CN1316544A - Process for preparing gas-sensitive allochroic WO3 film by vacuum evaporation - Google Patents
Process for preparing gas-sensitive allochroic WO3 film by vacuum evaporation Download PDFInfo
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- CN1316544A CN1316544A CN 01107472 CN01107472A CN1316544A CN 1316544 A CN1316544 A CN 1316544A CN 01107472 CN01107472 CN 01107472 CN 01107472 A CN01107472 A CN 01107472A CN 1316544 A CN1316544 A CN 1316544A
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Abstract
A process for preparing a gas-sensitive allochoroic WO3 film by vacuum evaporation includes such steps as cleaning substrate, loading WO3 powder (or tablets) into the crucible in vacuum chamber of electronic beam evaporator, putting Pt wire on resistor-type heat source, fixing substrate on specimen frame, sublimating WO3 by electronic beam heating to deposit it on the substrate, and evaporating a layer of catalyzing Pt on it by resistor heating. Its advantages include low cost, simple process, high film quality uniformity and high allochroic response speed.
Description
The present invention relates to method for manufacturing thin film, particularly a kind of method of preparing gas-sensitive allochroic WO 3 film by vacuum evaporation.
So-called gas chromism film is meant that reversible transformation can take place the film transmittance when this film successively contacts with the gas of certain kind.Can be with the bonding gas-discoloration device of making the hollow pair glass structure around coated glass (WO 3 film is in the inboard) and another sheet glass, when in glass sandwich, feeding low-concentration hydrogen, film is by the light yellow avy blue that becomes, the device transmittance descends, during bubbling air, the color of film and transmittance restore again.This gas-discoloration device can be regulated seeing through of light artificially, can be used as intelligent door and window, also can be used for billboard, display device etc.
Gas chromism film is made up of one deck transition metal oxide film (as Tungsten oxide 99.999, molybdenum oxide etc.) and one deck catalyst film (as rhodium, palladium, platinum, nickel etc.) usually.Wherein sull is with Tungsten oxide 99.999 ideal (color change interval is wide), and catalyzer is best with the effect of platinum.In the prior art, tungsten oxide film adopts method preparations such as sol-gel, magnetron sputtering usually, evaporates one deck platinum as catalyst layer on WO 3 film by resistive heating again.The sol-gel method cost is low, and method is simple, but film quality is not good.The film quality of magnetron sputtering method preparation is better, but the target preparation is complicated, and film is too fine and close, and the variable color time of response is long.With the tungsten trioxide powder is raw material, deposits WO 3 film with the electron beam heating sublimation on glass substrate, the film even compact of being produced, strong adhesion, surface hardness height.
Purpose of the present invention is exactly at above-mentioned the deficiencies in the prior art part, provides a kind of cost of the present invention low, and method is simple, and film quality is good, and evenly, variable color rings the method for short a kind of preparing gas-sensitive allochroic WO 3 film by vacuum evaporation of time.
The object of the present invention is achieved like this: a kind of electron beam adds the method for hot preparation gas-discoloration WO 3 film, it is characterized in that may further comprise the steps:
(1) cleans substrate;
(2) tungsten trioxide powder or pressed powder are put into the crucible of electron-beam evaporator vacuum chamber, platinum filament is placed on the resistance-type heating source, and the substrate of cleaning is fixed on the specimen holder;
(3) make the tungstic oxide distillation with electron beam heating and be deposited on the substrate.The vacuum plating unit vacuum chamber pressure is 10
-2-10
-3Pa, the about 200-300 of vacuum chamber temperature ℃, electronic beam current 0.1-0.2mA;
(4) by resistive heating evaporation one deck platinum Catalytic Layer.Vacuum chamber pressure 5-6.5 * 10
-3Pa, the vacuum chamber temperature is 200-300 ℃, resistance is steamed electric current between 120-245A.
(1) step, said substrate material can be the unclean purity that will influence the sticking power of film and substrate and influence film of glass, pottery or metal substrate, therefore, must be through cleaning the back plated film, the purity of tungsten trioxide powder will influence the purity of film, the present invention adopts analytically pure tungsten trioxide powder at least, or powder made compressing tablet, as evaporated material.(2) the step purity of said tungsten trioxide powder is at least analytical pure, platinum filament purity is at least 99.99%, said crucible material is a red copper, the resistance-type heating source is spiral helicine bifilar tungsten filament, and platinum filament is entangled on the tungsten filament, the density of film reduces with the reduction of vaporator rate, and vaporator rate raises, raises with gas pressure in vacuum and reduce with the temperature of evaporation source.The present invention need prepare the loose WO 3 film of texture ratio, mainly regulates vaporator rate by regulating gas pressure in vacuum and electron beam line.(3) step control tungstic oxide thicknesses of layers is 100nm-1000nm, and vacuum chamber pressure is controlled at 10
-2～10
-3Between the Pa, the electron beam line is between 0.1～0.2mA, the variable color degree of film increases with film thickness, the said WO 3 film thickness of step (3) can be controlled between the 100nm-1000nm as required, (4) step control platinum film layer thickness is at 15-40nm, it is heating source that electric current employing helical tungsten filamen is steamed in the resistance that raises gradually, and the platinized method of said steaming is (5-6.5 * 10 under certain vacuum chamber pressure
-3Pa), steam the temperature that electric current is controlled evaporation source by regulating resistance, for tungsten filament can not fused (at high temperature because of temperature is too high, tungsten filament is subjected to the influence of platinum, fusing point reduces), during start vaporizer, it is less that electric current is steamed in resistance, electric current is steamed in the resistance that raises gradually then, and its value is controlled between the 120-245A.The thickness of said platinum layer is between 15-50nm.
Reduction reaction will take place in the WO 3 film device when feeding contains the rare gas element of micro-hydrogen, gradually become blue from colourless; And gradually become colourless when aerating oxygen or air.This is that W in the tungstic oxide at platinum the reversible cause of appraising at the current rate and changing, i.e. redox reaction has taken place during as catalyzer respectively under the effect of hydrogen and oxygen.This change procedure is closely related with the structure and the factors such as reacting gas concentration and flow of the thickness of film and structure, device.In order to ensure safe in utilization, the concentration of generally controlling hydrogen in the mixed gas is less than 5%.
The present invention is raw material with the tungsten trioxide powder, deposits WO 3 film with the electron beam heating sublimation on glass substrate, evaporates one deck platinum as catalyst layer on WO 3 film by vacuum-evaporation appts again.The film of being produced is even, and the variable color time of response is short.
Concrete processing step of the present invention comprises:
(1) cleans substrate.
(2) tungsten trioxide powder or pressed powder are added in the crucible of vacuum chamber, platinum filament is placed on the resistance-type heating source, and the substrate of cleaning is fixed on the specimen holder.
(3) make the tungstic oxide distillation with electron beam heating and be deposited on the substrate.The vacuum plating unit vacuum chamber pressure is 10
-2-10
-3Pa, the about 200-300 of vacuum chamber temperature ℃, electron beam line 0.1-0.2mA.
(4) by resistive heating evaporation one deck platinum Catalytic Layer.Vacuum chamber pressure 5-6.5 * 10
-3Pa, the vacuum chamber temperature is 200-300 ℃, resistance is steamed electric current between 120-245A.
Embodiment one
(1) selecting sheet glass is substrate, cleans.(2) analytically pure tungsten trioxide powder is put into the crucible of electron-beam evaporator vacuum chamber, be that 99.99% platinum filament is entangled on the helical tungsten filamen with purity, and the substrate of cleaning is fixed on the specimen holder.(3) make the tungsten trioxide powder distillation with electron beam heating and be deposited on the glass substrate.The vacuum plating unit vacuum chamber pressure is 10
-2-10
-3Pa, the about 200-300 of vacuum chamber temperature ℃, the electron beam line is between 0.1-0.2mA.Quartz (controlled) oscillator on-line monitoring film thickness, the control film thickness is 500nm.(4) by resistive heating evaporation one deck platinum Catalytic Layer, vacuum chamber pressure 5-6.5 * 10
-3Pa, the vacuum chamber temperature is 200-300 ℃, resistance is steamed electric current between 120-245A.Quartz (controlled) oscillator on-line monitoring film thickness, control platinum film thickness is 20-30nm.
The made film of this example can reduce to 40% by 80% at the transmittance at 340nm-1100nm place, and the painted time is 20-30 second, and fading time is 1-2 minute.
Embodiment two
Different with embodiment one is that WO 3 film thickness is 1000nm.
The made film of this example can reduce to 15% by 80% at the transmittance at 340nm-1100nm place, and the painted time is 20-30 second, and fading time is 1-2 minute.
Embodiment three
Different with embodiment one is that platinum film thickness is 40-50nm.
The made film of this example can reduce to 40% by 70% at the transmittance at 340nm-1100nm place, and the painted time is 20-30 second, and fading time is 1-2 minute.
Claims (9)
1, a kind of method of preparing gas-sensitive allochroic WO 3 film by vacuum evaporation is characterized in that may further comprise the steps:
(1) cleans substrate;
(2) tungsten trioxide powder or pressed powder are put into the crucible of electron-beam evaporator vacuum chamber, platinum filament is placed on the resistance-type heating source, and the substrate of cleaning is fixed on the specimen holder;
(3) make the tungstic oxide distillation with electron beam heating and be deposited on the substrate.The vacuum plating unit vacuum chamber pressure is 10
-2-10
-3Pa, the about 200-300 of vacuum chamber temperature ℃, electronic beam current 0.1-0.2mA;
(4) by resistive heating evaporation one deck platinum Catalytic Layer.Vacuum chamber pressure 5-6.5 * 10
-3Pa, the vacuum chamber temperature is 200-300 ℃, resistance is steamed electric current between 120-245A.
2, by the described method of claim 1, it is characterized in that said substrate material can be glass, pottery or metal.
3, by the described method of claim 1, it is characterized in that the purity of said tungsten trioxide powder is at least analytical pure.
4, by the described method of claim 1, it is characterized in that said platinum filament purity is at least 99.99%.
5, by the described method of claim 1, it is characterized in that said crucible material is a red copper.
6, by the described method of claim 1, it is characterized in that said employing helical tungsten filamen is a heating source.
7, by the described method of claim 1, it is characterized in that said control tungstic oxide thicknesses of layers is 100nm-1000nm.
8, by the described method of claim 1, it is characterized in that said control platinum film layer thickness is at 15-40nm.
9,, it is characterized in that the said resistance steaming electric current that raises gradually by the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011074728A CN1142317C (en) | 2001-01-19 | 2001-01-19 | Process for preparing gas-sensitive allochroic WO3 film by vacuum evaporation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011074728A CN1142317C (en) | 2001-01-19 | 2001-01-19 | Process for preparing gas-sensitive allochroic WO3 film by vacuum evaporation |
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| Publication Number | Publication Date |
|---|---|
| CN1316544A true CN1316544A (en) | 2001-10-10 |
| CN1142317C CN1142317C (en) | 2004-03-17 |
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|---|---|---|---|
| CNB011074728A Expired - Fee Related CN1142317C (en) | 2001-01-19 | 2001-01-19 | Process for preparing gas-sensitive allochroic WO3 film by vacuum evaporation |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363759C (en) * | 2006-01-13 | 2008-01-23 | 中国科学院广州能源研究所 | Alloy gas chromism film material |
| CN100412227C (en) * | 2006-07-25 | 2008-08-20 | 天津大学 | Magnetically controlled opposite target sputtering process of preparing gas-sensitive WO3 film sensor |
| CN101767938B (en) * | 2009-10-30 | 2011-12-07 | 陕西科技大学 | Method for preparing WO3 hydrate nanometer film |
| CN101812093B (en) * | 2009-02-25 | 2012-12-26 | 中国科学院理化技术研究所 | One-dimensional micron or submicron material of polypyridine platinum complex and preparation method and application thereof |
| CN103160784A (en) * | 2011-12-19 | 2013-06-19 | 三菱综合材料株式会社 | Granular evaporation material, film forming method of evaporation film, and evaporation film |
| CN105506551A (en) * | 2015-11-26 | 2016-04-20 | 厦门虹鹭钨钼工业有限公司 | Preparation method of tungsten nickel alloy target for electrochromic glass film plating |
| CN105891126A (en) * | 2015-06-30 | 2016-08-24 | 四川智立方博导科技有限责任公司 | Low-cost portable hydrogen optical sensor |
| CN106932993A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | Magnesium yittrium alloy and tungsten oxide film are the total solids electrochromism light modulation device of base |
| CN113321427A (en) * | 2021-07-20 | 2021-08-31 | 上海交通大学 | WO capable of rapidly changing color by hydrogen3Film and preparation method thereof |
-
2001
- 2001-01-19 CN CNB011074728A patent/CN1142317C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363759C (en) * | 2006-01-13 | 2008-01-23 | 中国科学院广州能源研究所 | Alloy gas chromism film material |
| CN100412227C (en) * | 2006-07-25 | 2008-08-20 | 天津大学 | Magnetically controlled opposite target sputtering process of preparing gas-sensitive WO3 film sensor |
| CN101812093B (en) * | 2009-02-25 | 2012-12-26 | 中国科学院理化技术研究所 | One-dimensional micron or submicron material of polypyridine platinum complex and preparation method and application thereof |
| CN101767938B (en) * | 2009-10-30 | 2011-12-07 | 陕西科技大学 | Method for preparing WO3 hydrate nanometer film |
| CN103160784A (en) * | 2011-12-19 | 2013-06-19 | 三菱综合材料株式会社 | Granular evaporation material, film forming method of evaporation film, and evaporation film |
| CN105891126A (en) * | 2015-06-30 | 2016-08-24 | 四川智立方博导科技有限责任公司 | Low-cost portable hydrogen optical sensor |
| CN105506551A (en) * | 2015-11-26 | 2016-04-20 | 厦门虹鹭钨钼工业有限公司 | Preparation method of tungsten nickel alloy target for electrochromic glass film plating |
| CN105506551B (en) * | 2015-11-26 | 2017-09-19 | 厦门虹鹭钨钼工业有限公司 | A kind of preparation method of tungsten nickel target for electrochomeric glass plated film |
| CN106932993A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | Magnesium yittrium alloy and tungsten oxide film are the total solids electrochromism light modulation device of base |
| CN113321427A (en) * | 2021-07-20 | 2021-08-31 | 上海交通大学 | WO capable of rapidly changing color by hydrogen3Film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1142317C (en) | 2004-03-17 |
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