CN101660124A - Preparing method of porous tungsten oxide film - Google Patents
Preparing method of porous tungsten oxide film Download PDFInfo
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- CN101660124A CN101660124A CN200910192095A CN200910192095A CN101660124A CN 101660124 A CN101660124 A CN 101660124A CN 200910192095 A CN200910192095 A CN 200910192095A CN 200910192095 A CN200910192095 A CN 200910192095A CN 101660124 A CN101660124 A CN 101660124A
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Abstract
The invention provides a preparing method of a porous tungsten oxide film, which is characterized in that the preparing method comprises the following steps: adopting a tungsten-target and aluminum-target magnetic control co-sputtering technology to deposit tungsten and aluminum on a substrate to form an aluminum alloy film; dipping the obtained tungsten-aluminum alloy film into alkaline solutionfor selective corrosion and oxidation; and finally, obtaining the porous tungsten oxide film on the substrate. The porous tungsten oxide film prepared with the method has even aperture distribution, and the average aperture size is about 100nm. The invention has the following obvious advancement and originality of simple preparation, easy control of technological parameters, controllable porosityand aperture size and even aperture distribution. The product structure and the property thereof are very suitable for manufacturing electrochromic devices and air-sensitive devices.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate in particular to a kind of preparation method with the porous tungsten oxide film in nano level aperture.
Technical background
Tungsten oxide film has characteristics such as electrochromism and air-sensitive, can be applicable to smart window, indicating meter, H
2Fields such as transmitter.Tungsten oxide film with nano-porous structure, because high specific surface area and special spectral response can strengthen to some extent to its air-sensitive and electrochromism sensitivity, preparing porous tungsten oxide film in recent years becomes the research focus.
The method for preparing porous tungsten oxide film of report mainly is anonizing and sol-gel method at present.Anonizing can obtain the equally distributed tungsten oxide film in aperture on the surface, but because substrate is the tungsten thin slice, is not suitable for the application at optics and microelectronic.And sol-gel method needs organic polymer to make the pore-creating template, but because template molecule and tungsten ion binding ability are poor, formed vesicular structure is difficult to keep stablizing in high-temperature annealing process, is prone to the hole connection of caving in, the film porosity is out of control, the unequal problem of pore size distribution.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, technology is simple, porosity and pore size is controlled, the preparation method of the porous tungsten oxide film of even aperture distribution.This method does not have tangible restriction to the selection of substrate, is adapted at preparing porous tungsten oxide film on the substrate base of various unlike materials.
The present invention utilizes the active difference of metallic element in the alloy firm, active bigger aluminium in selective corrosion tungsten-aluminum alloy films; Owing to the nanoscale effect, oxidizing reaction easily takes place in the tungsten electrode of nano-porous structure, finally generates porous tungsten oxide film simultaneously.
Utilize above principle, the present invention realizes by following concrete steps:
(1) cleaned substrate base is put into the sputtering chamber of magnetic control sputtering system, adopted high-purity tungsten target and aluminium target, the sputtering chamber base vacuum is evacuated to 10 as sputtering target material
-3Below the Pa, substrate temperature is set in room temperature to 300 ℃;
(2) feed rare gas element to sputtering chamber, adjust operating air pressure, set the sputtering power of tungsten target and aluminium target power supply, adopt mode deposits tungsten-aluminum alloy films on substrate base of double target co-sputtering;
(3) on substrate, obtain argenteous tungsten-aluminum alloy films after sputter finishes;
(4) tungsten-aluminum alloy films is immersed corrosion oxidation in the basic solution, remove metallic aluminium, on substrate, obtain porous tungsten oxide film.
Said substrate base can be the substrate of glass or other materials.Mainly example in the following explanation with the glass substrate.Substrate base must clean up before film forming, as successively in deionized water, ethanol, acetone ultrasonic cleaning air-dry after ten minutes.
The preparation of tungsten-aluminum alloy films can be adopted various deposition methods, comprises magnetron sputtering method, vapour deposition method, ion plating, spraying or the like.The present invention adopts magnetron sputtering method.
Employed high-purity tungsten target of sputter procedure and aluminium target, purity all is not less than 99.9%.The temperature of glass substrate can be set at room temperature, also can heat, but top temperature is unsuitable for above 300 ℃.The sticking power of film and substrate was better when temperature was higher, but particle is bigger, and porosity is lower.Therefore, for obtaining the room temperature environment that greater porosity preferably adopts 20-30 ℃.Operating air pressure during spatter film forming is between the 0.1Pa to 2.0Pa, and air pressure is crossed to hang down in the time of can causing sputter and is difficult to build-up of luminance or aura instability, the too high sticking power that then can influence film and substrate of air pressure, and best effort air pressure is 0.5-1.0Pa.
In the film preparation process, tungsten target and aluminium target must adopt the mode film forming of cosputtering, that is to say, in the growth for Thin Film process, must have two kinds of compositions of tungsten and aluminium simultaneously.By regulating tungsten target and the aluminium target size of sputtering power to each other, can very easily regulate the relative proportion of tungsten and two kinds of compositions of aluminium in the alloy firm.Because aluminium is " sacrifice composition ", by following selective corrosion mechanism, aluminium simple substance is eliminated from alloy and stays corresponding hole.Thereby, can realize the porosity and the pore size of film are control effectively by the size of controlling aluminium composition ratio.The sputtering power of tungsten target and aluminium target is moderate.The too low meeting of sputtering power causes sputtering rate slow excessively, and the particle energy that sputters is low, is difficult to deposit on the film; And the too high meeting of sputtering power causes particle bigger, and porosity is lower, therefore selects for use the tungsten target sputtering power to be preferably 3-8W/cm
2, aluminium target sputtering power is preferably 5-10W/cm
2
Because tungsten-aluminum alloy films is to adopt the mode of tungsten target and aluminium target co-sputtering film forming, that is to say that on the rank of nanometer at least, tungsten composition and aluminium composition are even blend.After the aluminium composition was disallowable, the hole that carries in film was uniform on pore size distribution.
Described basic solution comprises the metal hydroxides aqueous solution, is preferably aqueous sodium hydroxide solution, and the concentration of solution is 0.5mol/L to 10.0mol/L, is preferably 2.5-5.0mol/L; Till stopping to separate out to hydrogen, corresponding corrosion process required time is about 20 minutes to 5 minutes.Aluminium component in the alloy firm and alkaline hydrated oxide solution reaction, dissolving and releasing hydrogen gas take place, and tungsten is insoluble to alkali and is kept, but the tungsten composition in the aluminium composition is corroded the dissolved process oxidizing reaction takes place, form the oxide compound of tungsten, obtain the porous tungsten oxide film at last.In the corrosion process, film gradually becomes translucent from the opaque shape of silvery white, becomes the dark brown translucent at last.Umbrinaceous formation means the generation of sull.
On the whole, the present invention has following obvious advance and originality: preparation is simple, and processing parameter is controlled easily, and porosity and pore size are controlled, even aperture distribution.Its product structure and character are highly suitable for making electrochromic device and gas sensitive device.
Description of drawings
Fig. 1 is the SEM image on the porous tungsten oxide film surface for preparing under embodiment 1 condition, and magnification is 10000 times;
Fig. 2 is the SEM image on the porous tungsten oxide film surface for preparing under embodiment 1 condition, and magnification is 50000 times;
Fig. 3 is the size distribution figure of the porous tungsten oxide film for preparing under embodiment 1 condition;
Fig. 4 is the XPS analysis figure of the W4f peak position of the porous tungsten oxide film for preparing under embodiment 1 condition;
Fig. 5 is the ultraviolet-visible-near-infrared transmission spectrum of the porous tungsten oxide film that makes under embodiment 1 condition.
Embodiment
Following examples are used for that the invention will be further described, but do not limit the scope that the present invention asks for protection.
The physical and chemical performance of the porous tungsten oxide film for preparing in following examples characterizes and comprises: the surface topography of scanning electronic microscope (SEM) viewing film; (XPS) analyzes the valence state of W elements in the film with x-ray photoelectron spectroscopy; With ultraviolet-visible-near infrared spectrometer the optical property of porous tungsten oxide film is analyzed.
Embodiment 1
(1) select for use the simple glass sheet as substrate, ultrasonic cleaning ten minutes in deionized water, ethanol, acetone successively.
(2) glass substrate that cleans up is sent into sputtering chamber, the purity of the tungsten target of selecting for use, aluminium target is 99.99%; Vacuum is evacuated to 10
-3Pa; The sputtering chamber temperature is a room temperature; Feed argon gas as working gas, flow is 60sccm, adjusts operating air pressure to 1.0Pa; After treating steady air current, open the RF radio-frequency power supply that connects tungsten target, aluminium target, wherein the radio-frequency power supply power that uses of tungsten target is 3.5W/cm
2, the radio-frequency power supply power that the aluminium target uses is 5W/cm
2Pre-sputter double target co-sputtering film forming after 30 minutes.Sputter finishes the back obtains silver color on substrate tungsten-aluminum alloy films.
(3) resulting tungsten-aluminum alloy films is immersed in the sodium hydroxide solution of 2.5mol/L, wherein aluminium component and sodium hydroxide solution react, and al dissolution is also continuous releasing hydrogen gas in solution; Tungsten composition in tungsten-aluminum alloy films then because scale effect by the dissolved oxygen oxidation in the solution, generates Tungsten oxide 99.999, and formed vesicular structure when the aluminium composition is corroded gradually, has obtained the porous tungsten oxide film.In the process of burn into oxidation, the opaque tungsten-aluminum alloy films of silver color becomes translucent gradually originally in sodium hydroxide solution, and it is translucent finally to be dark brown.From film begin to immerse sodium hydroxide solution to hydrogen stop to separate out, the film colour stable is approximately through 10 minutes.
(4) porous tungsten oxide film that makes is taken out from sodium hydroxide solution, the sodium hydroxide solution that adheres to is rinsed well through deionized water and ethanol, air-dry.
The prepared porous tungsten oxide film porosity of present embodiment is about 32%, even aperture distribution, and the aperture mean size is about 100nm, as Fig. 1, Fig. 2 and shown in Figure 3.And from Fig. 4 XPS collection of illustrative plates as can be seen, the peak position of W4f is at 34.9eV and 37.1eV, corresponding to the tungsten of+5 valencys, so in the film valence state of W elements based on+5 valencys.From the ultraviolet-visible-near-infrared transmission spectrum (Fig. 5) of film, as can be seen, have than higher transmittance, and have approximate straight transmittance curve near infrared region at the visible light wave range sample.This spectral response characteristic will very help the application of porous tungsten oxide film in electrochomeric glass.
The sputtering power of aluminium target was set at 5.2W/cm when difference from Example 1 was sputter
2
The film that the relative embodiment 1 of this routine prepared porous tungsten oxide film makes has higher porosity, is about 40%, even aperture distribution, and the aperture mean size is about 120nm.
Embodiment 3
Difference from Example 1 is that the sputtering power of aluminium target is set at 1.2W/cm
2
This routine prepared porous tungsten oxide film has lower porosity, is about 15%, even aperture distribution, and the aperture mean size is about 80nm.
Embodiment 4
Difference from Example 1 is that the sputtering power of tungsten target is set at 7W/cm
2
This routine prepared porous tungsten oxide film has lower porosity, is about 10%, even aperture distribution, and the aperture mean size is about 80nm.
Embodiment 5
Difference from Example 1 is that the sputtering power of tungsten target is set at 1.2W/cm
2, the employing monocrystalline silicon piece is a substrate.
This routine prepared porous tungsten oxide film has greater porosity, is about 40%, even aperture distribution, and the aperture mean size is about 130nm.
Embodiment 6
The working gas that uses when difference from Example 1 is sputter is nitrogen.
This routine prepared porous tungsten oxide film porosity is about 30%, even aperture distribution, and the aperture mean size is about 100nm.
Embodiment 7
The pressure of working gas was set at 0.1Pa when difference from Example 1 was sputter.
This routine prepared porous tungsten oxide film porosity is about 25%, even aperture distribution, and the aperture mean size is about 80nm.
Embodiment 8
Air pressure was 2.0Pa when difference from Example 1 was sputter, was substrate with the monocrystalline silicon piece.
This routine prepared porous tungsten oxide film porosity is about 40%, even aperture distribution, and the aperture mean size is about 120nm.
Embodiment 9
The temperature of substrate was set at 300 ℃ when difference from Example 1 was sputter.
This routine prepared porous tungsten oxide film porosity is about 30%, even aperture distribution, and the aperture mean size is about 120nm, the sticking power of film and substrate is good.
Embodiment 10
Difference from Example 1 is to use the potassium hydroxide solution corrosion, and concentration is identical.
This routine prepared porous tungsten oxide film porosity is about 32%, even aperture distribution, and the aperture mean size is about 100nm.
Embodiment 11
Difference from Example 1 is to use the sodium hydroxide solution of 0.5mol/L, and corrosion process approximately needs 20 minutes.
This routine prepared porous tungsten oxide film porosity is about 35%, even aperture distribution, and the aperture mean size is about 100nm.
Embodiment 12
Difference from Example 1 is to use the sodium hydroxide solution of 10.0mol/L, and corrosion process approximately needs 5 minutes.This routine prepared porous tungsten oxide film porosity is about 30%, even aperture distribution, and the aperture mean size is about 100nm.
Claims (7)
1. the preparation method of a porous tungsten oxide film is characterized in that may further comprise the steps:
(1) cleaned substrate base is put into the sputtering chamber of magnetic control sputtering system, adopted high-purity tungsten target and aluminium target, the sputtering chamber base vacuum is evacuated to 10 as sputtering target material
-3Below the Pa, substrate temperature is set in room temperature to 300 ℃;
(2) feed working gas to sputtering chamber, adjust operating air pressure, set the sputtering power of tungsten target and aluminium target power supply, with mode plated film on substrate base of double target co-sputtering;
(3) sputter finishes the back obtains Yin Baise on substrate tungsten-aluminum alloy films;
(4) tungsten-aluminum alloy films is immersed corrosion oxidation in the basic solution, remove metallic aluminium, on substrate, obtain porous tungsten oxide film.
2. the preparation method of porous tungsten oxide film as claimed in claim 1 is characterized in that working gas is a rare gas element in the described magnetron sputtering technique of step (2), and operating air pressure is between 0.1Pa～2.0Pa.
3. the preparation method of porous tungsten oxide film as claimed in claim 1 is characterized in that described step (4) neutral and alkali solution is the metal hydroxides aqueous solution.
4. the preparation method of porous tungsten oxide film as claimed in claim 3 is characterized in that described basic solution is an aqueous sodium hydroxide solution.
5. the preparation method of the porous tungsten oxide film described in claim 1 or 3 or 4 is characterized in that the concentration of described step (4) neutral and alkali solution is 0.5mol/L to 10.0mol/L, and the corrosion process required time is 5-20 minute.
6. the preparation method of porous tungsten oxide film as claimed in claim 5 is characterized in that the concentration of described step (4) neutral and alkali solution is 2.5-5.0mol/L.
7. the preparation method of porous tungsten oxide film as claimed in claim 1 is characterized in that described tungsten target sputtering power is 3-8W/cm
2, aluminium target sputtering power is 5-10W/cm
2
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102644050A (en) * | 2012-04-16 | 2012-08-22 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN103866256A (en) * | 2014-03-20 | 2014-06-18 | 常州大学 | Preparation method of metal oxide-porous nano films (MO-PNFs) |
| CN104711528A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Sheet-like tungsten trioxide photoelectrode and preparation method thereof |
| CN107299374A (en) * | 2017-06-16 | 2017-10-27 | 辽宁师范大学 | The porous WO of high transmittance3The preparation method of electrochomeric films |
| CN109343288A (en) * | 2017-08-01 | 2019-02-15 | 常州亚玛顿股份有限公司 | A kind of electrochomeric glass |
| CN112156769A (en) * | 2020-09-16 | 2021-01-01 | 北京工业大学 | Al/WO3Sodium (A)Rice composite film and preparation method and application thereof |
| CN114959662A (en) * | 2022-06-07 | 2022-08-30 | 哈尔滨工业大学 | Porous crystalline tungsten oxide film and method for preparing porous crystalline tungsten oxide film by adopting electrode electrospray |
-
2009
- 2009-09-08 CN CN2009101920950A patent/CN101660124B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102644050A (en) * | 2012-04-16 | 2012-08-22 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN102644050B (en) * | 2012-04-16 | 2014-01-08 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN104711528A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Sheet-like tungsten trioxide photoelectrode and preparation method thereof |
| CN103866256A (en) * | 2014-03-20 | 2014-06-18 | 常州大学 | Preparation method of metal oxide-porous nano films (MO-PNFs) |
| CN107299374A (en) * | 2017-06-16 | 2017-10-27 | 辽宁师范大学 | The porous WO of high transmittance3The preparation method of electrochomeric films |
| CN109343288A (en) * | 2017-08-01 | 2019-02-15 | 常州亚玛顿股份有限公司 | A kind of electrochomeric glass |
| CN112156769A (en) * | 2020-09-16 | 2021-01-01 | 北京工业大学 | Al/WO3Sodium (A)Rice composite film and preparation method and application thereof |
| CN112156769B (en) * | 2020-09-16 | 2023-08-29 | 北京工业大学 | Al/WO 3 Nano composite film, preparation method and application thereof |
| CN114959662A (en) * | 2022-06-07 | 2022-08-30 | 哈尔滨工业大学 | Porous crystalline tungsten oxide film and method for preparing porous crystalline tungsten oxide film by adopting electrode electrospray |
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