CN110642526A - Preparation method of tungsten oxide electrochromic film - Google Patents
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- CN110642526A CN110642526A CN201910869065.2A CN201910869065A CN110642526A CN 110642526 A CN110642526 A CN 110642526A CN 201910869065 A CN201910869065 A CN 201910869065A CN 110642526 A CN110642526 A CN 110642526A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/219—CrOx, MoOx, WOx
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
- C03C2217/231—In2O3/SnO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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Abstract
The invention provides a preparation method of a tungsten oxide electrochromic film, which comprises the following steps: 1) pouring tungsten oxide nano powder with the particle size of D50 being 100-500 nm into deionized water containing 0.1-3 wt% of dispersing agent, and performing ball milling for 8-24 h to form slurry; 2) the method comprises the following steps of (1) realizing the molding of a tungsten oxide target blank by adopting a slip casting mode, drying the molded blank, placing the dried blank into a cold isostatic pressing device, and carrying out cold isostatic pressing at 120-300 MPa for 60-600 s to form a tungsten oxide ceramic blank with the relative density of 60-75%; 3) sintering the tungsten oxide ceramic blank to obtain a tungsten oxide magnetron sputtering target material; the invention can utilize the ceramic target material of the tungsten oxide to deposit the tungsten oxide film with high-efficiency electrochromic performance by high-speed magnetron sputtering under the pure argon atmosphere, thereby meeting the use requirement of large-area electrochromic devices.
Description
Technical Field
The invention relates to the technical field of photoelectric thin films and devices, in particular to a preparation method of a tungsten oxide electrochromic thin film.
Background
Tungsten oxide, as a low-cost, non-toxic and environmentally friendly transition metal oxide, has been widely studied in the fields of photochromism, gasochromism, electrochromism and the like. Tungsten oxide has high contrast, high color change efficiency, fast response, stable physical and chemical properties, good cycling stability and low-voltage driving as an electrochromic film, and is increasingly applied to the fields of energy-saving glass for buildings, anti-dazzle rearview mirrors for automobiles, goggles, portholes of boeing airplanes and the like.
The preparation method of the tungsten oxide film mainly comprises thermal evaporation, chemical vapor deposition, sol-gel, magnetron sputtering and the like. The magnetron sputtering has the advantages of uniform components, strong adhesion between the film and the substrate, room-temperature sputtering, large-area coating and the like, and is widely used. The magnetron sputtering target is an important consumption type raw material in the magnetron sputtering film coating process and has important influence on a deposited film. The target materials for magnetron sputtering deposition of the tungsten oxide film are of two types, one is a metal simple substance target material of tungsten oxide, and the other is an oxide ceramic target material of tungsten oxide. The reactive sputtering of the former tungsten oxide metal simple substance target material to prepare the tungsten oxide film is the focus of the current industry and most research work. Kim et al (Japanese journal of Applied Physics 2013,52 (5S 2)) reported a typical tungsten oxide target reactive sputtering process to produce tungsten oxide, studied the discoloration of the deposited film at an oxygen ratio of 0.55 to 0.7, and showed that the film had the highest coloration efficiency when the oxygen content was increased to 0.7, and correspondingly, the sputtering rate of the film decreased from 3.1nm/min to 1.5 nm/min. Although the tungsten oxide target is relatively easy to obtain, the reactive sputtering of the tungsten oxide target still faces the following problems for uniform and rapid deposition of large-area films in the industry: (1) the performance of the film depends heavily on the content of oxygen, and the coloring characteristic and large-area uniformity of the film can be seriously influenced by the weak change or fluctuation of the oxygen in the sputtering cavity; (2) when the sputtering is carried out under the high-oxygen atmosphere, the surface of the target is easy to be poisoned, the sputtering voltage and power are difficult to be improved, and the sputtering rate is seriously reduced.
Therefore, the preparation of high-quality tungsten oxide color-changing films by using tungsten oxide ceramic targets with a certain tungsten-oxygen ratio is receiving more and more attention. For example, Hubert Camirand et al (Solar Energy Materials and Solar cells 2015,140, 77-85) reported that a film with the highest color change efficiency was prepared at 20mTorr using a tungsten oxide target in an atmosphere with an argon to oxygen ratio of 4:1, with a deposition rate of 9.6 nm/min. A small amount of oxygen is still used in the film magnetron sputtering process, but the uniform distribution of trace gas in the chamber is realized, and a plurality of new parts are additionally added to the coating equipment to ensure the uniformity of gas inflow, so that the cost of the equipment is increased.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the tungsten oxide film with high-efficiency electrochromic performance can be deposited by utilizing the ceramic target material of the tungsten oxide under the pure argon atmosphere through high-speed magnetron sputtering, and the use requirement of a large-area electrochromic device is met.
The technical solution of the invention is as follows: a preparation method of a tungsten oxide electrochromic film comprises the following steps:
1) pouring tungsten oxide nano powder with the particle size of D50 being 100-500 nm into deionized water containing 0.1-3 wt% of dispersing agent, and performing ball milling for 8-24 h to form slurry;
2) the method comprises the following steps of (1) realizing the molding of a tungsten oxide target blank by adopting a slip casting mode, drying the molded blank, placing the dried blank into a cold isostatic pressing device, and carrying out cold isostatic pressing at 120-300 MPa for 60-600 s to form a tungsten oxide ceramic blank with the relative density of 60-75%;
3) placing the tungsten oxide ceramic blank in a sintering furnace, under the oxygen pressure of 0.01-1 MPa, firstly heating to 1000-1200 ℃ from room temperature at the heating rate of 0.5-10 ℃/min, preserving the temperature for 60-300 min, and finally cooling to room temperature at the cooling rate of 0.5-10 ℃/min to obtain a tungsten oxide magnetron sputtering target material;
4) placing the tungsten oxide magnetron sputtering target material prepared in the step 3) in magnetron sputtering coating equipment, depositing a tungsten oxide film on an ITO transparent conductive glass substrate, and carrying out heat treatment on the sputtered tungsten oxide film at the temperature of 25-400 ℃ for 0-100 min in an air atmosphere to obtain the tungsten oxide electrochromic film.
Preferably, the purity of the tungsten oxide nano powder is more than 99.9%.
The target material is in a shape of a plane target material or a rotary target material.
Preferably, the dispersant is one or more of polyvinylpyrrolidone, polyvinyl alcohol and carboxymethyl cellulose.
As optimization, the relative density of the tungsten oxide magnetron sputtering target material prepared in the step 3) is more than 95%, and the atomic ratio of W to O in the target material is 1 (2.7 ~ 3).
As an optimization, the parameters of the sputtering process in step 4) are as follows:
(1) the sputtering mode is radio frequency sputtering or intermediate frequency sputtering;
(2) the substrate temperature is room temperature;
(3) background vacuum of 10-2Pa~10-4Pa, the sputtering pressure value is 0.8 ~ 2.0.0 Pa;
(4) the power density of sputtering is 2.2W/cm2~6.6W/cm2；
(5) The thickness of the film was 300 ~ 600 nm.
The invention has the beneficial effects that: the tungsten oxide film is sputtered under the pure argon atmosphere, the process becomes relatively simple, the uniformity of the plated film is improved, and the investment of equipment is relatively low; the deposition rate of the tungsten oxide film can reach 20nm/min at most, which is higher than the numerical values reported in other existing documents, so that the coating efficiency is improved, the number of target positions and coating chambers is reduced, and the investment on equipment is indirectly reduced; the tungsten oxide film prepared by the method has excellent electrochromic performance.
Drawings
FIG. 1 is an XRD pattern of a tungsten oxide film in film example 1.
FIG. 2 is a topographical view of a tungsten oxide film of film example 1: (a) surface topography, (b) cross-sectional topography.
FIG. 3 is a graph showing electrochromic characteristics of the tungsten oxide film of film example 1.
FIG. 4 is a graph of the cycling stability of the tungsten oxide film of film example 1.
FIG. 5 is an XRD pattern of the tungsten oxide film of example 2 after heat treatment at 200 ℃ for 30 min.
FIG. 6 shows the cycling stability of (a) a tungsten oxide film without heat treatment (b) a tungsten oxide film with heat treatment at 200 ℃ for 30min in film example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Preparation of target material
Tungsten oxide nano powder with the particle size of D50 being 100nm and the purity being more than 99.9 percent is poured into deionized water containing 1 weight percent of polyvinylpyrrolidone dispersant, and is ball-milled for 8 hours to form slurry; the forming of the tungsten oxide plane target blank is realized by adopting a slip casting mode, the formed blank is dried and then placed in a cold isostatic pressing device, and the tungsten oxide ceramic blank with the relative density of 60 percent is formed by cold isostatic pressing at 150MPa for 60 s; placing the tungsten oxide ceramic blank in a sintering furnace, firstly heating to 1100 ℃ from room temperature at a heating rate of 5 ℃/min under an oxygen pressure of 0.01MPa, preserving the temperature for 120min, and finally cooling to room temperature at a cooling rate of 3 ℃/min to obtain a tungsten oxide magnetron sputtering target material;
film example 1
The vacuum of the background is set to be 5 multiplied by 10 by adopting a radio frequency magnetron sputtering mode-4Pa, the power density of sputtering is 2.2W/cm2Preparing WO with the thickness of 500nm at room temperature by using a sputtering pressure of 0.8Pa3The prepared film is amorphous as shown in FIG. 1, and has a temperature of 20 ~ 25 deg.C and no WO3The peaks shown in the map are all proved to be characteristic peaks of ITO. The film prepared under the condition has the morphological characteristics of a loose porous structure, grows in a columnar shape, and is tightly combined with the substrate, as shown in figures 2(a) and (b) respectively.
The film prepared by the method is subjected to an electrochromic performance test, and is colored for 20s at-1V and bleached for 20s at +1V respectively, the result is shown in figure 3, and the maximum modulation amplitude of the film at 521nm wavelength is 71.1 percent, which is superior to that reported by most documents, commercial electrochromic glass can bear tens of thousands of coloring/fading processes without great performance attenuation, so that the cycle stability of the prepared film is tested under an electrochemical window of-1V ~ +1V, as shown in figure 4, the first CV cycle curve of the prepared film is shown in a typical 'dolphin' shape, and after 500 cycles, the area enclosed by the CV curve has certain attenuation, but the shape of the curve can be basically maintained till 3500 cycles, which shows that the prepared film has good cycle stability and commercial potential.
Film example 2
The background vacuum is set to 5 x 10 by adopting a radio frequency magnetron sputtering mode-2Pa, the power density of sputtering is 3.7W/cm2Preparing WO with the thickness of 400nm at room temperature by adopting the sputtering pressure of 1.2Pa3And annealing the film in air at 200 ℃ for 30 min. The annealed film showed a certain crystallinity, and as shown in FIG. 5, WO appeared in the spectrum except the ITO signal peak3The results show that the cycle stability of the tungsten oxide film after heat treatment is greatly superior to that of the film without heat treatment, as shown in fig. 6(a), (b), it can be seen from the figure that the tungsten oxide film without heat treatment loses electrochromic capability after 200 cycles under a larger electrochemical window (-1.5V ~ + 1V), and the tungsten oxide film after heat treatment at 200 ℃ for 30min still has good electrochromic capability after 500 cycles, which indicates that the heat treatment process can effectively improve the cycle life of the film.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (6)
1. The preparation method of the tungsten oxide electrochromic film is characterized by comprising the following steps of:
1) pouring tungsten oxide nano powder with the particle size of D50 being 100-500 nm into deionized water containing 0.1-3 wt% of dispersing agent, and performing ball milling for 8-24 h to form slurry;
2) the method comprises the following steps of (1) realizing the molding of a tungsten oxide target blank by adopting a slip casting mode, drying the molded blank, placing the dried blank into a cold isostatic pressing device, and carrying out cold isostatic pressing at 120-300 MPa for 60-600 s to form a tungsten oxide ceramic blank with the relative density of 60-75%;
3) placing the tungsten oxide ceramic blank in a sintering furnace, under the oxygen pressure of 0.01-1 MPa, firstly heating to 1000-1200 ℃ from room temperature at the heating rate of 0.5-10 ℃/min, preserving the temperature for 60-300 min, and finally cooling to room temperature at the cooling rate of 0.5-10 ℃/min to obtain a tungsten oxide magnetron sputtering target material;
4) placing the tungsten oxide magnetron sputtering target material prepared in the step 3) in magnetron sputtering coating equipment, depositing a tungsten oxide film on an ITO transparent conductive glass substrate, and carrying out heat treatment on the sputtered tungsten oxide film at the temperature of 25-400 ℃ for 0-100 min in an air atmosphere to obtain the tungsten oxide electrochromic film.
2. The method for preparing the tungsten oxide electrochromic film according to claim 1, wherein the purity of the tungsten oxide nano powder is more than 99.9%.
3. The method for preparing the tungsten oxide electrochromic film according to claim 1, wherein the tungsten oxide target blank is shaped as a planar target or a rotating target.
4. The method for preparing the tungsten oxide electrochromic film according to claim 1, wherein the dispersing agent is one or more of polyvinylpyrrolidone, polyvinyl alcohol and carboxymethyl cellulose.
5. The method for preparing the tungsten oxide electrochromic film according to claim 1, wherein the relative density of the tungsten oxide magnetron sputtering target prepared in the step 3) is more than 95%, and the atomic ratio of W to O in the target is 1 (2.7 ~ 3).
6. The method for preparing the tungsten oxide electrochromic film according to claim 1, wherein the parameters of the sputtering process in the step 4) are as follows:
(1) the sputtering mode is radio frequency sputtering or intermediate frequency sputtering;
(2) the substrate temperature is room temperature;
(3) background vacuum of 10-2Pa~10-4Pa, the sputtering pressure value is 0.8 ~ 2.0.0 Pa;
(4) the power density of sputtering is 2.2W/cm2~6.6W/cm2；
(5) The thickness of the film was 300 ~ 600 nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374887A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of tungsten oxide-based ceramic target material |
| CN112479707A (en) * | 2020-11-13 | 2021-03-12 | 北京航大微纳科技有限公司 | Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material |
| CN112626459A (en) * | 2020-12-14 | 2021-04-09 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of tungsten oxide layer in electrochromic composite film system |
| CN116813343A (en) * | 2023-07-04 | 2023-09-29 | 有研资源环境技术研究院(北京)有限公司 | Inorganic electrochromic film-forming material and preparation method thereof |
| CN116835981A (en) * | 2023-07-05 | 2023-10-03 | 宁波江丰电子材料股份有限公司 | Metal oxide target material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374887A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of tungsten oxide-based ceramic target material |
| CN112479707A (en) * | 2020-11-13 | 2021-03-12 | 北京航大微纳科技有限公司 | Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material |
| CN112626459A (en) * | 2020-12-14 | 2021-04-09 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of tungsten oxide layer in electrochromic composite film system |
| CN112626459B (en) * | 2020-12-14 | 2023-02-17 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of tungsten oxide layer in electrochromic composite film system |
| CN116813343A (en) * | 2023-07-04 | 2023-09-29 | 有研资源环境技术研究院(北京)有限公司 | Inorganic electrochromic film-forming material and preparation method thereof |
| CN116835981A (en) * | 2023-07-05 | 2023-10-03 | 宁波江丰电子材料股份有限公司 | Metal oxide target material and preparation method and application thereof |
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Application publication date: 20200103 |