CN104060241B - Liquid-phase preparation method of high-oriented vanadium dioxide film - Google Patents
Liquid-phase preparation method of high-oriented vanadium dioxide film Download PDFInfo
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Abstract
The invention discloses a liquid-phase preparation method of a high-oriented vanadium dioxide film, belonging to the field of chemical function materials. The preparation method comprises the following steps: preparing precursor liquid by taking triisopropoxyvanadium oxide as solute, coating a sapphire substrate with the obtained precursor liquid to prepare a precursor film, and finally sintering the precursor film in a vacuum environment. According to the preparation method, the vanadium dioxide film is prepared by controlling vacuum sintering conditions on the basis of a liquid-phase method, the obtained film is good in growth orientation, the phase change temperature of the film is about 60 DEG C, and the change of electrical resistivity before and after the phase change is more than three orders of magnitude; in addition, the preparation process is simple and suitable for large-range popularization.
Description
Technical field
The present invention relates to a kind of liquid phase preparation process of highly oriented vanadium dioxide film, belong to field of chemical functional materials.
Background technology
Vanadium dioxide (vo2) it is a kind of strong correlation electron material, body phase vo2Occur near 66 DEG C from high-temperature metal phase (gold
Red stone r phase) to cryogenic semiconductor phase (monocline m phase) structural mutation, along with the huge change of its resistivity and infrared light transmission rate
Change, and phase transition process is reversible.Due to this material, before and after phase transformation, electricity, magnetic, optical property have large change, thus in photoswitch
The aspects such as material, storage medium and intelligent window material have a wide range of applications demand.
vo2Thin film can experience phase transformation circulation repeatedly and not rupture, and therefore have the prospect that is more widely applied.
Highly oriented vo2Thin film is more orderly than polycrystalline because its crystal grain arranges, and leads to it to have more remarkable phase-change characteristic, such as before phase transformation
Change in resistance amplitude larger afterwards, and less transition temperature area scope etc..Common preparation method is sunk except pulse laser
Outside long-pending, the physics film-forming method such as magnetron sputtering, molecular beam epitaxy, the also liquid phase method such as sol-gal process.Comparatively, Physical
The membrane structure of preparation is fine and close, orientation is preferable；And the thin film general structure ratio of liquid phase method preparation is more loose, obtains Seedling height and take
To thin film relatively difficult, but have the advantages that process is simple, low cost, be easy to doping and can large area film forming.Undoubtedly, such as
Fruit can utilize liquid phase method, obtains highly oriented vo using the preparation technology simplifying2Thin film, will have very important significance.For
Above-mentioned target, current technology is primarily present the problem of following several respects: (1) sintering process needs gas shield, including reproducibility
Gas, noble gases and both mixed gas (cn201010126663.5) etc.；This need increase source of the gas, gas circuit and
The device of mixed gas, so that equipment and operation become more complicated, also increases cost of manufacture；(2) when sintering under vacuum environment
Vo that is too high to vacuum requirement, obtaining2Lack orientation；vo2Thin film is typically the oxide of some vanadium before sintering, by true
Empty sintering preparation vo2Vacuum is needed to be better than 10-2pa(surface&coatings technology,201,2007,6772-
6776) document report, is also had to be 1-2pa (applied surface science, 191,2002,176-160)；All in all,
The vo of preparation2Purity is not generally high, also has the barium oxide of other phases to occur, thin film does not have the orientation of growth in x-ray diffraction spectrum.
The reason above-mentioned phenomenon it is critical only that the uniformity of reduction not, in sintering process, film surface and thin film interior contact
Environment different, after leading to sintering, different vanadium oxide thing phases occur；In addition, the selection of backing material is orientated to preparing Seedling height
Vo2Thin film is also extremely important.For solving the above problems, the present invention develops a kind of highly oriented vo2The liquid phase preparation side of thin film
Method, is raw material using Triisopropoxyvanadium(V) oxide, and sapphire wafer is substrate, by omitting drying glue process, makes the predecessor before sintering
Certain organic principle is contained, these organic principles can be with homogeneous reduction v in vacuum-sintering in thin film5+Obtain highly oriented vo2
Thin film, reduces the requirement to vacuum during sintering, and does not need other gas shields, be to prepare highly oriented vo with liquid phase method2Thin film
Provide technical support.
Content of the invention
It is an object of the invention to provide a kind of liquid phase preparation process of highly oriented vanadium dioxide film, to overcome prior art
Deficiency.
The invention provides a kind of liquid phase preparation process of highly oriented vanadium dioxide film, its preparation method is first to use vanadium
Alkoxide prepares precursor liquid, then precursor liquid is applied to substrate surface and prepares precursor film, is finally dried directly without drying glue
Precursor film is placed in fire under vacuum condition and forms；Specific as follows:
(1) with Triisopropoxyvanadium(V) oxide as solute, isopropanol prepares precursor liquid for solvent；
(2) gained precursor liquid is applied to Sapphire Substrate, prepared precursor film；
(3) gained precursor film is placed in sintering in vacuum drying oven, is incubated 7 hours, that is, obtains vanadium dioxide film, its
In, sintering temperature controls at 530 DEG C, and sintering environment vacuum degree control is in 4pa.
When described step (1) prepares precursor liquid, add glacial acetic acid as stabilizer, the matter of glacial acetic acid and Triisopropoxyvanadium(V) oxide
Amount ratio is 1:1～6:1.
In precursor liquid prepared by step (1), Triisopropoxyvanadium(V) oxide is 1-15 with the mass volume ratio g:ml of isopropanol:
100.
The invention has the advantages that
1st, the precursor film of present invention preparation, directly inserts in vacuum drying oven and sinters without being dried process；This
Planting processing mode allows remaining more organic principles in thin film to play the effect of reducing agent in sintering process, and its benefit has
Be be not required under reproducibility or inert gas shielding prepare vo at two: one2Thin film, and, " thin to predecessor with respect to traditional
Film re-sinters after carrying out cold drying process " the process step that eliminates " cold drying ", make originally to pass through two-step reaction system
Standby vo2The process simplification of thin film is single step reaction, thus reducing the requirement to experimental facilitiess, also simplify operation sequence；Two
It is that this reducing agent is evenly distributed on inside thin film, more uniform to the reduction ratio of thin film, can effectively reduce other valence state vanadium oxygen
The generation of compound；The use of Sapphire Substrate, so that interface crystal lattice coupling is good, is conducive to obtaining pure phase, highly oriented vo2Thin
Film；
2nd, compared with prior art, due to the method for the present invention not expensive filming equipment of value on demand, vacuum used
(3pa～5pa) belongs to coarse vacuum it is only necessary to common mechanical pump just can reach requirement；Due to not needing to be passed through any gas, and
Eliminate the process of cold drying before sintering, so that whole operation process is more succinct, masking cost is lower；
3rd, the vanadium dioxide film prepared by the present invention, has higher quality, and macroscopical phase-change characteristic is notable, phase transformation
Change in resistance reaches more than 3 magnitudes in front and back；
4 test result indicate that, gained vo2Thin film, in x-ray diffraction spectrum, shows the good orientation of growth.
Brief description
The highly oriented vo that Fig. 1 prepares for the embodiment of the present invention 12The X-ray diffraction pattern of thin film；
The highly oriented vo that Fig. 2 prepares for the embodiment of the present invention 12Before and after thin film phase change critical temperature, resistance becomes with temperature
Change curve chart；
The highly oriented vo that Fig. 3 prepares for the embodiment of the present invention 22The X-ray diffraction pattern of thin film；
The highly oriented vo that Fig. 4 prepares for the embodiment of the present invention 22Before and after thin film phase change critical temperature, resistance becomes with temperature
Change curve chart；
The highly oriented vo that Fig. 5 prepares for the embodiment of the present invention 32The X-ray diffraction pattern of thin film；
The highly oriented vo that Fig. 6 prepares for the embodiment of the present invention 32Before and after thin film phase change critical temperature, resistance becomes with temperature
Change curve chart.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, but
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limit.
Embodiment 1
Prepare vanadium dioxide film in 430 DEG C of sintering temperature, insulation 4 hours, vacuum 5pa.
(1) precursor liquid preparation:
Take Triisopropoxyvanadium(V) oxide 0.6g, dissolve in 50ml isopropanol, then Deca 1.3g glacial acetic acid forms mixed solution, uses glass
Rod stirring 10 minutes, that is, obtain the precursor liquid of vanadium dioxide film.
(2) clean substrate:
Select sapphire wafer to do substrate, be put into respectively being cleaned by ultrasonic 5 minutes in acetone, ethanol and deionized water,
Finally dried up with nitrogen, standby.
(3) precursor liquid plated film:
Choose the precursor liquid of above-mentioned steps (1) gained, with sol evenning machine spin coating plated film；Spin coating process is: 200 turns of first low speed/
Minute, keep 9 seconds；2000 revolutions per seconds of high speed again, keeps 20 seconds；Then, the thin film obtaining is placed on 250 DEG C of roasting glue platforms, is dried
3 minutes, that is, obtain vanadium dioxide precursor film.
(4) vanadium dioxide film sintering:
The precursor film that above-mentioned steps are obtained puts into vacuum drying oven, start vacuum pump by system vacuum be evacuated to 3pa with
Under, adjust the valve between vacuum pump and system, make vacuum be maintained at 5pa；430 DEG C of sintering temperature of setting, heat up speed
6 DEG C/min of degree, temperature retention time 4 hours, Temperature fall after the completion of sintering, finally obtain the thick vanadium dioxide film of about 20nm.
Fig. 1 is the vo obtained by embodiment 12The x-ray diffraction spectrum of thin film, 39.6 ° of angles of diffraction correspond to vo2(020) spread out
Penetrate, in addition, do not find other significantly vo2Diffraction maximum exists, and shows that the thin film of present invention preparation has good crystallization
Performance and Seedling height orientation.
Fig. 2 is the vo obtained by embodiment 12Before and after phase transformation, the change curve of resistivity is it can be seen that thin before and after phase transformation
2m ω when room temperature for the membrane resistance changes to 1k ω when 90 DEG C, and the change of resistivity reaches more than 3 magnitudes, and phase transition temperature is
59.7 DEG C, phase Trapezoidal is 9.4 DEG C.
Embodiment 2
Prepare vanadium dioxide film in 530 DEG C of sintering temperature, insulation 7 hours, vacuum 4pa.
(1) precursor liquid preparation:
Take Triisopropoxyvanadium(V) oxide 1.9g, dissolve in 50ml isopropanol, then Deca 6.3g glacial acetic acid forms mixed solution, uses glass
Rod stirring 10 minutes, that is, obtain the precursor liquid of vanadium dioxide film.
(2) clean substrate:
Select sapphire wafer to do substrate, be put into respectively being cleaned by ultrasonic 5 minutes in acetone, ethanol and deionized water,
Finally dried up with nitrogen, standby.
(3) precursor liquid plated film:
Choose the precursor liquid of above-mentioned steps (1) gained, with sol evenning machine spin coating plated film；Spin coating process is: 200 turns of first low speed/
Minute, keep 9 seconds；2000 revolutions per seconds of high speed again, keeps 20 seconds, that is, obtains vanadium dioxide precursor film.
(4) vanadium dioxide film sintering:
The precursor film that above-mentioned steps are obtained puts into vacuum drying oven, start vacuum pump by system vacuum be evacuated to 3pa with
Under, adjust the valve between vacuum pump and system, make vacuum be maintained at 4pa；530 DEG C of sintering temperature of setting, heat up speed
6 DEG C/min of degree, temperature retention time 7 hours, Temperature fall after the completion of sintering, finally obtain the thick vanadium dioxide film of about 50nm.
Fig. 3 is the vo obtained by embodiment 22The x-ray diffraction spectrum of thin film, 39.6 ° of angles of diffraction correspond to vo2(020) spread out
Penetrate, in addition, do not find other significantly vo2Diffraction maximum exists, and shows that the thin film of present invention preparation has good crystallization
Performance and Seedling height orientation.
Fig. 4 is the vo obtained by embodiment 22Before and after phase transformation, the change curve of resistivity is it can be seen that thin before and after phase transformation
0.1m ω when room temperature for the membrane resistance changes to 100 ω when 90 DEG C, and the change of resistivity reaches 3 magnitudes, and phase transition temperature is
57.6 DEG C, phase Trapezoidal is 4.2 DEG C.
Embodiment 3
Prepare vanadium dioxide film in 590 DEG C of sintering temperature, insulation 10 hours, vacuum 6pa.
(1) precursor liquid preparation:
Take Triisopropoxyvanadium(V) oxide 4.5g, dissolve in 50ml isopropanol, then Deca 25g glacial acetic acid forms mixed solution, uses glass
Rod stirring 10 minutes, that is, obtain the precursor liquid of vanadium dioxide film.
(2) clean substrate:
Select sapphire wafer to do substrate, be put into respectively being cleaned by ultrasonic 5 minutes in acetone, ethanol and deionized water,
Finally dried up with nitrogen, standby.
(3) precursor liquid plated film:
Choose the precursor liquid of above-mentioned steps (1) gained, with sol evenning machine spin coating plated film；Spin coating process is: 200 turns of first low speed/
Minute, keep 9 seconds；2000 revolutions per seconds of high speed again, keeps 20 seconds；Then, the thin film obtaining is placed on 90 DEG C of roasting glue platforms, is dried 5
Minute, that is, obtain vanadium dioxide precursor film.
(4) vanadium dioxide film sintering:
The precursor film that above-mentioned steps are obtained puts into vacuum drying oven, start vacuum pump by system vacuum be evacuated to 3pa with
Under, adjust the valve between vacuum pump and system, make vacuum be maintained at 6pa；590 DEG C of sintering temperature of setting, heat up speed
6 DEG C/min of degree, temperature retention time 10 hours, Temperature fall after the completion of sintering, finally obtain the thick vanadium dioxide film of about 65nm.
Fig. 5 is the vo obtained by embodiment 32The x-ray diffraction spectrum of thin film, 39.6 ° of angles of diffraction correspond to vo2(020) spread out
Penetrate, in addition, do not find other significantly vo2Diffraction maximum exists, and shows that the thin film of present invention preparation has good crystallization
Performance and Seedling height orientation.
Fig. 6 is the vo obtained by embodiment 32Before and after phase transformation, the change curve of resistivity is it can be seen that thin before and after phase transformation
2m ω when room temperature for the membrane resistance changes to 500 ω when 90 DEG C, and the change of resistivity reaches more than 3 magnitudes, phase transition temperature
For 56.6 DEG C, phase Trapezoidal is 5.1 DEG C.
The above is only the preferred embodiment of the present invention it is noted that the ordinary person for the art comes
Say, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (3)
1. a kind of liquid phase preparation process of highly oriented vanadium dioxide film, its preparation method is that the alkoxide first using vanadium prepares forerunner
Then precursor liquid is applied to substrate surface and prepares precursor film by liquid, is finally dried directly by precursor film without drying glue
It is placed in fire under vacuum condition and form；Specific as follows:
(1) with Triisopropoxyvanadium(V) oxide as solute, isopropanol prepares precursor liquid for solvent；
(2) gained precursor liquid is applied to Sapphire Substrate, prepared precursor film；
(3) gained precursor film is placed in sintering in vacuum drying oven, is incubated 7 hours, that is, obtains vanadium dioxide film, wherein, burn
Junction temperature controls at 530 DEG C, and sintering environment vacuum degree control is in 4pa.
2. a kind of highly oriented vanadium dioxide film according to claim 1 liquid phase preparation process it is characterised in that: in step
Suddenly, when (1) prepares precursor liquid, add glacial acetic acid as stabilizer, glacial acetic acid is 1:1 ~ 6:1 with the mass ratio of Triisopropoxyvanadium(V) oxide.
3. a kind of highly oriented vanadium dioxide film according to claim 1 liquid phase preparation process it is characterised in that: in step
Suddenly, in the precursor liquid that prepared by (1), Triisopropoxyvanadium(V) oxide is 1-15:100 with the mass volume ratio g:ml of isopropanol.
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| CN105669248A (en) * | 2016-01-04 | 2016-06-15 | 北京理工大学 | Vanadium dioxide thin film having regular truss network structure and preparation method thereof |
| CN106012014A (en) * | 2016-06-06 | 2016-10-12 | 电子科技大学 | Vanadium dioxide film growing method |
| CN110306236B (en) * | 2019-07-12 | 2020-09-04 | 暨南大学 | Large size V6O13Single chip and preparation method thereof |
| CN112125337A (en) * | 2020-10-16 | 2020-12-25 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by using pentavalent vanadium alkoxide as raw material |
| CN113880138A (en) * | 2021-11-09 | 2022-01-04 | 成都先进金属材料产业技术研究院股份有限公司 | VO (vanadium oxide) directly prepared by using triisopropoxide vanadium as vanadium source2Method (2) |
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| CN101691658B (en) * | 2009-09-08 | 2011-07-27 | 中国科学院广州能源研究所 | Method for preparing vanadic oxide film growing along c-axis |
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