CN103981488B - A kind of method preparing vanadium oxide nano-grain array by rapid thermal treatment - Google Patents
A kind of method preparing vanadium oxide nano-grain array by rapid thermal treatment Download PDFInfo
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- CN103981488B CN103981488B CN201410222361.0A CN201410222361A CN103981488B CN 103981488 B CN103981488 B CN 103981488B CN 201410222361 A CN201410222361 A CN 201410222361A CN 103981488 B CN103981488 B CN 103981488B
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Abstract
The invention discloses a kind of method preparing vanadium oxide nano-grain array by rapid thermal treatment, comprise the steps: that (1) cleans aluminium sesquioxide substrate and wave carrier piece；(2) lifting monolayer silica nanosphere: on aluminium sesquioxide substrate, uses the method evenly distributed layer of silicon dioxide nanosphere of lifting plated film；(3) magnetron sputtering vanadium metal thin film: using vanadium metal as target, the method using facing-target magnetron sputtering system, deposit layer of metal vanadium thin film in above-mentioned steps (2) on full wafer aluminium sesquioxide substrate；(4) rapid thermal treatment forms vanadium dioxide film.The particle size of the array prepared by the present invention, in nanometer scale, arranges high-sequential, and preparation method is relatively simple simultaneously, and the process conditions of required control are less.In the case of experimental procedure is identical, by regulation experiment parameter, spherical and two kinds of vanadium oxide nano-grain arrays of triangle can be prepared, thus be greatly shortened experimental period in preparation.
Description
Technical field
The invention belongs to technical field of semiconductors, be specifically related to a kind of prepare vanadium oxide nano-grain array by rapid thermal treatment
Method.
Background technology
VO2Occur quasiconductor to the reversible transition of metal when 68 DEG C, its structure is converted to high temperature by monoclinic structure during low temperature
Time tetragonal crystalline structure.Along with the change of structure, the resistivity of material, susceptibility, light transmission rate and reflectance etc. occur prominent
Become, therefore have wide practical use at photoelectric device and smart window field.
As the basis of Nano-technology Development, nano material has the character such as the photoelectricity of uniqueness, calorifics, chemism, leads at each
Territory all has good development prospect, thus is paid close attention to by more and more research worker.Along with the improvement of preparation technology, VO2?
The size of grain can reach nanometer scale, and can be made into periodic nanometer array of particles.This periodic nanometer granule battle array
Row, combine the characteristic of nano material and the feature of array periodicity, and dimensional effect and form effect including optical resonance are inclined
Move, and the characteristic such as the near field of two-dimensional metallic nano-grain array and far field coupling, there is potential using value.Meanwhile, when
VO2When nano-grain array is in metallic state, its surface there will be plasma resonance.Surface plasma body resonant vibration is one
Plant physical optics phenomenon, be the collective oscillation of relevant free electron, form the charge density wave along dielectric surface.This ripple is at certain bar
Couple with incident light wave under part, i.e. produce resonance.In the process, material surface compactness all can obtain with phase transition temperature etc.
Significantly improve, therefore VO2Nano-grain array has very important researching value and application prospect widely.But with regard to mesh
Come to say, existing preparation VO2The shortcomings such as the procedure of nano-grain array is complicated, manufacturing cycle length are unfavorable for its performance
Research, therefore, optimize preparation process, shorten manufacturing cycle, work out the easiest a kind of preparation method and just seem particularly
Important.
Summary of the invention
In order to solve problems of the prior art, the present invention provides a kind of and prepares vanadium oxide nano-particle by rapid thermal treatment
The method of array, overcomes preparation VO in prior art2The procedure of nano-grain array is complicated, the problem of manufacturing cycle length.
The technical scheme is that
A kind of method preparing vanadium oxide nano-grain array by rapid thermal treatment, it is characterised in that comprise the steps:
(1) aluminium sesquioxide substrate and wave carrier piece are cleaned；
Aluminium sesquioxide substrate and wave carrier piece are sequentially placed in dehydrated alcohol, acetone solvent ultrasonic cleaning 20-30 minute respectively；
Aluminium sesquioxide substrate is washed with deionized water only, puts in dehydrated alcohol standby；Wave carrier piece is put into after rinsing and had previously been prepared
10-15% sodium lauryl sulphate (SDS) solution soaks more than 24h, standby as drainage piece.
(2) lifting monolayer silica nanosphere:
On aluminium sesquioxide substrate, use the method evenly distributed layer of silicon dioxide nanosphere of lifting plated film；Silica spheres
It is immersed in dehydrated alcohol and deposits, by liquid-transfering gun, silicon dioxide ethanol solution is added drop-wise to oblique cutting during use and enters deionization
On drainage piece in water, and slowly flow to the water surface, sprawl at the water surface and come, form high density, large-area monolayer silicon dioxide
Ball thin film, stands after liquid level stabilizing, is immersed in solution by aluminium sesquioxide substrate slowly with plated film pulling machine and vertically lifts
Going out liquid level, pull rate is 80-180 μm/min.
(3) magnetron sputtering vanadium metal thin film:
Using vanadium metal as target, the method using facing-target magnetron sputtering system, above-mentioned steps (2) gained sample deposits one layer of gold
Belong to vanadium thin film；Target used be quality purity be the vanadium metal of more than 99%, take out body vacuum to (3.0-4.0) × 10-4pa；Logical
Entering argon as working gas, flow is 40-50sccm；Operating pressure is to start sputtering during 2.0-3.0pa, and sputtering time is 10-30
Minute.
(4) rapid thermal treatment forms vanadium dioxide film；
Putting in quick anneal oven by the sample obtained in step (3), arrange annealing temperature and be 400-480 DEG C, heating rate is
40-50 DEG C/s, temperature retention time is 120-180s, temperature fall time 100-120s, and reacting gas is oxygen, oxygen stream when rising gentleness insulation
Amount is 3-4slpm, and during cooling, oxygen flow is 10slpm, and vanadium metal thin-films Oxygen is melted into vanadium dioxide film.
The invention have the advantage that
1) particle size of the array prepared by, in nanometer scale, arranges high-sequential, and preparation method is relatively simple simultaneously, required
The process conditions controlled are less.
2) in the case of experimental procedure is identical, by regulation experiment parameter, spherical and two kinds of vanadium oxides of triangle can be prepared and receive
Rice grain array, thus it is greatly shortened experimental period in preparation.
Accompanying drawing explanation
Fig. 1 (a) is spherical alumina vanadium nano-grain array schematic diagram in embodiment 1；
Fig. 1 (b) is the side view of Fig. 1；
Fig. 2 is the electron scanning micrograph of monolayer silica spheres thin film in embodiment 1；
Fig. 3 is the electron scanning micrograph of spherical alumina vanadium nano-grain array in embodiment 1；
Fig. 4 is the atomic force microscopy of spherical alumina vanadium nano-grain array in embodiment 1；
Fig. 5 (a) is embodiment 2 intermediate cam shape vanadium oxide nano-grain array schematic diagram；
Fig. 5 (b) is the side view of Fig. 5；
Fig. 6 is the electron scanning micrograph of monolayer silica spheres thin film in embodiment 2；
Fig. 7 is the electron scanning micrograph of embodiment 2 intermediate cam shape vanadium oxide nano-grain array；
Fig. 8 is the atomic force microscopy of embodiment 2 intermediate cam shape vanadium oxide nano-grain array；
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is elaborated.
Embodiment 1
Vanadium oxide nano-grain array schematic diagram is as shown in Figure 1.
1) the square aluminium sesquioxide substrate of a size of 1cm × 1cm is immersed in dehydrated alcohol, ultrasonic cleaning 20 minutes,
Rinse well with deionized water, then pour proper amount of acetone ultrasonic cleaning into 20 minutes, rinse well with deionized water, dry；Carry glass
Sheet (2cm × 2cm) puts in acetone, dehydrated alcohol ultrasonic cleaning 25 minutes respectively, then with deionized water rinsing, after flushing
Put into immersion 24h in 10% sodium lauryl sulphate (SDS) solution previously prepared, the most again with deionized water rinsing,
Microscope slide after cleaning uses as drainage piece in dropping silica spheres solution processes；
2) with syringe, silicon dioxide ethanol solution is added drop-wise on the drainage piece that oblique cutting enters in deionized water, and slowly flows
To the water surface, sprawl at the water surface and come, form high density, large-area monolayer silica spheres thin film, stand after liquid level stabilizing,
Being immersed in solution by aluminium sesquioxide substrate slowly with plated film pulling machine, pull rate is 100 μm/min, and substrate is vertical
Lift out liquid level.Surface topography such as Fig. 2 of monolayer silica spheres thin film；
3) using vanadium metal as target, the method using facing-target magnetron sputtering system, target used be quality purity be more than 99.99%
Vanadium metal, by step 2) in cleaned substrate be placed in vacuum chamber, take out body vacuum to 3.5 × 10-4pa.It is passed through argon, argon
Quality purity be 99.999%, flow is 48sccm；Starting sputtering when regulation operating pressure is to 3.0pa, sputtering time is 10
Minute；Deposition vanadium metal thin film uses ultrahigh vacuum facing-target magnetron sputtering system equipment；
4) by step 3) in sample put in quick anneal oven, arranging annealing temperature is 450 DEG C, and heating rate is 50 DEG C/s,
Temperature retention time 150s, temperature fall time 120s is passed through oxygen as reacting gas, and when heating up and be incubated, oxygen flow is 3slpm,
During cooling, protective gas is 10slpm, and vanadium metal thin-films Oxygen is melted into vanadium dioxide film.The quality purity of oxygen is 99.99%,
Annealing device uses the quick anneal oven that ALLwin21corp.USA company produces；
5) with scanning electron microscope and the surface topography of atomic force microscope test gained sample, such as Fig. 3 and Fig. 4；
Embodiment 2
Vanadium oxide nano-grain array schematic diagram is as shown in Figure 5.
1) the square aluminium sesquioxide substrate of a size of 1cm × 1cm is immersed in dehydrated alcohol, ultrasonic cleaning 20 minutes,
Rinse well with deionized water, then pour proper amount of acetone ultrasonic cleaning into 20 minutes, rinse well with deionized water, dry；Carry glass
Sheet (2cm × 2cm) puts in acetone, dehydrated alcohol ultrasonic cleaning 25 minutes respectively, then with deionized water rinsing, after flushing
Put into immersion 24h in 10% sodium lauryl sulphate (SDS) solution previously prepared, the most again with deionized water rinsing,
Microscope slide after cleaning uses as drainage piece in dropping silica spheres solution processes；
2) with syringe, silicon dioxide ethanol solution is added drop-wise on the drainage piece that oblique cutting enters in deionized water, and slowly flows
To the water surface, sprawl at the water surface and come, form high density, large-area monolayer silica spheres thin film, stand after liquid level stabilizing,
Being immersed in solution by aluminium sesquioxide substrate slowly with plated film pulling machine, pull rate is 150 μm/min, and substrate is vertical
Lift out liquid level.Surface topography such as Fig. 6 of monolayer silica spheres thin film；
3) using vanadium metal as target, the method using facing-target magnetron sputtering system, target used be quality purity be more than 99.99%
Vanadium metal, by step 2) in cleaned substrate be placed in vacuum chamber, take out body vacuum to 4.0 × 10-4pa.It is passed through argon, argon
Quality purity be 99.999%, flow is 46sccm；Starting sputtering when regulation operating pressure is to 2.5pa, sputtering time is 15
Minute；Deposition vanadium metal thin film uses ultrahigh vacuum facing-target magnetron sputtering system equipment；
4) by step 3) in sample put in quick anneal oven, arranging annealing temperature is 450 DEG C, and heating rate is 50 DEG C/s,
Temperature retention time 130s, temperature fall time 120s is passed through oxygen as reacting gas, and when heating up and be incubated, oxygen flow is 3.2slpm,
During cooling, protective gas is 10slpm, and vanadium metal thin-films Oxygen is melted into vanadium dioxide film.The quality purity of oxygen is 99.99%,
Annealing device uses the quick anneal oven that ALLwin21corp.USA company produces；
5) with scanning electron microscope and the surface topography of atomic force microscope test gained sample, such as Fig. 7 and Fig. 8；
The present invention can pass through regulation experiment parameter, has prepared spherical and triangle vanadium oxide nano-grain array respectively.In reality
Executing in example 1, through rapid thermal treatment, silica spheres is the most firmly attached in substrate, and obtain is spherical dioxy
Change vanadium nano-grain array；In example 2, through rapid thermal treatment, silica spheres is spontaneously decoupled substrate, and obtain is
Triangle vanadium dioxide nano array of particles.
Claims (2)
1. the method preparing vanadium oxide nano-grain array by rapid thermal treatment, it is characterised in that comprise the steps:
(1) aluminium sesquioxide substrate and wave carrier piece are cleaned；
Aluminium sesquioxide substrate and wave carrier piece are sequentially placed in dehydrated alcohol, acetone solvent ultrasonic cleaning 20-30 minute respectively；Will
Aluminium sesquioxide substrate is washed with deionized water only, puts in dehydrated alcohol standby；Wave carrier piece is put into after rinsing and had previously been prepared
10-15% sodium lauryl sulphate (SDS) solution soaks more than 24h, standby as drainage piece；
(2) lifting monolayer silica nanosphere:
On aluminium sesquioxide substrate, use the method evenly distributed layer of silicon dioxide nanosphere of lifting plated film；Will titanium dioxide
Silicon ball is immersed in dehydrated alcohol to be deposited, and by liquid-transfering gun, silicon dioxide ethanol solution is added drop-wise to oblique cutting and enters during use
On drainage piece in ionized water, and slowly flow to the water surface, sprawl at the water surface and come, form high density, large-area monolayer dioxy
SiClx ball thin film, stands after liquid level stabilizing, is immersed in solution by aluminium sesquioxide substrate slowly with plated film pulling machine and vertical
Lifting out liquid level, pull rate is 80-180 μm/min；
(3) magnetron sputtering vanadium metal thin film:
Using vanadium metal as target, the method using facing-target magnetron sputtering system, above-mentioned steps (2) gained sample deposits one layer of gold
Belong to vanadium thin film；
(4) rapid thermal treatment formation vanadium dioxide film:
Putting in quick anneal oven by the sample obtained in step (3), arrange annealing temperature and be 400-480 DEG C, heating rate is
40-50 DEG C/s, temperature retention time is 120-180s, temperature fall time 100-120s, and reacting gas is oxygen, oxygen stream when rising gentleness insulation
Amount is 3-4slpm, and during cooling, oxygen flow is 10slpm, and vanadium metal thin-films Oxygen is melted into vanadium dioxide film.
The method preparing vanadium oxide nano-grain array by rapid thermal treatment the most according to claim 1, it is characterised in that institute
State in step (3) target used be quality purity be the vanadium metal of more than 99%, take out body vacuum to 3.0-4.0 × 10-4pa；
Being passed through argon as working gas, flow is 40-50sccm；Operating pressure is to start sputtering, sputtering time during 2.0-3.0pa
For 10-30 minute.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104593738A (en) * | 2014-12-15 | 2015-05-06 | 天津大学 | Vanadium oxide thin film and preparation method thereof |
| CN104928636A (en) * | 2015-05-08 | 2015-09-23 | 天津大学 | Method for preparing vanadium dioxide anti-reflection coating through anti-reflection biomimetic surface |
| CN104878360A (en) * | 2015-06-12 | 2015-09-02 | 天津大学 | Preparation method for room-temperature methane gas sensor based on vanadium oxide |
| CN106220237A (en) * | 2016-07-15 | 2016-12-14 | 天津大学 | A kind of preparation method of monolayer ordered silica nanosphere array |
| CN106435472B (en) * | 2016-10-18 | 2018-09-25 | 天津大学 | A kind of preparation method of Golden Triangle nano-grain array and the compound nested structure of vanadium dioxide film |
| CN107988581A (en) * | 2017-11-06 | 2018-05-04 | 天津大学 | A kind of silica nanosphere array-VO2Film composite structure preparation method |
| CN108034927A (en) * | 2017-11-06 | 2018-05-15 | 天津大学 | VO for the more broad band absorbers of near-infrared2Film composite structure preparation method |
| CN107858649A (en) * | 2017-11-17 | 2018-03-30 | 天津大学 | One kind can improve VO2Film sunshine regulates and controls the preparation method of efficiency |
| CN108385064A (en) * | 2018-01-18 | 2018-08-10 | 天津大学 | A method of vanadium dioxide transmitted spectrum is regulated and controled by gold nano grain |
| CN108179394A (en) * | 2018-02-07 | 2018-06-19 | 天津大学 | A kind of method for improving vanadium dioxide phase time-varying amplitude by regulating and controlling sputtering power |
| CN109207929A (en) * | 2018-10-17 | 2019-01-15 | 天津大学 | A kind of porous periodic vanadium dioxide structure and preparation method thereof |
| CN110923628B (en) * | 2019-11-06 | 2021-11-26 | 南京理工大学 | Preparation method of novel surface cluster molecules |
| CN111411334A (en) * | 2020-02-29 | 2020-07-14 | 天津大学 | Silicon dioxide-vanadium dioxide multistage array structure and preparation method thereof |
| CN112871157B (en) * | 2021-02-20 | 2022-09-09 | 浙江工业大学上虞研究院有限公司 | Preparation method of mesoporous catalyst based on active alumina |
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| JP2000321124A (en) * | 1999-05-10 | 2000-11-24 | Nec Corp | Formation of vanadium oxide thin film and bolometer type infrared sensor employing vanadium oxide thin film |
| CN101174671A (en) * | 2007-10-18 | 2008-05-07 | 天津大学 | Production method for vanadium dioxide nano thin film with phase-change characteristic |
| CN102181827A (en) * | 2011-03-31 | 2011-09-14 | 天津大学 | Method for preparing nano vanadium dioxide film with phase change property on metal substrate |
| CN102732847A (en) * | 2012-06-18 | 2012-10-17 | 天津大学 | Phase change vanadium dioxide film prepared by rapid thermal oxidation method |
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