CN106517325A - W-and-Eu-codoped vanadium dioxide film and preparation method thereof - Google Patents
W-and-Eu-codoped vanadium dioxide film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a W-and-Eu-codoped vanadium dioxide film and a preparation method thereof, belonging to the field of functional materials. The atom percentage of the vanadium dioxide film satisfies the equation that (W+Eu)/(W+Eu+V) <= 5 at. %. The preparation method comprises the following steps: dissolving tungstic acid and europia in hydrogen peroxide to form a clear and transparent solution, and dispersing and dissolving the obtained solution and vanadium pentoxide in isobutanol so as to obtain a suspension A; adding concentrated hydrochloric acid and oxalic acid into the suspension A, carrying out heating and stirring so as to obtain sol B and ageing the sol B so as to obtain a sol-gel precursor solution; coating the surface of a clean substrate with the sol-gel precursor solution through rotation, then carrying out drying and repeating rotary coating so as to obtain a pre-deposited precursor film; and carrying out vacuum annealing treatment so as to obtain the W-and-Eu-codoped vanadium dioxide film. The film can maintain high-efficiency capability in adjusting of infrared transmission while greatly reducing phase-change temperature.
Description
Technical field：
The inventive method is related to vanadium dioxide film of a kind of W and Eu codopes and preparation method thereof.Belong to functional material
Field.
Technical background：
Vanadium dioxide is (VO2) a kind of intelligent thermochromic material.When near 68 DEG C, vanadium dioxide has reversible gold
Category-insulator transition (MIT), it is this transformation be a primary structure phase in version process, monocline M phase of its crystal structure from low temperature
High temperature four directions rutile R phases are converted to, electrical conductivity, region of ultra-red transmitance and reflectance are undergone mutation in transition process.
Quasiconductor phase, phonon energy are less than band gap, VO2Show high infrared light transmittance；Conversely, metal phase then show it is low red
Outer light transmission rate.Its phase transformation response speed is exceedingly fast, and can realize to MIT up to tens fs magnitudes, and extra electric field and stress field
The regulation and control of phase transformation, these excellent performances make VO2Lasing safety, smart window, heat/photoswitch, many regulation and control electronic device,
The fields such as light storage device are with a wide range of applications.
Vanadium dioxide block after multiple phase transformation, as the stress produced in phase transition process can cause the crystal of material
There is rupture or become fragment in size.And monocrystalline vanadium dioxide film after multiple phase transformation still can stable existence, thus
The vanadium dioxide film of monocrystalline mostly is in actual applications.
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
Indoor temperature, thus how to VO2Phase transition temperature and its infrared optics characteristic carry out regulation and control 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
20-26K is reduced by 1% phase transition temperature of often adulterating, was once becoming study hotspot, can be controlled by changing the doping content of tungsten
Phase transition temperature is in room temperature between 68 DEG C.But while being entrained in change phase transition temperature of the transition metal such as W, generally can
Cause the VO that adulterates2Phase-change characteristic of the thin film before and after phase transformation is obviously reduced, and such as nearby sudden change of resistivity amount reduces and infrared transformation temperature
Light ability of regulation and control is weakened.Although research report shows the VO of one-dimensional nano structure2Such as nano belt, nano wire, to a certain degree
On can overcome disadvantage mentioned above, but the current stage yet suffers from preparation technology and requires that complicated, high cost problem and phase transformation are special
Property have uncertainty.
Therefore new design of material and preparation process condition are explored, realizes reducing VO2The regulation and control of phase transition temperature are not dropped simultaneously
Before and after low phase change, vanadium dioxide optimizes optical tune ability and resistance transition ability for practical application to infrared light regulating power
For seem most important.
The content of the invention
In view of this, an object of the present invention is the vanadium dioxide film for providing a kind of W and Eu codopes, the thin film
Reducing VO2Vanadium dioxide film is not reduced while phase transition temperature before and after phase transformation to infrared light regulating power.The present invention's
The two of purpose are the preparation method for providing a kind of W and the vanadium dioxide film of Eu codopes.
To realize the purpose of the present invention, there is provided technical scheme below：
The vanadium dioxide film of a kind of W and Eu codopes, the vanadium dioxide film atomic percent is：(W+Eu)/(W+
Eu+V)≤5at.%, preferred W/ (W+Eu+V)=1at.%, Eu/ (W+Eu+V)=4at.%.
A kind of preparation method of the vanadium dioxide film of W of the present invention and Eu codopes, methods described include following step
Suddenly：
(1) by wolframic acid (H2WO4) ultrasonic dissolution is in hydrogen peroxide (H2O2) solution forms the solution of clear, and by institute
Obtain solution and vanadic anhydride (V2O5) dispersing and dissolving, in isobutanol, finally gives suspension A；In 60～80 DEG C of heated and stirred, together
When hydrochloric acid (HCl), europium oxide and oxalic acid (H are added in suspension A2C2O4·2H2O), nitrogen is passed through, in the atmosphere of nitrogen
More than stirring reaction 8h, obtain sol B；Jing Room-temperature seals are aged more than 2 days, obtain sol-gel precursor liquid.
(2) sol-gel precursor liquid is spun on into the dry substrate surface of cleaning, it is molten that drying removes unnecessary isobutanol
Agent.
(3) and repeat step more than (2) five times, obtain pre-deposition precursor thin-film；Then processed by vacuum annealing, obtained
To a kind of W and the vanadium dioxide film of Eu codopes.
Described ultrasonic dissolution is operated at room temperature, reacts more than 40min.
Described, in sol B, the concentration range of vanadium is 0.2～0.5mol/L.
Described, wolframic acid is 1 with the mol ratio of hydrogen peroxide:300.
Described, the oxalic acid of addition is 2 with the mol ratio of vanadic anhydride:1.
Described, the hydrochloric acid of addition is equal with hydrogen peroxide mole.
Described, spin coating 2500～3500rpm of the range of speeds, 70～80 DEG C of drying temperature.
Described, vacuum annealing is processed as：Vacuum≤10-3Pa, annealing temperature are 450～550 DEG C, are in order that five oxygen
It is vanadium dioxide to change two vanadium decomposition and inversion, and annealing time is >=4h.
Preferably, the substrate is c-Al2O3。
Preferably, in the sol B, the concentration of vanadium is 0.2mol/L.
Preferably, the vacuum annealing temperature is 470 DEG C.
A kind of preparation method of the vanadium dioxide film of W doping, by above-mentioned W and the system of the vanadium dioxide film of Eu codopes
Europium oxide in Preparation Method in step (1) removes, and other steps are identical, that is, obtain a kind of vanadium dioxide film of W doping.
Beneficial effect
There is the preferential crystallization of height according to the vanadium dioxide film of W and Eu codopes obtained in preparation method of the invention
Orientation, can keep the efficient regulating power to infrared transmission while phase transition temperature is greatly lowered.In above-mentioned condition
Under, the vanadium dioxide film transition temperature of the W and Eu codope of preparation drops to less than 45 DEG C, infrared regulation efficiency (2500nm)
Reach more than 43%；It is 29.2% that the vanadium dioxide film correspondence of single W doping prepared by same procedure adjusts efficiency.
Design of material method and preparation technology that the present invention is provided, it is possible to achieve the phase-change characteristic of material is carried out accurately
Control, with good repeatability and production meaning.The method also has process is simple, and raw material is easy to get low with energy consumption excellent
Point.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the vanadium dioxide film of W and Eu codopes prepared by the embodiment of the present invention 1；
Fig. 2 is Raman spectrum (Raman) figure of the vanadium dioxide film of W and Eu codopes prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope of the vanadium dioxide film of W and Eu codopes prepared by the embodiment of the present invention 1
(SEM) figure；
Fig. 4 be the embodiment of the present invention 1 prepare W and Eu codopes vanadium dioxide film wave number be 400～
4000cm-1In the range of, the infrared transmittivity test chart in 24 DEG C and 90 DEG C；
The vanadium dioxide film of W and Eu codopes prepared by Fig. 5 embodiment of the present invention 1 is in the transmission that wavelength is at 2500nm
The hysteresis curve that rate is varied with temperature；
Fig. 6 is X-ray diffraction (XRD) figure of the vanadium dioxide film of W doping prepared by the embodiment of the present invention 4；
Fig. 7 is Raman spectrum (Raman) figure of the vanadium dioxide film of W doping prepared by the embodiment of the present invention 4；
Fig. 8 is scanning electron microscope (SEM) figure of the vanadium dioxide film of W doping prepared by the embodiment of the present invention 4；
The vanadium dioxide film of the W doping that Fig. 9 is prepared for the embodiment of the present invention 4 is 400～4000cm in wave number-1Scope
Interior, in 24 DEG C and 90 DEG C infrared transmittivity test chart；
Figure 10 embodiment of the present invention 4 prepare W doping vanadium dioxide film wavelength be 2500nm at transmitance with
The hysteresis curve of temperature change
Specific embodiment
It is understandable to enable the above objects, features and advantages of the present invention to become apparent from, it is below in conjunction with the accompanying drawings and concrete real
The present invention is further detailed explanation to apply mode.
Following various characterization technique tests are carried out to vanadium dioxide film prepared by following examples：
(1) X-ray diffraction analysis：
Using XPERT-PRO types XRD (X-ray diffraction) the x ray diffraction analysis x instrument of Dutch PANalytical company,
Copper target Cu-K α is used as radiation sourcePipe presses 40kV, pipe flow 40mA, sweep limitss 15-50 °, and step-length is
0.02 °, the time of staying is 3s；Vanadium dioxide film prepared by embodiment is placed in into the middle of microscope slide, microscope slide is put into
The experimental tank center of instrument, is tested；The identification of thing phase and crystal structure information are by JADE6.0 software analysis.
(2) Raman spectrum analyses：
The LabRAM HR800 microscopic confocal Raman spectrometers produced using French HORIBAJOBIN YVON S.A.S.,
Spectrum repeatability, using 532nm (50mW) laser instrument, the signal to noise ratio at the three rank peaks of 532nm is better than 10%, and it is observed that quadravalence
Peak.Spatial resolution is laterally better than 1 micron, is longitudinally better than 2 microns.Peak position is corrected with standard silicon chip, room temperature embodiment system
Standby vanadium dioxide film is placed on direct measurement on piezoid.
(3) scanning electron microscope analysis
The titanium dioxide for using FDAC Hitachi company S4800 type field emission scanning electron microscopes (SEM) being prepared by embodiment
Vanadium thin film carries out microstructure test, needs the vanadium dioxide film prepared to embodiment to carry out metal spraying process, increase before test
The electric conductivity of vanadium dioxide film prepared by embodiment.
(4) Temperature-dependent IR transmission measurement
Using Perkin-Elmer companies 983 type infrared spectrometers test various temperature IR, 24～90 DEG C of test temperature,
Every a transmitance spectral line is tested twice, one circulation of test is warming up to from 24 DEG C and be cooled to after 90 DEG C again 24 DEG C, measures
Wave-number range is 400～4000cm-1。
(5) vanadium dioxide film of embodiment preparation is extracted in 4000cm-1At wave number, the transmitance of each temperature spot, obtains
The hysteresis curve that the transmitance of vanadium dioxide film prepared by embodiment is varied with temperature.
Embodiment 1
The vanadium dioxide film of a kind of W and Eu codopes, the vanadium dioxide film atomic percent is：W/(W+Eu+V)
=1at.%, Eu/ (W+Eu+V)=4at.%.
A kind of above-mentioned W and the preparation method of the vanadium dioxide film of Eu codopes, the method comprising the steps of：
(1) weigh the wolframic acid of 14mg to mix with the 30wt% hydrogen peroxide of 3ml, and ultrasonic agitation 40min under the conditions of 25 DEG C
Left and right.Now wolframic acid is dissolved in hydrogenperoxide steam generator, forms transparent settled solution.Sequentially add the isobutanol of 40ml, five oxygen of 1g
Change two vanadium to stir, system forms yellow suspension A after being changed into peony.In 70 DEG C of heated and stirred, while in suspension A
Add the H of the 37wt% concentrated hydrochloric acid of 3ml, 81.3mg europium oxides and 1.26g2C2O4·2H2O, is passed through nitrogen, in the atmosphere of nitrogen
Middle stirring reaction 8h, obtains aeruginouss vitreosol B.Sealing ageing at room temperature obtains sol-gel precursor liquid in 2 days.
(2) it is cleaned by ultrasonic c-Al with ethanol, acetone successively2O3Substrate 20min, by sol-gel precursor liquid spin coating after drying
In c-Al2O3Substrate surface, spin coater rotating speed are 3000rpm/min, and 70 DEG C dry.
(3) repeat step (2) 5 times, obtain pre-deposition precursor thin-film.Pre-deposition precursor thin-film is placed in into electron tubes type
Made annealing treatment in stove：Vacuum atmosphere is 10-3Pa, annealing temperature are 470 DEG C, and annealing time 4h obtains a kind of W and Eu
The vanadium dioxide film of codope.
W prepared by embodiment 1 has done XRD tests with the vanadium dioxide film of Eu codopes, as a result as shown in Figure 1.By scheming
Understand, the thin film occurs in that the peak of the crystalline orientation of vanadium dioxide at 39.8 °, illustrates to have obtained the vanadium dioxide that (020) is orientated
Thin film.
W prepared by embodiment 1 has done Raman spectrum test with the vanadium dioxide film of Eu codopes, as a result as shown in Figure 2.
As seen from the figure, the thin film is 194, and 223,264,307,338,387,440,498,617 and 825cm-1Dioxy is occurred in that at position
Change the Raman vibration peak of vanadium, other signal peak-to-average powers come from substrate, illustrate to have obtained vanadium dioxide film.
W prepared by embodiment 1 has done scanning electron microscope test with the vanadium dioxide film of Eu codopes, as a result as schemed
Shown in 3.As seen from the figure, the surface of the film sample contains substantial amounts of microcosmic particle, illustrates the flatness of sample surfaces, causes
Close property and homogeneity are good.
W and the vanadium dioxide film of Eu codopes prepared by embodiment 1 has done 24 DEG C and 90 DEG C of infrared transmittivity test,
As shown in figure 4, wherein (a1)、(a2) it is the vanadium dioxide film of W and Eu codopes prepared by embodiment 1 respectively at 24 DEG C, 90 DEG C
The infrared transmittivity curve for measuring.As seen from the figure, the thin film is in wave number 2000-4000cm-1In the range of, the table in 24 DEG C and 90 DEG C
Very big infrared transmittivity change is revealed, and in this wave-number range, when 24 DEG C and 90 DEG C respective transmitance is almost
It is straight, illustrate W with the thin film of Eu codopes to wave number 2000-4000cm-1In the range of infrared light have stable transmitance.
It is the VO at 2500nm that W prepared by embodiment 1 is analyzed in wavelength with the vanadium dioxide film of Eu codopes2Thin film
Transmitance vary with temperature, as a result as shown in figure 5, as seen from the figure, the phase transition temperature of the thin film is very low, is 43.5 DEG C, phase transformation
The change of transmitance in front and back has reached 47%.The result shows that W and Eu has effectively entered VO2In thin film, and the W for obtaining with
The vanadium dioxide film of Eu codopes has good infrared ray regulating power while phase transition temperature is reduced, and has very high
Actual application value.
Embodiment 2 (0.4mol/L)
The vanadium dioxide film of a kind of W and Eu codopes, the vanadium dioxide film atomic percent is：W/(W+Eu+V)
=1at.%, Eu/ (W+Eu+V)=4at.%.
A kind of above-mentioned W and the preparation method of the vanadium dioxide film of Eu codopes, the method comprising the steps of：
(1) weigh the wolframic acid of 14mg to mix with the 30wt% hydrogen peroxide of 3ml, and ultrasonic agitation 40min under the conditions of 25 DEG C
Left and right.Now wolframic acid is dissolved in hydrogenperoxide steam generator, forms transparent settled solution.20ml isobutanol is sequentially added, 1g five is aoxidized
Two vanadium stir, and system forms yellow suspension A after being changed into peony.In 60 DEG C of heated and stirred, while adding in suspension A
Enter the H of the 37wt% concentrated hydrochloric acid of 3ml, 81.3mg europium oxides and 1.26g2C2O4·2H2O, is passed through nitrogen, in the atmosphere of nitrogen
Stirring reaction 10h, obtains aeruginouss vitreosol B.Sealing ageing at room temperature obtains sol-gel precursor liquid in 2 days.
(2) it is cleaned by ultrasonic c-Al with ethanol, acetone successively2O3Substrate 20min, by sol-gel precursor liquid spin coating after drying
In c-Al2O3Substrate surface, spin coater rotating speed are 3000rpm/min, and 75 DEG C dry.
(3) repeat step (2) 5 times, obtain pre-deposition precursor thin-film.Pre-deposition precursor thin-film is placed in into electron tubes type
Made annealing treatment in stove：Vacuum atmosphere is 10-3Pa, annealing temperature are 450 DEG C, and annealing time 6h obtains a kind of W and Eu
The vanadium dioxide film of codope.
W prepared by embodiment 2 has done XRD tests with the vanadium dioxide film of Eu codopes, and from result, the thin film exists
The peak of 39.8 ° of crystalline orientations for occurring in that vanadium dioxide, illustrates to have obtained the vanadium dioxide film that (020) is orientated.
W prepared by embodiment 2 has done Raman spectrum test with the vanadium dioxide film of Eu codopes, from result, should
Thin film is 194,223,264,307,338,387,440,498,617 and 825cm-1Occur in that at position that the Raman of vanadium dioxide shakes
Dynamic peak, other signal peak-to-average powers come from substrate, illustrate to have obtained vanadium dioxide film.
W prepared by embodiment 2 has done scanning electron microscope test with the vanadium dioxide film of Eu codopes, can by result
Know, the surface of the thin film contains substantial amounts of microcosmic particle, illustrate that flatness, compactness and the homogeneity of sample surfaces is good.
W and the vanadium dioxide film of Eu codopes prepared by embodiment 2 has done 24 DEG C and 90 DEG C of infrared transmittivity test,
From result, the thin film is in wave number 2000-4000cm-1In the range of, show in 24 DEG C and 90 DEG C very big infrared
Transmitance changes, and in this wave-number range, when 24 DEG C and 90 DEG C, respective transmitance is almost straight, illustrates that embodiment 2 is made
The thin film of standby W and Eu codopes is to wave number 2000-4000cm-1In the range of infrared light have stable transmitance.
It is the VO at 2500nm that W prepared by embodiment 2 is analyzed in wavelength with the vanadium dioxide film of Eu codopes2Thin film
Transmitance vary with temperature, from result, the phase transition temperature of the thin film is very low, is 45 DEG C, the change of transmitance before and after phase transformation
Change has reached 45%.The result shows that W and Eu has been effectively entered in vanadium dioxide film, and the W for obtaining and Eu codopes
Vanadium dioxide film reduce phase transition temperature while there is good infrared ray regulating power, have very high reality should
With value.
Embodiment 3 (0.5mol/L)
The vanadium dioxide film of a kind of W and Eu codopes, the vanadium dioxide film atomic percent is：W/(W+Eu+V)
=1at.%, Eu/ (W+Eu+V)=4at.%.
A kind of above-mentioned W and the preparation method of the vanadium dioxide film of Eu codopes, the method comprising the steps of：
(1) weigh the wolframic acid of 14mg to mix with the 30wt% hydrogen peroxide of 3ml, and ultrasonic agitation 40min under the conditions of 25 DEG C
Left and right.Now wolframic acid is dissolved in hydrogenperoxide steam generator, forms transparent settled solution.16ml isobutanol is sequentially added, 1g five is aoxidized
Two vanadium stir, and system forms yellow suspension A after being changed into peony.In 80 DEG C of heated and stirred, while adding in suspension A
Enter the H of the 37wt% concentrated hydrochloric acid of 3ml, 81.3mg europium oxides and 1.26g2C2O4·2H2O, is passed through nitrogen, in the atmosphere of nitrogen
Stirring reaction 12h, obtains aeruginouss vitreosol B.Sealing ageing at room temperature obtains sol-gel precursor liquid in 2 days.
(2) it is cleaned by ultrasonic c-Al with ethanol, acetone successively2O3Substrate 20min, by sol-gel precursor liquid spin coating after drying
In c-Al2O3Substrate surface, spin coater rotating speed are 3000rpm/min, and 80 DEG C dry.
(3) repeat step (2) 5 times, obtain pre-deposition precursor thin-film.Pre-deposition precursor thin-film is placed in into electron tubes type
Made annealing treatment in stove：Vacuum atmosphere is 10-3Pa, annealing temperature are 550 DEG C, and annealing time 4h obtains a kind of W and Eu
The vanadium dioxide film of codope.
W prepared by embodiment 3 has done XRD tests with the vanadium dioxide film of Eu codopes, and from result, the thin film exists
The peak of 39.8 ° of crystalline orientations for occurring in that vanadium dioxide, illustrates to have obtained the vanadium dioxide film that (020) is orientated.
W prepared by embodiment 3 has done Raman spectrum test with the vanadium dioxide film of Eu codopes, from result, should
Thin film is 194,223,264,307,338,387,440,498,617 and 825cm-1Occur in that at position that the Raman of vanadium dioxide shakes
Dynamic peak, other signal peak-to-average powers come from substrate, illustrate to have obtained vanadium dioxide film.
W prepared by embodiment 3 has done scanning electron microscope test with the vanadium dioxide film of Eu codopes, can by result
Know, the surface of the thin film contains substantial amounts of microcosmic particle, illustrate that flatness, compactness and the homogeneity of sample surfaces is good.
W and the vanadium dioxide film of Eu codopes prepared by embodiment 3 has done 24 DEG C and 90 DEG C of infrared transmittivity test,
From result, the thin film is in wave number 2000-4000cm-1In the range of, show in 24 DEG C and 90 DEG C very big infrared
Transmitance changes, and in this wave-number range, when 24 DEG C and 90 DEG C, respective transmitance is almost straight, illustrates that embodiment 3 is made
The thin film of standby W and Eu codopes is to wave number 2000-4000cm-1In the range of infrared light have stable transmitance.
It is the VO at 2500nm that W prepared by embodiment 3 is analyzed in wavelength with the vanadium dioxide film of Eu codopes2Thin film
Transmitance vary with temperature, from result, the phase transition temperature of the thin film is very low, is 44 DEG C, the change of transmitance before and after phase transformation
Change has reached 43%.The result shows that W and Eu has been effectively entered in vanadium dioxide film, and the W for obtaining and Eu codopes
Vanadium dioxide film reduce phase transition temperature while there is good infrared ray regulating power, have very high reality should
With value.
Embodiment 4
(1) preparation of precursor sol liquid：Weigh the wolframic acid of 14mg to mix with the 30wt% hydrogen peroxide of 3ml, and in 25 DEG C of bars
Ultrasonic agitation 40min or so under part.Now wolframic acid is dissolved in hydrogenperoxide steam generator, forms transparent settled solution.Sequentially add
40ml isobutanol, 1g vanadic anhydrides stir, and system forms yellow suspension A after being changed into peony.Stir in 70 DEG C of heating
Mix, while the 37wt% concentrated hydrochloric acid and 1.26gH of 3ml is added in suspension A2C2O4·2H2O, is passed through nitrogen, in the atmosphere of nitrogen
Middle stirring reaction 8h is enclosed, aeruginouss vitreosol B is obtained.2 days sol-gel precursor liquids derived above are aged at room temperature.
(2) using spin-coating method film forming：Precursor sol liquid B is spun on into c-Al2O3Substrate surface, rotating speed 3000rpm/min,
Drying.
(3) repeat step (2) 5 times, obtain pre-deposition precursor thin-film.Pre-deposition thin film is placed in vacuum tube furnace
Row annealing：Vacuum atmosphere is 10-3Pa, annealing temperature are 470 DEG C, annealing time 4h, obtain a kind of vanadium dioxide of W doping
Thin film.
The vanadium dioxide film of W doping prepared by embodiment 4 has done XRD tests, as a result as shown in Figure 6.As seen from the figure, should
Thin film occurs in that the peak of the crystalline orientation of vanadium dioxide at 27.8 ° and 39.8 °, illustrates to have obtained two that (011) and (020) is orientated
Vanadium oxide film.
The vanadium dioxide film of W doping prepared by embodiment 4 has done Raman spectrum test, as a result as shown in Figure 7.Can by figure
Know, the thin film 194,223,264,307,338,387,440,498,617 and 825cm-1Vanadium dioxide is occurred in that at position
Raman peaks, illustrate to have obtained vanadium dioxide.
The vanadium dioxide film of W doping prepared by embodiment 4 has done scanning electron microscope test, as a result as shown in Figure 8.
As seen from the figure, the surface of the film sample contains substantial amounts of microcosmic particle, illustrate the flatness of sample surfaces, compactness and
Homogeneity is good.
The vanadium dioxide film of W doping prepared by embodiment 4 has been 24 DEG C and 90 DEG C of infrared transmittivity test, such as Fig. 9
It is shown, wherein (a1)、(a2) for embodiment 4 prepare W doping vanadium dioxide film respectively 24 DEG C, 90 DEG C measure it is infrared
Transmittance curve.As seen from the figure, the thin film is in wave number 2000-4000cm-1In the range of, show very in 24 DEG C and 90 DEG C
Big infrared transmittivity change, and in this wave-number range, when 24 DEG C and 90 DEG C, respective transmitance is almost straight, illustrates real
The vanadium dioxide film of W doping of the preparation of example 4 is applied to wave number 2000-4000cm-1In the range of infrared light have stable transmitance.
It is the VO at 2500nm that the vanadium dioxide film of W doping prepared by embodiment 4 is analyzed in wavelength2The transmission of thin film
Rate is varied with temperature, and as a result as shown in Figure 10, as seen from the figure, the thin film is being greatly lowered the feelings of phase transition temperature (44.2 DEG C)
Under condition, the change of transmitance turns to 29.2%.The result shows that effectively doping is entered in vanadium dioxide film W, and with this
Invention methods described prepare W doping vanadium dioxide film reduce phase transition temperature while, with certain infrared ray
Regulating power, has certain researching value.
The present invention includes but is not limited to above example, every any equivalent carried out under the principle of spirit of the present invention
Replace or local improvement, all will be regarded as within protection scope of the present invention.
Claims (10)
1. the vanadium dioxide film of a kind of W and Eu codopes, it is characterised in that：The vanadium dioxide film atomic percent is：
(W+Eu)/(W+Eu+V)≤5at.%.
2. the vanadium dioxide film of a kind of W as claimed in claim 1 and Eu codopes, it is characterised in that：The vanadium dioxide
Thin film atomic percent is：W/ (W+Eu+V)=1at.%, Eu/ (W+Eu+V)=4at.%.
3. the preparation method of a kind of a kind of W as claimed in claim 1 and the vanadium dioxide film of Eu codopes, its feature exist
In：Methods described is comprised the following steps that：
(1) wolframic acid ultrasonic dissolution is formed in hydrogenperoxide steam generator the solution of clear, and resulting solution is aoxidized into two with five
Vanadium dispersing and dissolving finally gives suspension A in isobutanol；In 60～80 DEG C of heated and stirred, while adding salt in suspension A
Acid, europium oxide and oxalic acid, are passed through nitrogen, more than stirring reaction 8h in the atmosphere of nitrogen, obtain sol B；Jing Room-temperature seals are old
Change more than 2 days, obtain sol-gel precursor liquid；
(2) sol-gel precursor liquid is spun on into the dry substrate surface of cleaning, drying removes unnecessary iso-butanol solvent；
(3) and repeat step more than (2) five times, obtain pre-deposition precursor thin-film；Then processed by vacuum annealing, obtain institute
State the vanadium dioxide film of a kind of W and Eu codopes；
Described ultrasonic dissolution is operated at room temperature, reacts more than 40min；
Described, in sol B, the concentration range of vanadium is 0.2～0.5mol/L；
Described, wolframic acid is 1 with the mol ratio of hydrogen peroxide：300；
Described, the oxalic acid of addition is 2 with the mol ratio of vanadic anhydride:1；
Described, the hydrochloric acid of addition is equal with hydrogen peroxide mole；
Described, spin coating 2500～3500rpm of the range of speeds, 70～80 DEG C of drying temperature；
Described, vacuum annealing is processed as：Vacuum≤10-3Pa, annealing temperature are 450～550 DEG C, and annealing time is >=4h.
4. the preparation method of a kind of W as claimed in claim 3 and the vanadium dioxide film of Eu codopes, it is characterised in that：Institute
Substrate is stated for c-Al2O3。
5. the preparation method of a kind of W as claimed in claim 3 and the vanadium dioxide film of Eu codopes, it is characterised in that：Institute
The concentration for stating vanadium in sol B is 0.2mol/L.
6. the preparation method of the vanadium dioxide film of a kind of W as described in any one of claim 3～5 and Eu codopes, which is special
Levy and be：The vacuum annealing temperature is 470 DEG C.
7. the preparation method of the vanadium dioxide film of a kind of W doping, it is characterised in that：The method comprising the steps of：
(1) wolframic acid ultrasonic dissolution is formed in hydrogenperoxide steam generator the solution of clear, and resulting solution is aoxidized into two with five
Vanadium dispersing and dissolving finally gives suspension A in isobutanol；In 60～80 DEG C of heated and stirred, while adding hydrochloric acid in suspension A
And oxalic acid, nitrogen is passed through, more than stirring reaction 8h in the atmosphere of nitrogen, sol B is obtained；Jing Room-temperature seals are aged more than 2 days,
Obtain sol-gel precursor liquid；
(2) sol-gel precursor liquid is spun on into the dry substrate surface of cleaning, drying removes unnecessary iso-butanol solvent；
(3) and repeat step more than (2) five times, obtain pre-deposition precursor thin-film；Then processed by vacuum annealing, obtain institute
State a kind of vanadium dioxide film of W doping；
Described ultrasonic dissolution is operated at room temperature, reacts more than 40min；
Described, in sol B, the concentration range of vanadium is 0.2～0.5mol/L；
Described, wolframic acid is 1 with the mol ratio of hydrogen peroxide：300；
Described, the oxalic acid of addition is 2 with the mol ratio of vanadic anhydride:1；
Described, the hydrochloric acid of addition is equal with hydrogen peroxide mole；
Described, spin coating 2500～3500rpm of the range of speeds, 70～80 DEG C of drying temperature；
Described, vacuum annealing is processed as：Vacuum≤10-3Pa, annealing temperature are 450～550 DEG C, and annealing time is >=4h.
8. the preparation method of the vanadium dioxide film of a kind of W doping as claimed in claim 7, it is characterised in that：The substrate
For c-Al2O3。
9. the preparation method of the vanadium dioxide film of a kind of W doping as claimed in claim 8, it is characterised in that：The sol B
The concentration of middle vanadium is 0.2mol/L.
10. the preparation method of the vanadium dioxide film of a kind of W doping as described in any one of claim 7～9, its feature exist
In：The vacuum annealing temperature is 470 DEG C.
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| CN109594065A (en) * | 2018-11-28 | 2019-04-09 | 东莞理工学院 | A kind of preparation method of In and the vanadium dioxide film of Zn codope |
| CN113149074A (en) * | 2020-01-07 | 2021-07-23 | 北京理工大学 | Intelligent window material and preparation method thereof |
| CN113149074B (en) * | 2020-01-07 | 2022-11-15 | 北京理工大学 | Intelligent window material and preparation method thereof |
| WO2024040429A1 (en) * | 2022-08-23 | 2024-02-29 | 中国科学院深圳先进技术研究院 | Electromagnetic shielding composite material with temperature response characteristic, and preparation method therefor and application thereof |
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