CN101608293A - A kind of method for preparing WO 3 film - Google Patents
A kind of method for preparing WO 3 film Download PDFInfo
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- CN101608293A CN101608293A CNA2009101577871A CN200910157787A CN101608293A CN 101608293 A CN101608293 A CN 101608293A CN A2009101577871 A CNA2009101577871 A CN A2009101577871A CN 200910157787 A CN200910157787 A CN 200910157787A CN 101608293 A CN101608293 A CN 101608293A
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Abstract
The invention provides a kind of method for preparing WO 3 film.Described method comprises: first step places the tungsten sheet flat-temperature zone of vacuum tube furnace; Second step, temperature is when being elevated to 140-160 ℃ in will managing with the temperature rise rate of 8-12 ℃/min, the beginning aerating oxygen, ventilation relief pipe internal pressure slowly raises, make when temperature is elevated to 790-810 ℃ in pipe, the pipe internal pressure reaches 0.7atm-1.3atm, at 790-810 ℃ of insulation 13-17min, afterwards temperature is naturally cooled to room temperature then.Adopt method of the present invention, can direct oxidation prepare the good uniformity of large-area WO 3 film and WO 3 film, the more important thing is the repeatable high of preparation technology, be convenient to industrialization production.And the required equipment of the inventive method is simple, easy to operate, has avoided the use of big electric current.
Description
Technical field
The present invention relates to the preparation method of WO 3 film, particularly, relate to the method for direct oxidation growth WO 3 film on the tungsten sheet.
Background technology
Tungstic oxide has the photoelectricity double-bang firecracker and answers effect, stable, low, the hydrogen generation efficiency advantages of higher of light cut-in voltage as the catalytic material of water of decomposition generation hydrogen, also is a kind of good electrochromic material in addition.So it is favored by numerous investigators.Electron beam evaporation, magnetron sputtering, sol-gel technique are mainly adopted in the preparation of WO 3 film at present.Preceding two kinds of film techniques need expensive equipment (magnetic control sputtering device, electron beam evaporation instrument), and cost height, rate of film build are low; Sol-gel method film forming equipment comparatively speaking is simple, and cost is low, but this method is repeatable poor, and the tack of film and substrate is not good enough yet, is difficult for the big area film forming.The direct growth method be in the oxygen atmosphere on the tungsten sheet direct oxidation growth tungsten trioxide film, this method technological operation is convenient, required equipment is simple, greatly reduces cost, rate of film build is also higher.
Document Nanotechnology 19 (2008) 065704 (6pp) has reported a kind of technology of WO 3 film direct growth, mainly be that tungsten sheet with 80mm * 5mm * 0.2mm specification places the stainless steel reaction chamber, direct oxidation generates WO 3 film by the alternating-current that the tungsten sheet is applied voltage generation 55A in the oxygen atmosphere, naturally cools to room temperature then.
The direct growth technology of above-mentioned tungstic oxide, need carry out in the stainless steel reaction chamber, required equipment cost height will be realized its oxidation by the alternating-current that directly the tungsten sheet is applied 55A in addition, prepared sample specification is the small area of 80mm * 5mm, and homogeneity is not enough.Therefore, to realize low cost, produce the hydrogen technology efficiently as photoelectrocatalysis agent hydrogen production by water decomposition with tungstic oxide, just must reduce the preparation cost of catalytic material, but large-area preparation and good uniformity, the more important thing is the repeatable high of preparation technology, be convenient to industrialization production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method that can overcome above-mentioned prior art defective.Therefore, the present invention relates to following several aspect:
A first aspect of the present invention is a kind of method for preparing WO 3 film, and described method comprises:
First step places the tungsten sheet flat-temperature zone of vacuum vacuum tube furnace;
Second step, temperature is when being elevated to 140-160 ℃ in will managing with the temperature rise rate of 8-12 ℃/min, the beginning aerating oxygen, ventilation relief pipe internal pressure slowly raises, make when temperature is elevated to 790-810 ℃ in pipe, the pipe internal pressure reaches 0.7-1.3atm, at 790-810 ℃ of insulation 13-17min, afterwards temperature is naturally cooled to room temperature then.
A second aspect of the present invention is a kind of method for preparing WO 3 film, and described method comprises:
First step places the tungsten sheet flat-temperature zone of vacuum tube furnace;
Second step, temperature when being elevated to 150 ℃ in will managing with the temperature rise rate of 10 ℃/min, the beginning aerating oxygen, and according to the 40-220cm of placement tungsten sheet
2The total area, ventilation relief pipe internal pressure slowly raises, and makes when temperature is elevated to 800 ℃ in pipe, the pipe internal pressure reaches 1atm, is incubated 15min at 800 ℃ then, afterwards temperature is naturally cooled to room temperature.
The 3rd aspect of the present invention is that described method also comprises: after first step and before second step with the vacuum tube furnace extracting vacuum so that the pressure in the vacuum tube furnace reaches the step of 2-5 handkerchief.
A fourth aspect of the present invention is the 40-225cm of the flow of described oxygen according to placement tungsten sheet
2The total area, be arranged in the scope of 50-210sccm.
A fifth aspect of the present invention be wherein described in second step, when described temperature naturally cools to room temperature, switch by the control air outlet valve allows the interior gaseous tension of pipe slowly descend, and can open air outlet valve fully and take residual gas in the pipe away when temperature drops to about 400-600 ℃.
A sixth aspect of the present invention is that described method also comprises: before first step, the tungsten sheet is cut.
A seventh aspect of the present invention is the described line cutting that is cut into.
A eighth aspect of the present invention is that the purity of wherein said tungsten sheet is more than 99.9%.
A ninth aspect of the present invention is that described method also comprises: before first step, the tungsten sheet is comprised handle the early stage of mechanical polishing and ultrasonic cleaning.
A tenth aspect of the present invention is the center, flat-temperature zone that wherein said tungsten sheet is placed in described vacuum tube furnace.
A eleventh aspect of the present invention is that wherein said tungsten sheet is one or more.
A twelveth aspect of the present invention is that wherein said tungsten sheet is under a plurality of situation, leaves the slit between described a plurality of tungsten sheets to guarantee and fully the contacting of oxygen.
A thirteenth aspect of the present invention is the tungsten sheet that wherein said tungsten sheet also comprises into web-like.
The advantage of the inventive method is can direct oxidation to prepare the good uniformity of large-area WO 3 film and WO 3 film, the more important thing is the repeatable high of preparation technology, is convenient to industrialization production.And the required equipment of the inventive method is simple, easy to operate, has avoided the use of big electric current.
Description of drawings
Fig. 1 is according to one embodiment of the invention, has only a tungsten sheet to carry out the synoptic diagram of oxidation in vacuum tube furnace;
Fig. 2 is the synoptic diagram of heating schedule;
Fig. 3 is according to another embodiment of the invention, and a plurality of tungsten sheets carry out the synoptic diagram of oxidation in vacuum tube furnace; And
Fig. 4 is according to another embodiment more of the present invention, the tungsten sheet of one-tenth web-like carries out oxidation in vacuum tube furnace synoptic diagram.
Embodiment
The present invention is a kind of method for preparing WO 3 film, belongs to the direct oxidation technology of preparing of WO 3 film, and described method comprises: first step places the tungsten sheet flat-temperature zone of vacuum tube furnace; Second step, temperature is when being elevated to 140-160 ℃ in will managing with the temperature rise rate of 8-12 ℃/min, the beginning aerating oxygen, ventilation relief pipe internal pressure slowly raises, make when temperature is elevated to 790-810 ℃ in pipe, the pipe internal pressure reaches 0.7-1.3atm then at 790-810 ℃ of insulation 13-17min, afterwards temperature is naturally cooled to room temperature.
Vacuum tube furnace used in the present invention is the OTF-1200X tube furnace, is produced by brilliant Materials Technology Ltd. of Hefei section.Also can adopt the vacuum tube furnace of other models of the said firm such as GSL1600X.The not special restriction of described in this article vacuum tube furnace, if can satisfy as shown in Figure 1 have resistance wire heating system and a flat-temperature zone, and the accurate control of assurance oxygen flow gets final product.The inventor finds to guarantee preferably that in order to realize the oxidation homogeneity of prepared WO 3 film the tungsten sheet is placed in the center, flat-temperature zone.By accurately measuring the distance between the center, flat-temperature zone and the mouth of pipe, and guarantee its with begin from the mouth of pipe when the flat-temperature zone direction advances the tungsten sheet process be placed in the center, flat-temperature zone apart from the consistent tungsten sheet of realizing.
In addition, described method mainly also comprises: to the vacuum tube furnace extracting vacuum; The selection of tungsten sheet; Handle the early stage of tungsten sheet and clean; The cutting of tungsten sheet; After experiment finishes, the processing of gas in the pipe.
The selection of tungsten sheet is before described first step, and preferred purity is the tungsten sheet 99.9% or more, and what just prepared is best, the surperficial natural oxidation that can as far as possible avoid metal to put for a long time like this causing and pollution layer is handled in earlier stage to us and the influence of preparation process.In the present invention, a selected example is that the purity that " Beijing Chinese incense cedar woods non-ferrous metal technology development center " provides is 99.9%, and model is W1, storage period at one month with interior tungsten sheet.
Choose after the tungsten sheet, then the tungsten sheet is carried out early stage and handle, comprise mechanical polishing and ultrasonic cleaning.For example, ultrasonic cleaning comprises used acetone, dehydrated alcohol, deionized water each ultrasonic 10 minutes successively, and ultrasonic power is 100W.The big sand paper of order number is adopted in mechanical polishing, to avoid serious damage tungsten sheet surface.For example, elder generation polishes with 1200 purpose sand paper, finish grindes with 2000 purpose sand paper to reach ideal effect again.
Experimental different demand often needs to prepare the WO 3 film material of different area, so the tungsten sheet will be cut into different areas before the experiment.If the improper meeting of cutting method cause after the oxidation the WO 3 film crack at edge, come off.We cut by preferred line, and its basic functional principle is to utilize the fine wire (being called wire electrode) that moves continuously to make electrode, and workpiece is carried out pulse spark discharge ablation metal, excision forming.Positive magnificent digital control processing factory finishes the cutting of the line mentioned herein in Beijing, and it adopts miramint as wire electrode, the about 10-12mm/min of wire travelling speed, and the tungsten sheet neat in edge after guaranteeing to cut does not have burr.For further experiment is created good condition.The cutting of tungsten sheet can eliminate prepared WO 3 film edge cracking, come off, make its complete no burr.
It is worthy of note, also can carry out above-mentioned comprising after the cutting and handle the early stage of mechanical polishing and ultrasonic cleaning.
Below, will describe the first step of the present invention and second step in detail.
At first step of the present invention, that is, in the dress sample step, the tungsten sheet is installed in the flat-temperature zone of tube furnace, preferably as for the center of flat-temperature zone, can obtain the more uniform WO 3 film in surface like this.Whether the tungsten sheet is placed in the preparation not influence of center, flat-temperature zone for the small area WO 3 film, only can have influence on the oxidation homogeneity of big area WO 3 film.
In the method for the invention, can the experiment condition of described second step be a most important step of whole process, be related to WO 3 film and reach suitable thickness, form suitable crystalline structure.Below, describe choosing and preferred result of experiment parameter involved in this step in detail.
Temperature rise rate in second step is 8-12 ℃/min, and passing through at temperature rise rate is the experiment comparison of 8,9,10,11 and 12 ℃/min, and discovery is under the situation of the temperature rise rate of 10 ℃/min, and effect of the present invention is best.Because temperature rise rate is too fast, the internal stress that thermal expansion causes can not get timely release, cause the be full of cracks of film easily, and temperature rise rate is slow excessively, and rate of film build is slow excessively.The temperature rise rate of 8-12 ℃/min both can make internal stress in time be discharged not cause be full of cracks, and it is slow that rate of film build was unlikely to again.
Press heating schedule, begin aerating oxygen when temperature is elevated to 140-160 ℃ in will managing.Because tungsten begins oxidation in the time of 300-400 ℃, in order to guarantee to choose from 140-160 ℃ of beginning aerating oxygen being warming up to the preparation work of finishing logical oxygen before 300-400 ℃ to the adjusting of oxygen flow and stable.The purity of oxygen is for being equal to or greater than 99.9%.The flow of described oxygen changes according to the placement tungsten sheet total area, normally, is 40-225cm for the total area
2The tungsten sheet, the flow of oxygen is set in the scope of 50-210sccm.The flow of oxygen must more accurately be controlled, and is guaranteeing that the flow of oxygen can not be excessive too big under the situation about fully contacting of tungsten sheet and oxygen, otherwise what may cause obtaining is not WO 3 film, but the tungsten oxide film of high oxidation more.In this application, whether obtaining WO 3 film mainly judges by color.It is successful obtaining the experiment that the xanchromatic film is considered to us on the tungsten sheet.Because those skilled in the art knows that according to general knowledge the color of the Tungsten oxide 99.999 of different degree of oxidations is different, for example, W
18O
49Be purple, W
20O
58Be blue.In addition, those skilled in the art is not difficult to determine, under the environment, the oxidation products that obtains can only be a Tungsten oxide 99.999 in the pipe that has only tungsten and oxygen.
Then, make when temperature is elevated to 790-810 ℃ in pipe that the pipe internal pressure reaches 0.7atm-1.3atm.The inventor is through repeatedly changing experiment condition, comprise and making when temperature is elevated to 790,792,795,797,800,802,804,806,808,810 ℃ etc., the pipe internal pressure reaches under about 1 atmospheric situation, all obtained experiment effect well of the present invention, promptly, obtained surperficial uniform yellow WO 3 film, and found it most preferably is when temperature is elevated to 800 ℃, to make the pipe internal pressure reach about 1 normal atmosphere.
At 790-810 ℃ of insulation 13-17min, afterwards temperature is naturally cooled to room temperature then.The length of soaking time relates to the film thickness that can reach suitable equally and forms suitable crystal formation.Experiment through choosing insulation 13,13.5,14,14.5,15,15.5,16,16.5,17min finds that soaking time is that 15min is most preferred.
In addition, the inventor also finds, in described second step, when temperature naturally cools to room temperature in making pipe, switch by the control air outlet valve allows the interior gaseous tension of pipe slowly descend, when temperature drops to the 400-600 ℃ of left and right sides, can open air outlet valve fully and take residual gas in the pipe away, can realize the present invention better like this.The slow decline of intraductal atmospheric pressure can make the oxidation of WO 3 film more even, abundant.
What be worth proposition is that tungsten plate shape of the present invention can be sheet, web-like, random shape etc.The method according to this invention can realize the preparation of a plurality of equal area or a plurality of different area WO 3 film simultaneously.For example, Fig. 3 has shown that schematically a plurality of tungsten sheets carry out oxidizing process in tube furnace.Thereby, can obtain the WO 3 film of different area according to the present invention.
As seen, be the OTF-1200X vacuum tube furnace because the present invention prepares the employed equipment of WO 3 film, equipment is simple, the resistance wire direct heating, operating procedure is convenient, and has avoided big electric current.The more important thing is that the technology of the present invention can realize the direct oxidation method preparation of single small area, a plurality of same size size or different specification size and big area WO 3 film, repeatability can reach more than 98%, and the processing parameter mobility scale is big, promptly except oxidizing temperature relative with soaking time more constant, other parameters such as oxygen flow, can in a big way, change to some extent according to the different area of tungsten sheet, as shown in table 2 below.In addition, reaction pressure then all can carry out suitable adjustment according to different condition in the 0.7atm-1.3atm scope, thereby adaptability is strong, is easy to apply.
Embodiment
Below, will the present invention will be described in more detail by embodiment, but these embodiment do not limit the intention of the scope of the invention.
Present embodiment only uses a tungsten sheet to carry out oxidation in vacuum tube furnace, and vacuum tube furnace is connected to vacuum pump.As shown in Figure 1,1 is tensimeter, is used for measuring and the demonstration reaction gas pressure, 2 is vacuum flange, the effective vacuum tightness of guarantee system, and 3 is resistance heating wire's heating region, the built-in resistor silk, 4 is the air outlet valve switch, is used for controlling the speed of giving vent to anger, make to keep certain reaction pressure in the pipe, 5 is the flat-temperature zone, and a thermopair is wherein arranged, be used for testing the temperature of flat-temperature zone, 6 are dress sample district, and 7 is inlet mouth, and 8 is the air outlet.Fig. 2 is a preferred version of the heating schedule of embodiment shown in Figure 1.1 is room temperature among Fig. 2, and t1 is the heating-up time, and t2 is a soaking time.And it is worthy of note that in this article, identical Reference numeral is represented identical implication.
The purity that choosing " Beijing Chinese incense cedar woods non-ferrous metal technology development center " provides is 99.9%, and model is W1, storage period one month with interior tungsten sheet, the specification of tungsten sheet is 45mm * 95mm * 0.2mm.The tungsten sheet finish grinded to cut disappearance, metallic surface smooth soft after 1200 purpose sand paper polishings again with 2000 purpose sand paper, with behind the deionized water rinsing in acetone, dehydrated alcohol, deionized water each ultrasonic 10 minutes successively.Tungsten sheet after cleaning is finished is dried, and adorns sample afterwards at once, by accurately measuring the distance of 8 of flat-temperature zone 5 and air outlets, guarantees that the tungsten sheet places central position, flat-temperature zone (position shown in Fig. 1 5), shown among Fig. 16 before the dress sample.First-class vacuum flange shown among Fig. 12, opening the vacuum pump (not shown) is evacuated to more than the 2-5Pa, start heating power supply, be starting resistance silk heating (in Fig. 13 in), set heating schedule as shown in Figure 2, wherein temperature rise rate, oxidizing temperature and soaking time are as shown in table 1 below respectively.Open gas meter simultaneously and begin preheating, district to be heated, temperature rises to 150 ℃ shown among Fig. 13, aerating oxygen (7,8 represent inlet mouth and air outlet respectively among Fig. 1), Flow-rate adjustment is 50sccm, suitably adjusts air valve 4 switches, and the interior gaseous tension of pipe is slowly raise, pressure was about 1 normal atmosphere when temperature arrived 800 ℃, and registration is shown by the tensimeter shown in 1 among Fig. 1.Heating schedule is slowly opened air outlet valve 4 switches after finishing, and the pipe internal pressure is slowly descended, and temperature then selects to naturally cool to room temperature (1 expression room temperature among Fig. 2).
Open tube furnace, take out the tungsten sheet that is obtained.Detect by an unaided eye, find to have covered the thin yellow film of one deck on the tungsten sheet, can confirm that this yellow film is a tungstic oxide, and, find that the surface of film is even.Because employed starting material are tungstens, and the atmosphere of reaction has only oxygen (purity is equal to or greater than 99.9%), so product can only be a Tungsten oxide 99.999, and the color distinction that different oxygen levels demonstrates in the Tungsten oxide 99.999 is very big, and experience confirms to show that xanchromatic is a tungstic oxide.
Repeatedly repeat present embodiment, wherein Shi Yan processing condition and result are presented in the following table 1.Surface color and uniformity coefficient according to products therefrom judge that the repeatability of the tungstic oxide that obtains can reach more than 98%.
Table 1
| Temperature rise rate (℃/min) | Oxidizing temperature (℃) | Oxygen flow (sccm) | Soaking time (min) | The result |
| ??10 | ??780 | ??50 | ??15 | Be the deep green rete |
| ??10 | ??790 | ??50 | ??15 | Be yellow rete, owe even, continuous slightly |
| ??10 | ??800 | ??50 | ??15 | Be even, continuous, fine and close yellow rete |
| ??10 | ??810 | ??50 | ??15 | Be uniform yellow rete, but the edge there is a little be full of cracks |
| ??10 | ??820 | ??50 | ??15 | Be yellow rete, but the edge chaps obviously |
On oxidizing temperature and oxygen flow are under the situation shown in the table 1, only when soaking time is changed to 11, during 12min, be the deep green rete, illustrate that oxidation is insufficient, the oxygen level deficiency, what obtain is not the tungstic oxide rete, and when soaking time is changed to 13, yellow rete occurs during 14min but do not reach best uniformity coefficient.Continue to prolong oxidization time then the oxidation meeting too fully begin to occur in various degree edge be full of cracks.
Present embodiment uses a plurality of tungsten sheets to experimentize simultaneously.Shown among Fig. 36, five specifications tungsten sheet that is 45mm * 95mm * 0.2mm staggered successively be placed in the corundum boat (the boat shape container that corundum material is made), all leave the slit about 1mm between per two tungsten sheets, make its all with the abundant contact reacts of oxygen.This compares different with experiment condition shown in Figure 1 be that only to need to change an oxygen flow be 190sccm.In addition, we realize also that with same procedure four specifications are the preparation of 54mm * 97mm * 0.2mm WO 3 film, and this moment, the oxygen optimum flow was 200sccm.Certainly the research staff of this area also can select the tungsten sheet of other a plurality of same sizes or a plurality of different sizes and corresponding optimum oxygen flow to test according to concrete needs, wherein Zui Jia oxygen flow is corresponding, as shown in table 2 below with the tungsten sheet total area of all size:
Table 2
| Oxygen flow (scccm) | ??50 | ??190 | ??200 | ??210 |
| Tungsten sheet area (cm 2) | ??40-50 | ??190-200 | ??200-210 | ??210-225 |
Set heating schedule as shown in Figure 2, wherein temperature rise rate, oxidizing temperature and soaking time are as shown in table 3 below respectively.What experiment obtained is the xanchromatic WO 3 film, and thin surface is even.Repeatedly repeat this experiment, wherein Shi Yan processing condition and result are presented in the following table 3, find that the repeatability that obtains tungstic oxide also can reach more than 98%.
Table 3
| Temperature rise rate (℃/min) | Oxidizing temperature (℃) | Oxygen flow (sccm) | Soaking time (min) | The result |
| ??10 | ??800 | ??200 | ??12 | Be the deep green rete |
| ??10 | ??800 | ??200 | ??13 | Be yellow rete, owe even, continuous slightly |
| ??10 | ??800 | ??200 | ??15 | Be even, continuous, fine and close yellow rete |
| ??10 | ??800 | ??200 | ??17 | Be uniform yellow rete, but the edge there is a little be full of cracks |
| ??10 | ??800 | ??200 | ??18 | Be yellow rete, but the edge chaps obviously |
The tungsten sheet that present embodiment uses into web-like carries out oxidation in tube furnace, as shown in Figure 4.The difference of inventive method shown in Figure 4 and Figure 1 and Figure 2 inventive method is: realized the preparation of big area WO 3 film, as 6 to be depicted as specification be that the tungsten sheet of 150mm * 150mm * 0.2mm becomes web-like to be placed on the center, flat-temperature zone among Fig. 4, the optimum oxygen flow of this moment is 210sccm.
Set heating schedule as shown in Figure 2, wherein temperature rise rate, oxidizing temperature and soaking time are as shown in table 4 below respectively.What experiment obtained is the xanchromatic WO 3 film, and thin surface is even.Repeatedly repeat this experiment, wherein Shi Yan processing condition and result are presented in the following table 4, and find that the repeatability that obtains tungstic oxide also can reach more than 98%.
Table 4
| Temperature rise rate (℃/min) | Oxidizing temperature (℃) | Oxygen flow (sccm) | Soaking time (min) | The result |
| ??8 | ??800 | ??210 | ??15 | Be the deep green rete |
| ??9 | ??800 | ??210 | ??15 | Be yellow rete, owe even, continuous slightly |
| ??10 | ??800 | ??210 | ??15 | Be even, continuous, fine and close yellow rete |
| ??11 | ??800 | ??210 | ??15 | Be uniform yellow rete, but the edge there is a little be full of cracks |
| ??12 | ??800 | ??210 | ??15 | Be yellow rete, but the edge chaps obviously |
Industrial applicability
The used equipment of preparation WO 3 film can be the OTF-1200X vacuum tube furnace, and equipment is simple, and resistance wire directly heats, and operating procedure is convenient, and has avoided large electric current. The more important thing is that the technology of the present invention can realize the direct oxidation method preparation of single small size, a plurality of same size size or different specification size and large tracts of land WO 3 film, repeatability can reach more than 98%, and the technological parameter mobility scale is large, except oxidizing temperature and temperature retention time are relatively constant, other parameters such as oxygen flow, can change to some extent within the specific limits according to the different area of tungsten sheet, as shown in table 2, reaction pressure then all can carry out suitable adjustment according to different condition in the 0.7atm-1.3atm scope, strong adaptability is easy to apply.
Claims (13)
1. method for preparing WO 3 film, described method comprises:
First step places the tungsten sheet flat-temperature zone of vacuum tube furnace;
Second step, temperature is when being elevated to 140-160 ℃ in will managing with the temperature rise rate of 8-12 ℃/min, the beginning aerating oxygen, ventilation relief pipe internal pressure slowly raises, make when temperature is elevated to 790-810 ℃ in pipe, the pipe internal pressure reaches 0.7-1.3atm, at 790-810 ℃ of insulation 13-17min, afterwards temperature is naturally cooled to room temperature then.
2. the method for preparing WO 3 film according to claim 1, described method comprises:
First step places the tungsten sheet flat-temperature zone of vacuum tube furnace;
Second step, temperature is when being elevated to 150 ℃ in will managing with the temperature rise rate of 10 ℃/min, the beginning aerating oxygen, ventilation relief pipe internal pressure slowly raises, make when temperature is elevated to 800 ℃ in pipe, the pipe internal pressure reaches 1atm, at 800 ℃ of insulation 15min, afterwards temperature is naturally cooled to room temperature then.
3. the method for preparing WO 3 film according to claim 1 and 2, described method also comprises: after described first step and before second step, with the vacuum tube furnace extracting vacuum so that the pressure in the vacuum tube furnace reaches the step of 2-5 handkerchief.
4. the method for preparing WO 3 film according to claim 1 and 2, the flow of wherein said oxygen is according to the total area 40-225cm of placement tungsten sheet
2, be arranged in the scope of 50-210sccm.
5. the method for preparing WO 3 film according to claim 1 and 2, wherein described in second step, when described temperature naturally cools to room temperature, switch by the control air outlet valve allows the interior gaseous tension of pipe slowly descend, and can open air outlet valve fully and take residual gas in the pipe away when temperature drops to about 400-600 ℃.
6. the method for preparing WO 3 film according to claim 1 and 2, described method also comprises:
Before first step, described tungsten sheet is cut.
7. the method for preparing WO 3 film according to claim 6 describedly is cut into line cutting.
8. the method for preparing WO 3 film according to claim 1 and 2, the purity of wherein said tungsten sheet are more than 99.9%.
9. the method for preparing WO 3 film according to claim 1 and 2, described method also comprises:
Before first step, described tungsten sheet is comprised handle the early stage of mechanical polishing and ultrasonic cleaning.
10. the method for preparing WO 3 film according to claim 1 and 2, wherein said tungsten sheet is placed in the center, flat-temperature zone of described vacuum tube furnace.
11. the method for preparing WO 3 film according to claim 1 and 2, wherein said tungsten sheet is one or more.
12. the method for preparing WO 3 film according to claim 11, wherein said tungsten sheet are under a plurality of situation, leave the slit between described a plurality of tungsten sheets to guarantee and fully the contacting of oxygen.
13. the method for preparing WO 3 film according to claim 1 and 2, wherein said tungsten sheet also comprises into the tungsten sheet of web-like.
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| CN102674463A (en) * | 2012-05-21 | 2012-09-19 | 上海交通大学 | Tungsten-base tungsten trioxide nano film, and preparation method and application thereof |
| CN110040976A (en) * | 2019-05-16 | 2019-07-23 | 合肥工业大学 | A kind of tungsten oxide electrochomeric films material and preparation method thereof |
| CN110040976B (en) * | 2019-05-16 | 2021-09-10 | 合肥工业大学 | Tungsten oxide electrochromic film material and preparation method thereof |
| CN112875836A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Tungsten trioxide electrode with controllable oxygen vacancy distribution and preparation and application thereof |
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| CN101608293B (en) | 2011-06-29 |
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