication date: 20121017 |