CN109594065A - A kind of preparation method of In and the vanadium dioxide film of Zn codope - Google Patents
A kind of preparation method of In and the vanadium dioxide film of Zn codope Download PDFInfo
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- CN109594065A CN109594065A CN201811434671.3A CN201811434671A CN109594065A CN 109594065 A CN109594065 A CN 109594065A CN 201811434671 A CN201811434671 A CN 201811434671A CN 109594065 A CN109594065 A CN 109594065A
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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Abstract
The present invention relates to the preparation methods of a kind of In and the vanadium dioxide film of Zn codope, it is characterized in that, include the following steps: S1: indium trichloride ultrasonic dissolution is formed to the solution of clear in hydrogenperoxide steam generator, and acquired solution and vanadic anhydride dispersing and dissolving are finally obtained into suspension A in isobutanol；Heating stirring at a certain temperature, while hydrochloric acid, zinc oxide and oxalic acid being added into suspension A, it is passed through nitrogen, 10h or more is stirred to react in the atmosphere of nitrogen, obtains sol B；Be aged 1 day through Room-temperature seal or more, obtain sol-gel precursor liquid；S2: sol-gel precursor liquid is spun on the dry substrate surface of cleaning, drying removes extra iso-butanol solvent；S3: it repeats step S2 more than five times, obtains pre-deposition precursor thin-film；Then by vacuum annealing process, the vanadium dioxide film of the In Yu Zn codope are obtained.
Description
Technical field
The method of the present invention is related to the preparation method of a kind of In and the vanadium dioxide film of Zn codope, belongs to vanadium dioxide and mixes
Miscellaneous Material Field.
Background technique
Vanadium dioxide is (VO2) a kind of intelligent thermochromic material；When near 68 DEG C, vanadium dioxide has reversible gold
Belong to an insulator transition (MTT), this transformation is the process of a primary structure phase transition, monocline M of the crystal structure from low temperature
Phase transition is to high temperature four directions rutile R phase, and conductivity, infrared region transmitance and reflectivity mutate in transition process；
In semiconductor phase, phonon energy is lower than band gap, VO2Show high infrared light transmittance；On the contrary, metal phase then show it is low
Infrared light transmittance；Its phase transformation response speed is exceedingly fast, and up to tens fs magnitudes, and extra electric field and stress field may be implemented pair
The regulation of MTT phase transformation, these excellent performances make VO2In lasing safety, smart window, heat/optoelectronic switch, more regulation electronics devices
The fields such as part, light storage device are with a wide range of applications.
Vanadium dioxide block is after multiple phase transformation, since the stress generated in phase transition process will lead to the crystal of material
Size occurs rupture or becomes fragment；And monocrystalline vanadium dioxide film can be still stabilized after multiple phase transformation, thus
It is in practical applications mostly the vanadium dioxide film of monocrystalline.
For in application aspects such as smart windows, VO268 DEG C of phase transition temperature it is obviously higher, it is difficult to accomplish Effective Regulation
Room temperature, thus how to VO2Phase transition temperature and its infrared optics characteristic, which carry out regulation, becomes most important；Numerous research tables
Bright, chemical element doping is to change VO2The effective means of phase transition temperature；In the research that doping reduces phase transition temperature, tungsten atom
1% phase transition temperature of every doping can reduce 20-26K, once become research hotspot, and the doping content by changing tungsten can control
Phase transition temperature is in room temperature between 68 DEG C；However while being entrained in change phase transition temperature of the transition metal elements such as W, generally can
Cause to adulterate VO2Phase-change characteristic of the film after before phase change is obviously reduced, as near transformation temperature sudden change of resistivity amount reduce and it is infrared
The reduction of light ability of regulation and control；Although research report shows the VO of one-dimensional nano structure2Such as nanobelt, nano wire, to a certain degree
On can overcome disadvantage mentioned above, but the current stage still has preparation process and requires complicated, the excessively high problem of cost and phase transformation special
Property have uncertainty；Prior art discloses carrying out codope using W and Eu to vanadium dioxide, but its phase transition temperature is higher,
To infrared regulating power, there is also deficiencies.
Therefore new design of material and preparation process condition are explored, realizing reduces VO2The regulation of phase transition temperature is not dropped simultaneously
Low vanadium dioxide rear before phase change optimizes optical tune ability and resistance transition ability for practical application to infrared light regulating power
For seem most important.
Summary of the invention
In view of this, one of the objects of the present invention is to provide the vanadium dioxide film of a kind of In and Zn codope, this is thin
Film is reducing VO2Vanadium dioxide film is not reduced while phase transition temperature before phase change afterwards to infrared light regulating power；The present invention
The second purpose be to provide a kind of In and Zn codope vanadium dioxide film preparation method.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of In and the vanadium dioxide film of Zn codope, which comprises the steps of:
1. a kind of preparation method of the vanadium dioxide film of In and Zn codope, which comprises the steps of:
S1: indium trichloride ultrasonic dissolution is formed to the solution of clear in hydrogenperoxide steam generator, and by acquired solution and five oxygen
Change two vanadium dispersing and dissolvings in isobutanol, finally obtains suspension A；Heating stirring at a certain temperature, while into suspension A
Hydrochloric acid, zinc oxide and oxalic acid is added, is passed through nitrogen, is stirred to react 10h or more in the atmosphere of nitrogen, obtains sol B；Through room temperature
Sealing ageing 1 day or more, obtain sol-gel precursor liquid；
S2: sol-gel precursor liquid is spun on the dry substrate surface of cleaning, drying removes extra iso-butanol solvent；
S3: and repeat step S2 more than five times, obtain pre-deposition precursor thin-film；Then by vacuum annealing process, institute is obtained
State the vanadium dioxide film of In Yu Zn codope.
Preferably, the substrate is Al2O3。
Preferably, the ultrasonic dissolution operates at room temperature, reacts 60min or more.
Preferably, the concentration range of vanadium is 0 .6-0.8mol/L in sol B.
Preferably, the concentration of vanadium is 0.8mo1/L in the sol B.
Preferably, described, spin coating range of speeds 4000-5000rpm, 90 DEG C -100 DEG C of drying temperature.
Preferably, described, vacuum annealing process are as follows: vacuum degree 1-10Pa, annealing temperature are 600 DEG C -700 DEG C, are moved back
The fiery time is >=7h, it is further preferred that vacuum annealing process are as follows: vacuum degree 6Pa, annealing temperature are 650 DEG C, annealing time
For 10h.
Preferably, the rate for being passed through nitrogen is 10mL/min.
Beneficial effect
There is the vanadium dioxide film of In made from preparation method according to the present invention and Zn codope the preferential crystallization of height to take
To being able to maintain the efficient regulating power to infrared transmission while phase transition temperature is greatly lowered；Under the above conditions,
The vanadium dioxide film transition temperature of In and the Zn codope of preparation drops to 30 DEG C hereinafter, infrared adjusting efficiency (2500nm) reaches
To 60% or more.
Design of material method and preparation process provided by the invention may be implemented to carry out accurately the phase-change characteristic of material
Control has good repeatability and production meaning；This method also has a simple process, and it is excellent that raw material is easy to get and low energy consumption
Point.
Detailed description of the invention
Fig. 1 is the X-ray diffraction ((XRD) of the vanadium dioxide film of In prepared by the embodiment of the present invention 1 and Zn codope
Figure；
Fig. 2 is Raman spectrum (Raman) figure of the vanadium dioxide film of In prepared by the embodiment of the present invention 1 and Zn codope；
Fig. 3 is the scanning electron microscope (SEM) of the vanadium dioxide film of In prepared by the embodiment of the present invention 1 and Zn codope
Figure.
Specific embodiment
To facilitate the understanding of the present invention, below will be to invention is more fully described, still, the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein；On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
The present invention will be further described With reference to embodiment.
Embodiment 1
S1, the indium trichloride for weighing 18mg are mixed with the 30wt% hydrogen peroxide of 2.5mL, and 60min is stirred by ultrasonic under the conditions of 22 DEG C
Left and right；Indium trichloride is dissolved in hydrogenperoxide steam generator at this time, forms transparent clear solution；Sequentially add the isobutanol of 50m1,1g
Vanadic anhydride stirs evenly, and obtains suspension A；In 70 DEG C of heating stirrings, while into suspension A, it is added 2.5mL's
37wt% concentrated hydrochloric acid, the H of 100mg zinc oxide and 1.30g2C2O4, it is passed through nitrogen, 10h is stirred to react in the atmosphere of nitrogen, obtains
Blue-green vitreosol B；Sealing ageing at room temperature obtains so-gel precursor liquid in 1 day.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min revolves so-gel precursor liquid after drying
It is applied to c-Al2O3Substrate surface, spin coater revolving speed are 4000rpm/min, 70 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 10Pa, annealing temperature be 600 DEG C, annealing time 4h, obtain a kind of In with
The vanadium dioxide film of Zn codope.
The vanadium dioxide film of In and Zn codope prepared by embodiment 1 have done XRD test, as a result as shown in Figure 1；By scheming
1 it is found that the film occurs the peak of the crystalline orientation of vanadium dioxide at 39.8 °, illustrates to have obtained the vanadium dioxide of (020) orientation
Film.
The vanadium dioxide film of In and Zn codope prepared by embodiment 1 have done Raman spectrum test, as a result such as Fig. 2 institute
Show；As seen from the figure, the film is in 194,223,264,307,338,387,440,498,617 and 825cm-1Occur two at position
The Raman vibration peak of vanadium oxide, other signal peak-to-average powers illustrate to have obtained vanadium dioxide film from substrate.
The infrared transmittivity that the vanadium dioxide film of In and Zn codope prepared by embodiment 1 have done 24 DEG C and 90 DEG C is surveyed
Examination, as a result, it has been found that the film of In and Zn codope is to wave number 2000-4000cm-1Infrared light in range has stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of In and Zn codope prepared by embodiment 1, which are analyzed in wavelength,2It is thin
The transmitance of film varies with temperature, as a result, it has been found that the phase transition temperature of film is very low, it is 30 DEG C, the variation of rear transmitance reaches before phase change
To 70%；The result shows In and Zn to have effectively entered VO2In film, and the titanium dioxide of obtained In and Zn codope
Vanadium film has good infrared ray regulating power while reducing phase transition temperature, there is very high practical application value.
Embodiment 2
A kind of preparation method of above-mentioned In and the vanadium dioxide film of Zn codope, the described method comprises the following steps:
S1, the indium trichloride for weighing 18mg are mixed with the 30wt% hydrogen peroxide of 3m1, and the left side 70min is stirred by ultrasonic under the conditions of 22 DEG C
It is right；Indium trichloride is dissolved in hydrogenperoxide steam generator at this time, forms transparent clear solution；Sequentially add 40m1 isobutanol, five oxygen of 1g
Change two vanadium to stir evenly, obtains suspension A；In 60 DEG C of heating stirrings, at the same into suspension A be added 3m1 the dense salt of 37wt%
Acid, the H of 100mg zinc oxide and 1.30g2C2O4, it is passed through nitrogen, 10h is stirred to react in the atmosphere of nitrogen, it is saturating to obtain blue-green
Bright sol B；Sealing ageing at room temperature obtains sol-gel precursor liquid in 1 day.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min, by sol-gel precursor liquid spin coating after drying
In c-Al2O3Substrate surface, spin coater revolving speed are 4000rpm/min, 100 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 10Pa, annealing temperature are 700 DEG C, annealing time 4h, obtain a kind of In
With the vanadium dioxide film of Zn codope.
The vanadium dioxide film of In and Zn codope prepared by embodiment 2 have done XRD test, as can be seen from the results, the film
Occur the peak of the crystalline orientation of vanadium dioxide at 39.8 °, illustrates to have obtained the vanadium dioxide film of (020) orientation.
The vanadium dioxide film of In and Zn codope prepared by embodiment 2 have done Raman spectrum test, as can be seen from the results, should
Film is in 194,223,264,307,338,387,440,498,617 and 825cm-1Occurs the Raman vibration of vanadium dioxide at position
Dynamic peak, other signal peak-to-average powers illustrate to have obtained vanadium dioxide film from substrate.
The vanadium dioxide film of In and Zn codope prepared by embodiment 2 have done scanning electron microscope test, by result
It is found that the surface of the film contains a large amount of microcosmic particle, the flatness, compactness and homogeneity of sample surfaces are illustrated
It is good.
The infrared transmittivity that the vanadium dioxide film of In and Zn codope prepared by embodiment 2 have done 24 DEG C and 90 DEG C is surveyed
Examination, as can be seen from the results, embodiment 2 make the film of each In and Zn codope to wave number 2000-4000cm-1Infrared light in range
There is stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of In and Zn codope prepared by embodiment 2, which are analyzed in wavelength,2It is thin
The transmitance of film varies with temperature, as can be seen from the results, the phase transition temperature of the film is very low, is 28 DEG C, before phase change after transmitance
Variation has reached 65%；The result shows In and Zn the In and Zn for having effectively entered in vanadium dioxide film, and having obtained to be co-doped with
Miscellaneous vanadium dioxide film has good infrared ray regulating power while reducing phase transition temperature, there is very high reality
Application value.
Embodiment 3
A kind of preparation method of In and the vanadium dioxide film of Zn codope, the described method comprises the following steps:
S1, the indium trichloride for weighing 18mg are mixed with the 30wt% hydrogen peroxide of 3m1, and the left side 80min is stirred by ultrasonic under the conditions of 22 DEG C
It is right；Indium trichloride is dissolved in hydrogenperoxide steam generator at this time, forms transparent clear solution；Sequentially add 20m1 isobutanol, five oxygen of 1g
Change two vanadium to stir evenly, obtains suspension A；In 80 DEG C of heating stirrings, at the same into suspension A be added 3m1 the dense salt of 37wt%
Acid, the H of 100mg zinc oxide and 1.30g2C2O4, it is passed through nitrogen, 12h is stirred to react in the atmosphere of nitrogen, it is saturating to obtain blue-green
Bright sol B；Sealing ageing at room temperature obtains so-gel precursor liquid in 1 day.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min revolves so-gel precursor liquid after drying
It is applied to c-Al2O3Substrate surface, spin coater revolving speed are 4000rpm/min, 100 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 10Pa, annealing temperature are 800 DEG C, annealing time 4h, obtain a kind of In
With the vanadium dioxide film of Zn codope.
The vanadium dioxide film of In and Zn codope prepared by embodiment 3 have done XRD test, as can be seen from the results, the film
Occur the peak of the crystalline orientation of vanadium dioxide at 39.8 °, illustrates to have obtained the vanadium dioxide film of (020) orientation.
The vanadium dioxide film of In and Zn codope prepared by embodiment 3 have done Raman spectrum test, as can be seen from the results, should
Film is in 194,223,264,307,338,387,440,498,617 and 825cm-1Occurs the Raman vibration of vanadium dioxide at position
Dynamic peak, other signal peak-to-average powers illustrate to have obtained vanadium dioxide film from substrate.
The vanadium dioxide film of In and Zn codope prepared by embodiment 3 have done scanning electron microscope test, by result
It is found that the surface of the film contains a large amount of microcosmic particle, the flatness, compactness and homogeneity of sample surfaces are illustrated
It is good.
The infrared transmittivity that the vanadium dioxide film of In and Zn codope prepared by embodiment 3 have done 24 DEG C and 90 DEG C is surveyed
Examination, as can be seen from the results, the film of In and Zn codope prepared by embodiment 3 are to wave number 2000-4000cm-1Infrared light in range
There is stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of In and Zn codope prepared by embodiment 3, which are analyzed in wavelength,2It is thin
The transmitance of film varies with temperature, as can be seen from the results, the phase transition temperature of the film is very low, is 27 DEG C, before phase change after transmitance
Variation has reached 66%；The result shows In and Zn the In and Zn for having effectively entered in vanadium dioxide film, and having obtained to be co-doped with
Miscellaneous vanadium dioxide film has good infrared ray regulating power while reducing phase transition temperature, there is very high reality
Application value.
Embodiment 4
A kind of preparation method of In and the vanadium dioxide film of Zn codope, the described method comprises the following steps:
S1, the indium trichloride for weighing 18mg are mixed with the 30wt% hydrogen peroxide of 3m1, and the left side 80min is stirred by ultrasonic under the conditions of 28 DEG C
It is right；Indium trichloride is dissolved in hydrogenperoxide steam generator at this time, forms transparent clear solution；Sequentially add 35m1 isobutanol, five oxygen of 1g
Change two vanadium to stir evenly, obtains suspension A；In 80 DEG C of heating stirrings, at the same into suspension A be added 3m1 the dense salt of 37wt%
Acid, the H of 100mg zinc oxide and 1.30g2C2O4, it is passed through nitrogen, 12h is stirred to react in the atmosphere of nitrogen, it is saturating to obtain blue-green
Bright sol B；Sealing ageing at room temperature obtains so-gel precursor liquid in 1 day.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min revolves so-gel precursor liquid after drying
It is applied to c-Al2O3Substrate surface, spin coater revolving speed are 4500rpm/min, 100 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 1Pa, annealing temperature be 800 DEG C, annealing time 4h, obtain a kind of In with
The vanadium dioxide film of Zn codope.
The vanadium dioxide film of In and Zn codope prepared by embodiment 4 have done XRD test, as can be seen from the results, the film
Occur the peak of the crystalline orientation of vanadium dioxide at 39.8 °, illustrates to have obtained the vanadium dioxide film of (020) orientation.
The vanadium dioxide film of In and Zn codope prepared by embodiment 4 have done Raman spectrum test, as can be seen from the results, should
Film is in 194,223,264,307,338,387,440,498,617 and 825cm-1Occurs the Raman vibration of vanadium dioxide at position
Dynamic peak, other signal peak-to-average powers illustrate to have obtained vanadium dioxide film from substrate.
The vanadium dioxide film of In and Zn codope prepared by embodiment 4 have done scanning electron microscope test, by result
It is found that the surface of the film contains a large amount of microcosmic particle, the flatness, compactness and homogeneity of sample surfaces are illustrated
It is good.
The infrared transmittivity that the vanadium dioxide film of In and Zn codope prepared by embodiment 4 have done 24 DEG C and 90 DEG C is surveyed
Examination, as can be seen from the results, the film of In and Zn codope prepared by embodiment 4 are to wave number 2000-4000cm-1Infrared light in range
There is stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of In and Zn codope prepared by embodiment 4, which are analyzed in wavelength,2It is thin
The transmitance of film varies with temperature, as can be seen from the results, the phase transition temperature of the film is very low, is 27 DEG C, before phase change after transmitance
Variation has reached 66%；The result shows In and Zn the In and Zn for having effectively entered in vanadium dioxide film, and having obtained to be co-doped with
Miscellaneous vanadium dioxide film has good infrared ray regulating power while reducing phase transition temperature, there is very high reality
Application value.
Comparative example 1
S1, the indium trichloride for weighing 18mg are mixed with the 30wt% hydrogen peroxide of 2.5mL, and 60min is stirred by ultrasonic under the conditions of 22 DEG C
Left and right；Indium trichloride is dissolved in hydrogenperoxide steam generator at this time, forms transparent clear solution；Sequentially add the isobutanol of 50m1,1g
Vanadic anhydride stirs evenly, and obtains suspension A；In 70 DEG C of heating stirrings, while into suspension A, it is added 2.5mL's
The H of 37wt% concentrated hydrochloric acid and 1.30g2C2O4, it is passed through nitrogen, is stirred to react 10h in the atmosphere of nitrogen, it is transparent molten to obtain blue-green
Glue B；Sealing ageing at room temperature obtains so-gel precursor liquid in 1 day.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min revolves so-gel precursor liquid after drying
It is applied to c-Al2O3Substrate surface, spin coater revolving speed are 4000rpm/min, 70 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 10Pa, annealing temperature are 600 DEG C, annealing time 4h, obtain a kind of In and mix
Miscellaneous vanadium dioxide film.
The vanadium dioxide film of In codope prepared by comparative example 1 has done XRD test, which occurs two at 39.8 °
The peak of the crystalline orientation of vanadium oxide illustrates to have obtained the vanadium dioxide film of (020) orientation.
The vanadium dioxide film of In doping prepared by comparative example 1 has done Raman spectrum test, as a result it is found that the film exists
194,223,264,307,338,387,440,498,617 and 825cm-1Occur the Raman vibration peak of vanadium dioxide at position,
Other signal peak-to-average powers illustrate to have obtained vanadium dioxide film from substrate.
The vanadium dioxide film of In codope prepared by comparative example 1 has done 24 DEG C and 90 DEG C of infrared transmittivity test, knot
Fruit finds In with the film of Zn codope to wave number 2000-4000cm-1Infrared light in range has stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of In and Zn codope prepared by comparative example 1, which are analyzed in wavelength,2It is thin
The transmitance of film varies with temperature, as a result, it has been found that the phase transition temperature of film is 45 DEG C, the variation of rear transmitance reaches before phase change
50%。
Comparative example 2
S1, the 30wt% hydrogen peroxide for weighing 2.5mL, and 60min or so is stirred by ultrasonic under the conditions of 22 DEG C；Indium trichloride is molten at this time
Solution forms transparent clear solution in hydrogenperoxide steam generator；The isobutanol of 50m1 is sequentially added, 1g vanadic anhydride stirs evenly,
Obtain suspension A；In 70 DEG C of heating stirrings, while into suspension A, the 37wt% concentrated hydrochloric acid of 2.5mL, 100mg zinc oxide is added
With the H of 1.30g2C2O4, it is passed through nitrogen, is stirred to react 10h in the atmosphere of nitrogen, obtains blue-green vitreosol B；In room temperature
Lower sealing is aged 1 day and obtains so-gel precursor liquid.
S2, ethyl alcohol, acetone is successively used to be cleaned by ultrasonic c-Al2O3Substrate 20min revolves so-gel precursor liquid after drying
It is applied to c-Al2O3Substrate surface, spin coater revolving speed are 4000rpm/min, 70 DEG C of drying.
S3, it repeats step S2 totally 5 times, obtains pre-deposition precursor thin-film；Pre-deposition precursor thin-film is placed in vacuum tube
Made annealing treatment in formula furnace: vacuum atmosphere 10Pa, annealing temperature be 600 DEG C, annealing time 4h, obtain a kind of In with
The vanadium dioxide film of Zn codope.
The vanadium dioxide film of Zn doping prepared by comparative example 2 has done XRD test, which dioxy occurs at 39.8 °
The peak for changing the crystalline orientation of vanadium illustrates to have obtained the vanadium dioxide film of (020) orientation.
The vanadium dioxide film of Zn doping prepared by comparative example 2 has done Raman spectrum test, knot it is found that the film 194,
223,264,307,338,387,440,498,617 and 825cm-1Occur the Raman vibration peak of vanadium dioxide at position, it is other
Signal peak-to-average power from substrate, illustrate to have obtained vanadium dioxide film.
The vanadium dioxide film of Zn doping prepared by comparative example 2 has done 24 DEG C and 90 DEG C of infrared transmittivity test, as a result
It was found that the film of In and Zn codope is to wave number 2000-4000cm-1Infrared light in range has stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of Zn doping prepared by comparative example 2, which is analyzed in wavelength,2Film it is saturating
The rate of mistake varies with temperature, as a result, it has been found that the phase transition temperature of film is 46 DEG C, the variation of rear transmitance has reached 48% before phase change.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the vanadium dioxide film of In and Zn codope, which comprises the steps of:
S1: indium trichloride ultrasonic dissolution is formed to the solution of clear in hydrogenperoxide steam generator, and by acquired solution and five oxygen
Change two vanadium dispersing and dissolvings in isobutanol, finally obtains suspension A；Heating stirring at a certain temperature, while into suspension A
Hydrochloric acid, zinc oxide and oxalic acid is added, is passed through nitrogen, is stirred to react 10h or more in the atmosphere of nitrogen, obtains sol B；Through room temperature
Sealing ageing 1 day or more, obtain sol-gel precursor liquid；
S2: sol-gel precursor liquid is spun on the dry substrate surface of cleaning, drying removes extra iso-butanol solvent；
S3: it repeats step S2 more than five times, obtains pre-deposition precursor thin-film；Then it by vacuum annealing process, obtains described
The vanadium dioxide film of In and Zn codope.
2. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: institute
Stating substrate is Al2O3。
3. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: institute
The ultrasonic dissolution stated operates at room temperature, reacts 60min or more.
4. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: molten
The concentration range of vanadium is 0 .6-0.8mol/L in glue B.
5. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: institute
The concentration for stating vanadium in sol B is 0.8mo1/L.
6. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: institute
The spin coating range of speeds 4000-5000rpm stated, 90 DEG C -100 DEG C of drying temperature.
7. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: institute
The vacuum annealing process stated are as follows: vacuum degree 1-10Pa, annealing temperature are 600 DEG C -700 DEG C, and annealing time is >=7h.
8. the preparation method of the vanadium dioxide film of a kind of In as claimed in claim 7 and Zn codope, it is characterised in that: institute
The vacuum annealing process stated are as follows: vacuum degree 6Pa, annealing temperature are 650 DEG C, annealing time 10h.
9. the preparation method of the vanadium dioxide film of a kind of In as described in claim 1 and Zn codope, it is characterised in that: logical
The rate for entering nitrogen is 10mL/min.
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| CN112919820A (en) * | 2021-01-21 | 2021-06-08 | 大连工业大学 | Zn-doped VO2Powder and method for preparing composite film by using same |
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| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN106517325A (en) * | 2016-11-15 | 2017-03-22 | 北京理工大学 | W-and-Eu-codoped vanadium dioxide film and preparation method thereof |
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| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN106517325A (en) * | 2016-11-15 | 2017-03-22 | 北京理工大学 | W-and-Eu-codoped vanadium dioxide film and preparation method thereof |
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| CN112919820A (en) * | 2021-01-21 | 2021-06-08 | 大连工业大学 | Zn-doped VO2Powder and method for preparing composite film by using same |
| CN112919820B (en) * | 2021-01-21 | 2022-05-27 | 大连工业大学 | Zn-doped VO2Powder and method for preparing composite film by using same |
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