CN106634940B - A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure and preparation method thereof - Google Patents
A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure and preparation method thereof Download PDFInfo
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Abstract
A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure and preparation method thereof, belong to electrochromism technical field.Using element doping and control adjustment average coordination counting method, (ITO) is prepared by optimizing pulsed laser depositionx(Nb2O5)y(Ga2O3)1‑x‑yThe technique of film, monolithic film membrane are prepared as unified nanocrystalline and amorphous mixing crystalline state.Operation of the present invention is simple, is not easily introduced impurity, and preparation temperature is low, and preparation condition is easy to control, (ITO) of prepared nanocrystalline and amorphous composite constructionx(Nb2O5)y(Ga2O3)1‑x‑yThe electrochomeric films response time is fast, has preferable flexibility and apparent color change, provides material support and process modification for flexible intelligent color-changing window device.
Description
Technical field
The invention belongs to electrochromism technical fields, and in particular to a kind of indium tin niobium of amorphous state-nanocomposite structure
Gallium oxide electrochomeric films and preparation method thereof.
Background technique
Non-crystalline solids long-range unordered structure feature with short-range order.Non-crystalline solids macroscopically show as it is each to
The same sex only gradually softens with the raising of temperature without apparent fusing point when melting, and viscosity reduces, and is gradually transitions liquid
State.Non-crystalline solids are also known as glassy state, can regard the very big subcooled liquid of viscosity as.The long range ordered structure of crystal makes in it
It can be in minimum state, and non-crystalline solids make that minimum state can be not in it due to longrange disorder, therefore amorphous state is solid
Body is to belong to metastable phase, can release energy when converting to crystalline state.Common non-crystalline solids have high molecular polymer, oxide glass
Glass, amorphous metal and amorphous semiconductor etc..
The trend of display technology flexibility and ultrathin causes global researcher and industry to amorphous state transparent Indium
The very big concern of object semiconductive thin film (TAOS, Transparent Amorphous Oxide Semiconductor).2003
Year, J.F.Wager et al. has been delivered on the periodicals such as Science respectively about amorphous transparent oxide semiconductor thin-film transistor
The report of good characteristic start, the whole world has started research boom.Amorphous state transparent oxide semiconductor thin film (TAOS) is at full speed
Today of development, researcher have found many useful photoelectric characteristics, and based on this production photoelectric device or electrochemistry
Device.Amorphous material characteristic depends primarily on covalent bond structure arrangement, but the ambiguity of its Structural assignments makes control structure
It is still problem.Nanocrystalline structure is introduced in non crystalline structure, by controlling covalent bond between nanocrystalline structure and amorphous state, into
And the photoelectric characteristic of amorphous structure material is controlled, even it will appear new functional material on the handover interface of two kinds of structures,
There is new excellent characteristics to occur.For example, the hardness of nanocrystalline introducing enhancing bulk glass, improves the optical nonlinearity system of glass
Number leads to the opaque SPECTRAL REGION appearance transparency originally, and in nanocrystalline and glass interfaces, Particle Delivery ability enhances
There are problems to be: 1, the new function material of nanocrystalline and amorphous mixed structure mostly uses hydro-thermal method or chemical method, glass
State or colloidal state contact growth with crystalline state nanometer, and two kinds of materials have obvious interface, which exists only near interface, new function
Energy material is unable to large area or large volume growth, and material growth method and traditional industry growth pattern are incompatible.
2, nanocrystalline and amorphous mixed structure oxide semiconductor thin-film, when according to conventional sputter technique large area deposition, temperature
Degree-time changing curve is growth deposition key parameter, but temperature height is conducive to crystal growth, and temperature is low to be conducive to amorphous life
It is long, the growth of crystalline state is mixed so that temperature is set into a dilemma, allows traditional handicraft by temperature controlled material crystalline state
The method of structure can not mix crystalline state new material suitable for nanocrystalline and amorphous.
The Anna Llordes group that Nature in 2013 is delivered on interface realize glassy state NbO material mixing receive
Rice crystalline state ITO material, can be in Visible-to-Near InfaRed wave band electrochromic conducting oxide semiconductor thin-film.The material can be applied to
In electrochromic intelligent window, visible-infrared sensing sensitive detection parts, but the problem of proposing before, becomes and limits the material and widely popularize
Bottleneck: new function material only exists at interface, and area is too small to use size, the chemical method mentioned in document and quotient without business
The problems such as industryization manufacture is incompatible, and traditional handicraft temperature parameter can not regulate and control mixing crystalline state.Shi-na Li group attempts in ITO
The monocrystal thin films that middle doping Nb film preparation goes out, but the material does not have electrochromic property.
The present invention by adjusting transparent oxide semiconductor thin film doped chemical type and composition proportion approach, in tradition
On the basis of technique meets large area business preparation, nanocrystalline and amorphous mixing crystalline state transparent oxide semiconductor thin film is prepared,
And realize Visible-to-Near InfaRed wave band electrochromic effect, for this novel electrochromic functional material apply Intelligent energy-saving window,
The various fields such as the infrared stealth of low energy consumption display, automobile Anti-glare rearview mirror and satellite, weaponry, provide material branch
It holds and process modification.
Summary of the invention
Object of the present invention is to invent a kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure
And preparation method thereof, gained film has preferable electrochromic property and amorphous-nano-crystalline under flexible substrate bending condition
Mixed structure.
A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure and preparation method thereof, benefit
With element doping and control adjustment average coordination counting method, (ITO) is prepared by optimizing pulsed laser depositionx(Nb2O5)y
(Ga2O3)1-x-yThe technique of film, monolithic film membrane are prepared as unified nanocrystalline and amorphous mixing crystalline structure, specifically include following step
It is rapid:
Step 1, by 4N grades of ITO, Nb2O5、Ga2O3High-purity powder mixed grinding, it is high-purity mixed to obtain indium tin niobium gallium oxide
Close powder；
Step 2, mixed powder is put into high temperature process furnances, high temperature is pre-sintered；
Step 3, mixed powder after pre-sintering is put into pressure target drone, is pressed into cylindrical target；
Step 4, target after compacting is placed again into high temperature process furnances, high temperature sintering；
Step 5, target after high temperature sintering is put into vacuum chamber, is evacuated to background vacuum, close molecular pump and slide valve,
It is passed through oxygen, with 355nm pulsed laser ablation target, deposition obtains the flexible electrical of amorphous-nano-crystalline composite construction in substrate
Cause optically variable films.
Further, a kind of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films
And preparation method thereof, ITO, Nb described in step 12O5、Ga2O3Molar ratio, that is, x:y (1-x-y) of high-purity mixed-powder be
0.7-0.9:0.05-0.25:0.05-0.25。
Further, a kind of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films
And preparation method thereof, ITO, Nb described in step 12O5、Ga2O3High-purity mixed-powder in high-throughput beveller, use
800-1700 revs/min of revolving speed, milling time 2-10 hours；
Further, a kind of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films
And preparation method thereof, mixed powder described in step 2 and compacting target 1000 DEG C of pre-sintering temperature-in high temperature process furnances
1300 DEG C, the time is -15 hours 6 hours.
Further, a kind of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films
And preparation method thereof, compacting target pressure described in step 3 is 8-12MPa, and the pressing time is 5-20 minutes；
Further, a kind of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films
And preparation method thereof, background vacuum described in step 5 is 8*10-4Pa-1*10-5Pa, work atmosphere pressure are 0.1Pa-
5Pa, base reservoir temperature are 15 DEG C -45 DEG C, substrate distance target 3-6cm.
Amorphous state of the present invention-nanocomposite structure indium tin niobium gallium oxide electrochomeric films thickness is in 210nm-
3000nm。
A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure provided by the invention and its
Preparation method changes molecular structure based on element doping and functional performance has an important influence on, indium (In) element doping
With crystalline state nanometer and near infrared region light transmittance castering action is generated, there is gallium (Ga) element doping molecule to keep non crystalline structure
Effect, niobium (Nb) element doping improves electrochromic effect color contrast and forms glassy state covalent structure, to make thin
Film has preferable electrochromic property and amorphous-nano-crystalline mixed structure under the conditions of flexible bending.
The present invention uses solid-phase sintering and pulsed laser deposition technique, effectively improves flexible oxide semiconductor thin-film
Electrochromic property.
Detailed description of the invention
Fig. 1 is that the electrochomeric films electrochromism of 1 amorphous-nano-crystalline composite construction indium tin niobium gallium oxide of embodiment is saturating
Penetrate spectrum；
Fig. 2 is the X of amorphous-nano-crystalline composite construction electrochromic layer indium tin niobium gallium oxide film prepared by embodiment 1
X ray diffraction map.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
A kind of indium tin niobium gallium oxide electrochomeric films of amorphous state-nanocomposite structure and preparation method thereof, benefit
With element doping and control adjustment average coordination counting method, (ITO) is prepared by optimizing pulsed laser depositionx(Nb2O5)y
(Ga2O3)1-x-yThe technique of film, searches out the phase transformation threshold value of mean field theory, and monolithic film membrane is prepared as unified nanocrystalline and amorphous
Mix crystalline structure.Specifically includes the following steps:
Step 1, by 4N grades of ITO, Nb2O5、Ga2O3High-purity powder mixing, the molar ratio of mixed-powder is 0.7:0.05:
0.25, in high-throughput beveller, using 1500 revs/min of revolving speeds, grinds within milling time 2 hours, obtain indium tin niobium gallium oxide
High-purity mixed powder；
Step 2, mixed powder is put into high temperature process furnances, at a temperature of 1000 DEG C, is sintered 6 hours.
Step 3, mixed powder after pre-sintering is put into pressure target drone, at pressure 10MPa, suppresses 5 minutes, 4mm is made
Thick cylinder target；
Step 4, target after compacting is placed again into high temperature process furnances, at a temperature of 1200 DEG C, high temperature sintering 6 hours；
Step 5, target is put into vacuum chamber, is evacuated to 4*10-4Pa background vacuum closes molecular pump and slide valve,
Oxygen is passed through at 18 DEG C to 3Pa oxygen pressure, with the 355nm pulsed laser ablation target of mean power 400mW, in substrate distance 5cm
Place deposits the flexible electrochomeric films of 100nm-400nm amorphous-nano-crystalline composite construction in substrate.
Claims (7)
1. a kind of preparation method of amorphous state-nanocomposite structure indium tin niobium gallium oxide electrochomeric films, feature
It is, using element doping and control adjustment average coordination counting method, prepares (ITO) by optimizing pulsed laser depositionx
(Nb2O5)y(Ga2O3)1-x-yThe technique of film, monolithic film membrane is prepared as unified nanocrystalline and amorphous mixing crystalline structure, specific to wrap
Include following steps:
Step 1, by 4N grades of ITO, Nb2O5、Ga2O3High-purity powder mixed grinding, obtain the high-purity mixed powder of indium tin niobium gallium oxide
Material；
Step 2, mixed powder is put into high temperature process furnances, high temperature is pre-sintered；
Step 3, mixed powder after pre-sintering is put into pressure target drone, is pressed into cylindrical target；
Step 4, target after compacting is placed again into high temperature process furnances, high temperature sintering；
Step 5, target after high temperature sintering is put into vacuum chamber, is evacuated to background vacuum, closed molecular pump and slide valve, be passed through
Oxygen, with 355nm pulsed laser ablation target, deposition obtains the flexible electrical mutagens of amorphous-nano-crystalline composite construction in substrate
Color film；
ITO, Nb described in step 12O5、Ga2O3High-purity mixed-powder molar ratio, that is, x:y (1-x-y) be 0.7-0.9:
0.05-0.25:0.05-0.25。
2. a kind of indium tin niobium gallium oxide electrochromism of amorphous state-nanocomposite structure described in accordance with the claim 1 is thin
The preparation method of film, which is characterized in that ITO, Nb described in step 12O5、Ga2O3High-purity mixed-powder high throughput grind
In instrument, using 800-1700 revs/min of revolving speed, milling time 2-10 hours.
3. a kind of indium tin niobium gallium oxide electrochromism of amorphous state-nanocomposite structure described in accordance with the claim 1 is thin
The preparation method of film, which is characterized in that pre-sintering temperature 1000 in high temperature process furnances are become in high temperature pre-burning described in step 2
DEG C -1300 DEG C, the time is -15 hours 6 hours.
4. a kind of indium tin niobium gallium oxide electrochromism of amorphous state-nanocomposite structure described in accordance with the claim 1 is thin
The preparation method of film, which is characterized in that compacting target pressure described in step 3 is 8-12MPa, and the pressing time is 5-20 points
Clock.
5. a kind of indium tin niobium gallium oxide electrochromism of amorphous state-nanocomposite structure described in accordance with the claim 1 is thin
The preparation method of film, which is characterized in that background vacuum described in step 5 is 8*10-4Pa-1*10-5Pa, work atmosphere pressure
It is by force 0.1Pa-5Pa, base reservoir temperature is 15 DEG C -45 DEG C, substrate distance target 3-6cm.
6. a kind of indium tin niobium gallium oxide electrochromism of amorphous state-nanocomposite structure described in accordance with the claim 1 is thin
The preparation method of film, which is characterized in that film thickness is in 210nm-3000nm.
7. the amorphous state being prepared according to method described in any one of claims 1-6-nanocomposite structure indium tin niobium
Gallium oxide electrochomeric films.
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