CN105937019A - VO2 thin film doped with metallic element Mg and preparation method thereof - Google Patents
VO2 thin film doped with metallic element Mg and preparation method thereof Download PDFInfo
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- CN105937019A CN105937019A CN201610417173.2A CN201610417173A CN105937019A CN 105937019 A CN105937019 A CN 105937019A CN 201610417173 A CN201610417173 A CN 201610417173A CN 105937019 A CN105937019 A CN 105937019A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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Abstract
The invention relates to a VO2 thin film doped with the metallic element Mg and a preparation method thereof. The VO2 thin film doped with the metallic element Mg is provided with nano air holes distributed irregularly and the main phase is a monoclinic phase; the crystal orientation (011) is a crystal face; and the crystalline grain size is 90-165 nm. The VO2 thin film doped with the metallic element Mg and the preparation method thereof have the beneficial effects that the metallic element Mg is evenly doped into the VO2 thin film, the air holes are formed in the surface of the obtained doped VO2 thin film, the density is reduced, and the hole diameter is reduced along with the increasing of the Mg doping concentration; since the air holes are formed in the surface of the thin film, the density of the thin film is reduced, the transmittance of the visible near-infrared band is increased, and the light modulation capability is enhanced.
Description
Technical field
The present invention relates to a kind of metallic element Mg doping VO2The preparation method of thin film.Specifically utilize MSP-3200 tri-target
Cosputtering coater, with O2For reacting gas, Ar is working gas, and vanadium metal target is radio frequency reaction target, and magnesium metal target is straight
Stream reaction target, pyroreaction cosputtering prepares metallic element Mg doping VO2The method of thin film, belongs to inorganic thin film material and prepares
Field.
Background technology
VO2It is a kind of thermal induced phase transition material, occurs when about T=68 DEG C monoclinic phase (M phase) to Tetragonal (R phase)
Reversible phase in version, because its phase transition temperature becomes the study hotspot of phase-change material in recent years close to room temperature.Research shows, VO2's
Phase transformation is along with optical property, electric property, the sudden change of magnetic performance so that it is be widely used in smart window, lasing safety, electricity
In the photoelectric devices such as mutagens color, photoswitch, photocatalysis, photovoltaic, solar cell and Terahertz and infrared regulation and control.
VO2Phase transition temperature be TcAbout=68 DEG C, although the phase transition temperature in VOx difference oxide is closest to room
Temperature, but at smart window, photoswitch, the application of the aspects such as the photoelectric device of room temperature is still restricted.In order to reduce
VO2Phase transition temperature, doping is modal method, by mix high-valence state transition metal (such as W6+、Mo6+、Nb6+
Deng) or nonmetalloid F, all can effectively reduce VO2The phase transition temperature of thin film, and its light transmission characteristic is produced certain
Impact.
Additionally, for doping VO2The more doping concentrating on metal elements W of research of thin film, such as Yuankai in 2014
Liu et al. have studied W6+Doping is to VO2Thin film infrared passes through, Hysteresis cycle width and the impact of microscopic appearance；2009
Jamie M and Yanfei Wu in 2014 et al. utilizes XAFS (X-ray fine-structure distribution) and EXAFS (extension X
Ray fine-structure distribution have studied W6+Doping to VO2The impact of film crystal structure.Although the doping of W element is permissible
Effectively reduce phase transition temperature, but the incorporation of W element also results in VO2The transmitance of thin film reduces, Hysteresis cycle becomes
Wide, the modulation capability of light diminishes.Its application in the field such as smart window and energy saving building is made to be restricted.
Additionally, there is researcher that the sight of research has been invested metallic element Mg doping VO2Research, research find Mg mix
Miscellaneous VO2Transmitance near infrared band increases, and the modulation capability of light strengthens, and leads in smart window, energy saving building etc. for it
The application in territory is significant.At present, metallic element Mg is mixed block VO by the method having researcher hydrothermal method2, grind
Study carefully and show before and after phase transformation, VO2Crystal structure change with volume, block materials destroys through becoming different mutually,
And VO2Thin film can stand phase transition process repeatedly and the most impaired, the therefore VO of thin-film state2There is wider application prospect.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide the preparation Mg doping VO of a kind of stable process conditions2Thin film
Method.
On the one hand, the invention provides the VO of a kind of Mg doping2Thin film, the VO of described metallic element Mg doping2Thin
Film has the nanometer pore of irregular distribution and principal phase is monoclinic phase, and high preferred orientation is (011) crystal face, and crystallite dimension is 90
Nm～165nm.
It is preferred that described nanometer air vent aperture is 15.20nm～30.60nm.About doping content, it is preferred that described gold
The doping content belonging to element M g is 0.88at%～7.19at%.Additionally, what the described metallic element Mg that the present invention provides adulterated
VO2Film absorption peak can be blue shifted to 619nm.Metallic element Mg is mixed VO uniformly2In thin film, the doping obtained
VO2The generation that film surface is porose, consistency reduces, and pore size reduces, by adulterating along with the increase of Mg doping content
Concentration is that 30.60nm during 0.88at% is reduced to 15.20nm when doping content is 7.19at%, and crystallite dimension reduces.Separately
Outward, Mg doping VO2Thin film has more preferable light transmission characteristic at Visible-to-Near InfaRed wave band, visible light wave range mixing along with Mg
Enter so that semiconductor form VO2The transmitance of thin film increases, and the phenomenon of absworption peak blue shift occurs, 0.0at%Mg adulterate
709nm be blue shifted to 7.19at%Mg doping 619nm.
It is preferred that the VO of described metallic element Mg doping2The thickness of thin film is 50nm-80nm, preferably 70nm.
It is preferred that the VO of described metallic element Mg doping2Thin film near-infrared band light transmission rate maximum reaches
64.17%.
Mg doping VO prepared by the present invention2The principal crystalline phase of thin film is monoclinic phase, and high preferred orientation is (011) face, Er Qiesui
The incorporation of Mg, VO2The main diffraction maximum of thin film is moved slightly towards right avertence；The crystallite dimension of doping film reduces, and film surface occurs
Irregular nanometer pore, and aperture increases along with the power of direct current Mg target and reduces, the consistency of thin film reduces.It addition,
Mg adulterates VO2Thin film has more preferable light transmission characteristic at Visible-to-Near InfaRed wave band, along with the incorporation of Mg makes semiconductor form
The transmitance of the light of thin film increases, and the phenomenon of absworption peak blue shift occurs.At near infrared band along with the increasing of Mg constituent content
Adding, the transmitance of light increases, and the modulation capability of light strengthens.
On the other hand, the invention provides the VO of a kind of Mg doping2The preparation method of thin film, it is characterised in that with stone
English sheet is as at the bottom of reactive group, and vanadium metal target reacts target as radio-frequency sputtering, and magnesium metal target reacts target as d.c. sputtering, and oxygen is made
For reacting gas, quartz substrate, as working gas, is heated to reaction temperature by argon, by plasma emission spectrum detecting system
(PEM) feedback control reaction, cosputtering synthesis metallic element Mg doping VO2Thin film.
It is preferred that first carry out pre-sputtering, then carry out cosputtering, to remove target material surface impurity that may be present, and make anti-
Balance should be reached.The pre-sputtering time is preferably 4～7 minutes, till reaching the aura intensity stabilization of vanadium metal.
It is preferred that during described cosputtering, quartz substrate is heated to reaction temperature is 460 DEG C～480 DEG C；Working gas Ar gas
Flow be 180sccm；O2Flow-control be 2.2sccm～2.4sccm.Background vacuum ＜ 1.0 × 10-5Pa；Reaction
Pressure is 0.5Pa.Described cosputtering radio-frequency power is 200W～350W, and dc power is 25W～40W；During cosputtering
Between be 25～33 minutes.Additionally, above-mentioned each parameter is same as cosputtering during described pre-sputtering.
Wherein, PEM feedback control refers in reactive sputtering process, by the glow discharge optical emission spectrometry signal collected, mass spectrum letter
Number, voltage signal, the signal such as reacting gas dividing potential drop feeds back to target power supply or mass flow controller, according to the numerical value gathering signal
Regulate power size or the reaction gas flow being passed through in real time, thus realize reactive sputtering process moving at a certain process window
State balances.The present invention be the glow discharge optical emission spectrometry signal by controlling metal V atom as feedback signal, by regulating the phase of V atom
Size to glow discharge optical emission spectrometry intensity, O in plasma emission spectrum detecting system feedback control course of reaction2The size of flow.
The invention has the beneficial effects as follows: metallic element Mg is mixed VO uniformly2In thin film, the doping VO obtained2Thin film table
The generation that face is porose, consistency reduces, and pore size reduces, the porose product of film surface along with the increase of Mg doping content
Raw, the consistency of thin film reduces, and in the transmitance increase of Visible-to-Near InfaRed wave band, the modulation capability of light strengthens.
Accompanying drawing explanation
Fig. 1 be Mg doping content be the VO of 7.19at%2The V-O collection of illustrative plates of the XPS collection of illustrative plates of thin film；
Fig. 2 be Mg doping content be the VO of 7.19at%2The Mg1s collection of illustrative plates of the XPS collection of illustrative plates of thin film；
Fig. 3 is the VO that Mg doping content is respectively 0.0at%, 0.88at%, 3.78at%, 7.19at%2The X-ray of thin film sample
(XRD) diffraction pattern；
Fig. 4 be Mg doping content be the VO of 0.0at%2Scanning electron microscope (SEM) photo of film sample；
Fig. 5 be Mg doping content be the VO of 0.88at%2Scanning electron microscope (SEM) photo of film sample；
Fig. 6 be Mg doping content be the VO of 3.78at%2Scanning electron microscope (SEM) photo of film sample；
Fig. 7 be Mg doping content be the VO of 7.19at%2Scanning electron microscope (SEM) photo of film sample；
Fig. 8 a and Fig. 8 b is the VO that Mg doping content is respectively 0.0at%, 0.88at%, 3.78at%, 7.19at%2Film sample
Phase transformation before and after the transmittance curve figure of light, Fig. 8 a figure is the figure before phase transformation, and Fig. 8 b figure is the figure after phase transformation；
Fig. 9 is the VO that Mg doping content is respectively 0.0at%, 0.88at%, 3.78at%, 7.19at%2Film sample at wavelength
The curve chart changed for the modulation capability of light during 2500nm.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that following embodiment is merely to illustrate this below by way of following embodiment
Bright, and the unrestricted present invention.
The present invention utilizes three target co-sputtering coaters (such as, MSP-3200 tri-target co-sputtering coater), anti-by high temperature
Answer the VO of the metallic element Mg doping of the nanometer pore with irregular distribution that cosputtering method obtains2Thin film, nanometer pore
Aperture be 15.20～30.60nm.Its principal crystalline phase remains monoclinic phase, and high preferred orientation is (011) face, and crystallite dimension is
90nm～165nm, the doping content of described Mg can be 0.88at%～7.19at%.
The VO of the metallic element Mg doping that the explanation present invention in following exemplary ground provides2Thin film obtains preparation method.
The present invention utilizes MSP-3200 tri-target co-sputtering coater, reacts target, magnesium metal using vanadium metal target as radio-frequency sputtering
Target reacts target, O as d.c. sputtering2(purity is not less than 99.99%), as reacting gas, (purity is not less than Ar
99.99%) as working gas.O can not led to2Under conditions of, first pre-sputtering 4～7 minutes, with remove target material surface can
The impurity that can exist, and make reaction reach balance.Wherein the parameter of pre-sputtering can be that to be heated to reaction temperature be 460 to quartz substrate
DEG C～480 DEG C so that it is melted；The flow of working gas Ar gas is 180sccm；O2Flow be 2.3sccm～2.4
sccm；Background vacuum ＜ 1.0 × 10-5Pa；Reaction pressure is 0.5Pa；Radio-frequency power is set as that 300W keeps constant, directly
Stream power is 25W～40W.
Pre-sputtering utilizes plasma emission spectrum detecting system (PEM) feedback control to react after terminating, cosputtering synthesis gold
Belong to element M g doping VO2Thin film.The parameter of wherein said cosputtering can be: it is 460 that quartz substrate is heated to reaction temperature
DEG C～480 DEG C so that it is melted；The flow of working gas Ar gas is 180sccm；O2Flow by PEM control be
2.3sccm～2.4sccm；Background vacuum ＜ 1.0 × 10-5Pa；Reaction pressure is 0.5Pa；Radio-frequency power may be set to 300
W keeps constant, and dc power is 25W～40W；The cosputtering time is 25～33 minutes.PEM feedback control refers to
In reactive sputtering process, by the glow discharge optical emission spectrometry signal collected, mass signal, voltage signal, the signal such as reacting gas dividing potential drop is anti-
Feeding target power supply or mass flow controller, the numerical value according to gathering signal regulates power size or the reaction gas being passed through in real time
Body flow, thus realize the reactive sputtering process dynamic equilibrium at a certain process window.The present invention is former by controlling metal V
The glow discharge optical emission spectrometry signal of son controls reaction gas flow as feedback signal, mass flowmenter.Experimental Research relative to aura intensity and
The relation of oxygen flow (signal value near target surface after relative aura intensity=be passed through oxygen/enter the signal value before oxygen i.e. REI
=Vreactive/Vmetallic), find always to exist the scope of relative aura intensity, can stablize in this range to obtain VO2
(M) phase.From experiment, may determine that this scope is REI=0.6～0.65.Mg doped VO_2 thin films is prepared at cosputtering
During, set V atom relative to aura intensity REI=0.63, mass flowmenter feedback regulation O2The size of flow.
As an example, first putting quartz substrate on specimen disc, vanadium metal target reacts target, metal as radio-frequency sputtering
Magnesium target reacts target, O as d.c. sputtering2As reacting gas, reaction chamber, as working gas, is extracted into vacuum ＜ by Ar
1.0×10-5Pa, quartz substrate is heated to reaction temperature 470 DEG C, then sets reaction pressure, after pressure is stable, sets reaction
Radio-frequency power, dc power, and pre-sputtering 5 minutes, finally by plasma emission spectrum detecting system (PEM) feedback control
System is synthesized the VO of metallic element Mg doping2Thin film.What above-mentioned specimen disc was to be selected is graphite plate, and substrate can be 0.5
The fused silica glass sheet of mm thickness.Wherein, the flow of working gas Ar gas is 180sccm, O2Flow by PEM
Controlling flow is 2.3sccm～2.4sccm.Radio-frequency power be set as 300W keep constant, dc power be 25W, 30
W、40W。
Metallic element Mg is mixed VO by the present invention uniformly2In thin film, the doping VO obtained2The product that film surface is porose
Raw, consistency reduces, and pore size reduces along with the increase of Mg doping content, doping content be 0.88at% (doping
Concentration is by XPS data measured, according to formula n1/n2=(I1/S1)/(I2/S2) calculate thin film mg-doped ratio, wherein I is strong
Degree, corresponding to the area at peak, S is the Sensitivity Factor of element.Use Mg1s peak and V2p peak in the calculation) time
30.60nm is reduced to 15.20nm when doping content is 7.19at%, and crystallite dimension reduces.Additionally Mg doping VO2Thin film
More preferable light transmission characteristic is had, at visible light wave range along with the incorporation of Mg so that semiconductor form at Visible-to-Near InfaRed wave band
VO2The transmitance of thin film increases, and the phenomenon of absworption peak blue shift occurs, 0.0at%Mg the 709nm adulterated is blue shifted to
The 619nm of 7.19at%Mg doping.Increase along with the increase of Mg constituent content, the transmitance of light near infrared band,
Big transmitance is increased to the 64.17% of 7.19at%Mg doping by 0.0at%Mg doping 43.36%, and maximum increasing degree reaches
20.81%, and the modulation capability enhancing of light, maximum increasing degree is 21.61%.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1-3
The filming equipment that the present invention uses is the MSP-3200 tri-target co-sputtering coater that Beijing Chuangshi Weina Technology Co., Ltd. assembles,
With quartz glass as substrate, vanadium metal target is radio frequency target, and magnesium metal target is direct current target, and oxygen (99.99%), for reacting gas
Being monitored system (PEM) feedback control by plasma emission spectroscopy, argon is working gas (99.99%), background vacuum
Value < 1.0 × 10-5Pa, radio-frequency power is 300W, and dc power is respectively 25W, 30W and 40W, operating pressure 0.5
Pa, quartz substrate is heated to 470 DEG C；
The step of the inventive method is described below:
1) piezoid is placed on graphite plate feeding reaction chamber；2) reaction chamber is evacuated to vacuum < 1.0 × 10-5Pa；
3) open infrared lamp light pipe and be heated to 470 DEG C；4) opening oxygen and argon gas circuit, Ar throughput is set to 180sccm, sets
Reaction pressure is 0.5Pa；5) after pressure is stable, open radio-frequency power supply, set V target and the sputtering power of Mg target, V target
The sputtering power of sputtering power Pr=300W, Mg target be respectively 25W, 30W, 40W, pre-sputtering 5min；6) pre-
Sputtering sets the relative glow discharge optical emission spectrometry intensity level of vanadium metal and is REI=0.63 after terminating, PEM feedback control cosputtering react
Carry out respectively 30 minutes.Obtain Mg doping content and be respectively the VO of 0.88at%, 3.78at%, 7.19at%2Thin film, uses
The V-VASE ellipsometer test test of J.A.Woollam company of the U.S., modeling analysis obtains VO2Film thickness is respectively 54.7
nm、52.8nm、62.3nm。
Comparative example 1
Using filming equipment is the MSP-3200 tri-target co-sputtering coater that Beijing Chuangshi Weina Technology Co., Ltd. assembles, with quartz glass
Glass is substrate, and vanadium metal target is radio frequency target, and magnesium metal target is direct current target, and oxygen (99.99%), for reacting gas by plasma
Body emission spectrum monitoring system (PEM) feedback control, argon is working gas (99.99%), base vacuum angle value
<1.0×10-5Pa, quartz substrate is heated to 470 DEG C；More specifically:
1) piezoid is placed on graphite plate feeding reaction chamber；2) reaction chamber is evacuated to vacuum < 1.0 × 10-5Pa；3)
Open infrared lamp light pipe and be heated to 470 DEG C；4) opening oxygen and argon gas circuit, Ar throughput is set to 180sccm, sets reaction
Pressure is 0.5Pa；5) after pressure is stable, open radio-frequency power supply, set V target and the sputtering power of Mg target, spattering of V target
Penetrating power P r=300W, the sputtering power of Mg target is 0W, pre-sputtering 5min；6) vanadium metal is set after pre-sputtering terminates
Glow discharge optical emission spectrometry intensity level 0.63 relatively, is carried out 30 minutes by the reaction of PEM feedback control cosputtering.Obtaining Mg doping content is
The VO of 0.0at%2Thin film, uses the V-VASE ellipsometer test test using J.A.Woollam company of the U.S., modeling analysis
Obtain VO2Film thickness is 72.1nm.
Fig. 1 be Mg doping content be the VO of 7.19at%2The V-O collection of illustrative plates of the XPS collection of illustrative plates of thin film, permissible from Fig. 1
Find out, except V4+Peak there is not the peak of V ion of other quantivalences, illustrate that the principal phase of thin film is VO2.Fig. 2 is Mg
Doping content is the VO of 7.19at%2The Mg1s collection of illustrative plates of the XPS collection of illustrative plates of thin film, as can be seen from Figure 2 has significantly
Mg1s peak, illustrates that Mg element successfully mixes VO2Thin film.
Fig. 4 be Mg doping content be the VO of 0.0at%2Scanning electron microscope (SEM) photo of film sample；Figure
5 is the VO of 0.88at% for Mg doping content2Scanning electron microscope (SEM) photo of film sample；Fig. 6 is Mg
Doping content is the VO of 3.78at%2Scanning electron microscope (SEM) photo of film sample；Fig. 7 is Mg doping content
VO for 7.19at%2Scanning electron microscope (SEM) photo of film sample.From SEM figure it can be seen that along with
The introducing of Mg element, the generation that film surface is porose, and along with the increase of Mg doping content, aperture reduces, dense by doping
Degree is reduced to 15.20nm during doping content 7.19at% for 30.60nm during 0.88at%；Crystallite dimension is by unadulterated
165nm is reduced to Mg doping content 7.19at% 90nm (seeing Fig. 4～Fig. 7) constantly.
Fig. 3 is the VO that Mg doping content is respectively 0.0at%, 0.88at%, 3.78at%, 7.19at%2Thin film sample
X-ray (XRD) diffraction pattern, as can be seen from Figure 3 the Mg doping of embodiment of the present invention 1-3 reaction cosputtering gained
It is respectively the VO of 0.88at%, 3.78at%, 7.19at%2Thin film, the VO of doping2Thin film has one by force at 2 θ=27.8 °
Spending obvious diffraction maximum, this peak corresponds respectively to monoclinic phase VO2(M) (011) crystal face diffraction (JCPDF card 72-in
0514).In addition, not having the diffraction maximum corresponding to other crystal faces occur, this shows the doping VO of preparation2Thin film has bright
(011) high preferred orientation shown.From Fig. 3, it can also be seen that the Mg doping of embodiment of the present invention 1-3 reaction cosputtering gained is divided
Wei the VO of 0.88at%, 3.78at%, 7.19at%2Thin film is along with the increase of metal Mg doping content, the diffraction of X-ray
There is the tendency moved to right at peak, and Mg element may mix VO2The lattice of thin film.
Fig. 8 is the VO that Mg doping content is respectively 0.0at%, 0.88at%, 3.78at%, 7.19at%2Film sample
Phase transformation before and after the transmittance curve figure of light, a figure is the figure before phase transformation, and b figure is the figure after phase transformation.Fig. 9 is Mg doping
Concentration is respectively the VO of 0.0at%, 0.88at%, 3.78at%, 7.19at%2Film sample when wavelength is 2500nm
Light modulation capability change curve chart.The Mg doping VO of reaction cosputtering gained2Thin film, along with gold when T=20 DEG C
Belonging to the incorporation of element M g, the transmitance at Visible-to-Near InfaRed wave band increases, and maximum changing value is 20.81% (λ=2500
Nm), the transmitance after phase transformation reduces, and (a figure and the b that see Fig. 8 scheme), the regulating power of light strengthens, at λ=2500nm
Time, increased to Mg doping content 7.19at% 64.47% (seeing Fig. 9) constantly by unadulterated 42.86%.
Additionally Mg doping VO2Thin film makes semiconductor form VO2There is absworption peak blue shift while increasing in the transmitance of thin film
Phenomenon, 0.0at%Mg the 709nm adulterated be blue shifted to 7.19at%Mg doping 619nm, the incorporation of Mg is described
Making the band gap broadening of thin film, absorption weakens, and transmitance increases, and sees Fig. 8 a (dotted line table of labelling " 6 " indication in figure
The implication shown is the VO of 0.0at%Mg doping2The absworption peak of film sample is 709nm, the void of labelling " 5 " indication in figure
The implication that line represents is the VO of 7.19at%Mg doping2The absworption peak of film sample is 619nm).
Claims (10)
1. the VO of a metallic element Mg doping2Thin film, it is characterised in that the VO of described metallic element Mg doping2Thin film has the nanometer pore of irregular distribution and principal phase is monoclinic phase, and high preferred orientation is (011) crystal face, and crystallite dimension is 90 nm～165 nm.
The VO of metallic element Mg the most according to claim 1 doping2Thin film, it is characterised in that the aperture of described nanometer pore is 15.20 nm～30.60 nm.
The VO of metallic element Mg the most according to claim 1 and 2 doping2Thin film, it is characterised in that the doping content of described metallic element Mg is 0.88～7.19 at%.
4. the VO adulterated according to the metallic element Mg according to any one of claim 1-32Thin film, it is characterised in that the VO of described metallic element Mg doping2Film absorption peak is blue shifted to 619 nm.
5. the VO adulterated according to the metallic element Mg according to any one of claim 1-42Thin film, it is characterised in that the VO of described metallic element Mg doping2Thin film near-infrared band light transmission rate reaches 64.17 %.
6. the VO of metallic element Mg doping as according to any one of claim 1-52The preparation method of thin film, it is characterized in that, using piezoid as at the bottom of reactive group, vanadium metal target reacts target as radio-frequency sputtering, and magnesium metal target reacts target as d.c. sputtering, and oxygen is as reacting gas, argon is as working gas, quartz substrate is heated to reaction temperature, plasma emission spectrum detecting system feedback control reacts, cosputtering synthesis metallic element Mg doping VO2Thin film.
Preparation method the most according to claim 6, it is characterised in that quartz substrate is heated to reaction temperature 460 DEG C～480 DEG C.
8. according to the preparation method described in claim 6 or 7, it is characterised in that the flow of described working gas Ar gas is 170 sccm～200 sccm；O2Flow be 2.2 sccm～2.4 sccm.
9. according to the preparation method according to any one of claim 6-8, it is characterised in that described background vacuum ＜ 1.0 × 10-5 Pa；Reaction pressure is 0.4 Pa～0.8 Pa.
10., according to the preparation method according to any one of claim 6-9, it is characterised in that described cosputtering radio-frequency power is 200 W～350 W, dc power is 25 W～40 W；The cosputtering time is 25～33 minutes.
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