CN110331367B - Preparation method of stannous tungstate film - Google Patents
Preparation method of stannous tungstate film Download PDFInfo
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- CN110331367B CN110331367B CN201910740581.5A CN201910740581A CN110331367B CN 110331367 B CN110331367 B CN 110331367B CN 201910740581 A CN201910740581 A CN 201910740581A CN 110331367 B CN110331367 B CN 110331367B
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- stannous
- tungstate film
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
Abstract
The invention belongs to the technical field of conductive oxide films, and particularly discloses a preparation method of a stannous tungstate film. The invention utilizes a radio frequency co-sputtering method, and the vacuum degree is 4-7x10‑4Introducing mixed gas of oxygen and argon into a Pa reaction cavity, respectively applying 80-150W of power to a tin target and a tungsten target through a radio frequency power supply to form plasma, wherein the partial pressure of the argon is 0.9Pa, and O is2Partial pressure of 0 to 0.42Pa, deposition time of 30 seconds to 10 minutes, and after completion of the deposition, vacuum annealing at 600 ℃ for 20 minutes. The stannous tungstate film is prepared by adopting a radio frequency co-sputtering method, so that the optical band gap of the stannous tungstate film is reduced, the stannous tungstate film is adaptive to photo-hydrolysis, and the stannous tungstate film can be better applied to photo-hydrolysis, such as hydrogen evolution reaction.
Description
Technical Field
The invention belongs to the technical field of conductive oxide films, and particularly relates to a preparation method of a stannous tungstate film.
Background
Ternary oxides have attracted extensive attention in oxygen generation reactions (OERs), which greatly increases the range of materials available for oxygen generation reactions. The best performing material of the ternary compound over the last decade has been BiVO4The band gap is 2.5-2.7 eV, and the maximum photocurrent is 6.9 mA cm-2The maximum hydrogen evolution efficiency (STH) is up to 8%. However, since the band gap of the material is too large, the STH efficiency thereof remains low, and it is necessary to lower the band gap thereof and improve the STH efficiency by an appropriate method. Stannous tungstate alpha-SnWO4The electron band of (a) spans the conduction band and the valence band of the water-splitting redox potential ifThe band gap range can be adjusted to a small range, which is very advantageous for the water splitting reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a stannous tungstate film.
The invention adopts a radio frequency Reaction (RF) magnetron co-sputtering method to prepare the stannous tungstate film and control the components of the film.
The technical scheme adopted by the invention is as follows:
a preparation method of a stannous tungstate film utilizes a radio frequency co-sputtering method and a vacuum degree of 4-7x10-4And introducing mixed gas of oxygen and argon into a reaction cavity of the Pa, applying 80-150W of power to the tin target and the tungsten target through a radio frequency power supply to form plasma, wherein the partial pressure of the argon is 0.9Pa, the partial pressure of the oxygen is 0-0.42 Pa, the deposition time is 30 seconds-10 minutes, and after the deposition is finished, performing vacuum annealing at 600 ℃ for 20 minutes.
In order to realize an efficient photo-oxidation process, the band gap of the photoelectric material must be larger than the photo-hydrolysis energy by 1.23V, and the optimal band gap is between 1.5 and 1.7 eV. To achieve this band gap range, the composition of the film must be changed.
The method prepares the stannic tungstate film by changing the conditions of a magnetron co-sputtering method.
Preferably, the oxygen partial pressure is 0.15 Pa.
Because the oxygen content affects the deposition rate of Sn and W, thereby affecting the content of Sn and W in the film, the invention adjusts the oxygen partial pressure to obtain the stannum tungstate film with the optimal stoichiometric ratio, thereby obtaining the film with good performance.
Compared with the prior art, the invention has the beneficial effects that:
the stannous tungstate film is prepared by adopting a radio frequency co-sputtering method, so that the optical band gap of the stannous tungstate film is reduced, the stannous tungstate film is adaptive to photo-hydrolysis, and the stannous tungstate film can be better applied to photo-hydrolysis, such as hydrogen evolution reaction.
Drawings
FIG. 1 is a schematic view of a thin film deposition process according to the present invention.
FIG. 2 is a schematic view of a method for preparing a thin film according to the present invention.
FIG. 3 shows the composition of Sn/W with O in the RF co-sputtering process, with Sn and W powers of 100W, during crystallization of Sn-tungstate film at 600 deg.C2And (3) a change law graph of partial pressure.
FIG. 4 shows the optical band gap of a stannous tungstate film crystallized in vacuum at 600 ℃ along with O2Graph of variation of partial pressure.
Detailed Description
The following further describes the embodiments of the present invention with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The operation steps are as follows:
1. and (4) placing the cleaned FTO and Si sheets on a sample table.
2. The vacuum degree of the reaction chamber is pumped to 4 x10-4Pa（4~7*10-4Pa, the vacuum degree in the above range).
3. Introduction of O2And Ar.
4. 100W of power was applied to the Sn (99.99%) and W (99.95%) targets, respectively, by a radio frequency power supply.
The specific process is as follows:
preparing the stannous tungstate film at room temperature, and pumping the vacuum degree of the reaction cavity to 4-7x10-4After Pa, O is introduced2And Ar, by applying 100W of power to Sn (99.99%) and W (99.95%) targets, respectively, by a radio frequency power supply. When current is passed through the target, a plasma is formed in front of the target, sputtering atoms of the target.
The thickness of the film is controlled by varying the deposition time. For example, as the deposition time is increased from 30 seconds to 8 minutes, the film thickness is increased from 50 nm to 350 nm.
To control the ratio of Sn to W, the partial pressure of Ar was fixed at 0.9Pa, and O was varied2Partial pressure, so that it varies between 0 and 0.42 Pa. And the samples were vacuum annealed in a muffle furnace for 20 minutes at 600 ℃. FIG. 2 shows a process for preparing a thin film. When O is present2When the partial pressure is reduced from 0.42Pa to 0, the tin concentration increases and the film color changes from yellow to brown.
O was investigated by investigating the effect of different oxygen partial pressures on Sn or W film thickness2Influence of partial pressure on the composition of the tin tungstate film. The thickness of the thin film was measured with a Quartz Crystal Microbalance (QCM) (fig. 3). When mixing O2Increasing the partial pressure from 0 to 0.24Pa increases the deposition rate of W, which increases relative thickness by 13%. This is because of O2Bombarding the W target such that its sputtering rate increases. When mixing O2When the partial pressure was increased to 0.42Pa, the relative thickness was reduced by 22% because of O2The sputtered atoms are subjected to additional O2The resistance of (1). The same phenomenon occurs with Sn targets. The relative thickness increased by 9% at an oxygen partial pressure of 0.12Pa, and the relative thickness decreased by 40% at an oxygen partial pressure of 0.42 Pa. Since the melting point of Sn (232 ℃) is significantly lower than that of W (3422 ℃), the sputtering rate of Sn is significantly higher than that of W.
The optical bandgap of the stannous tungstate film is reduced from 1.87 eV to 1.57 eV, which means that the increase in Sn concentration causes it to generate additional energy levels within the bandgap (fig. 4). When mixing O2When the partial pressure is reduced to 0.075 Pa, the Sn/W ratio is reduced to 0.7, resulting in a reduction in the optical absorption of the material and an increase in its bandgap to 1.89 eV. When O is present2When the partial pressure is 0.15Pa, the sputtering speed of Sn is faster, thereby being beneficial to SnWO4Is performed. Therefore, whether the oxygen partial pressure is higher or lower than 0.15Pa, the Sn concentration is reduced, and a non-stoichiometric tin tungstate film is formed, causing defects, because: when the material composition is in a non-stoichiometric ratio, vacancy or interstitial energy defects are generated inside the material, so that the band gap of the material is larger, the optical performance of the material is reduced, and the catalytic effect and the like are influenced.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (6)
1. The preparation method of the stannous tungstate film is characterized in that a radio frequency co-sputtering method is utilized, and the vacuum degree is 4-7x10-4And introducing mixed gas of oxygen and argon into a reaction cavity of the Pa, applying 80-150W of power to the tin target and the tungsten target through a radio frequency power supply to form plasma, wherein the partial pressure of the argon is 0.9Pa, the partial pressure of the oxygen is 0.15Pa, the deposition time is 30 seconds to 10 minutes, and after the deposition is finished, performing vacuum annealing at 400-600 ℃ for 20-40 minutes.
2. The method for preparing a stannous tungstate film as claimed in claim 1, wherein a radio frequency power supply is used to apply 100W of power to the tin target and the tungsten target.
3. The method for preparing a stannous tungstate film as claimed in claim 1, wherein the purity of the tin target is 99.99%.
4. The method for preparing a stannous tungstate film as claimed in claim 1, wherein the purity of the tungsten target is 99.95%.
5. A stannous tungstate film obtained by the method for preparing a stannous tungstate film as claimed in claim 1.
6. The use of a stannous tungstate film as claimed in claim 5 in a hydrogen desorption reaction by light water.
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| CN110295355A (en) * | 2019-08-12 | 2019-10-01 | 肇庆市华师大光电产业研究院 | A kind of preparation method of wolframic acid stannous film that realizing continuous photocatalytic water |
| CN111020501A (en) * | 2019-11-28 | 2020-04-17 | 肇庆市华师大光电产业研究院 | Preparation method of copper bismuthate film |
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Non-Patent Citations (2)
| Title |
|---|
| A Study of Gas-sensing properties of sputtered alpha-SnWO4 Thin-films,Solis,JL et al,5th International Meeting on Chemical Sensors;SOLIS，JL 等;《5th International Meeting on CHemical Sensors》;19940711(第25期);591-595 * |
| 新型SnO_2_WO_3双层薄膜NO_2敏感性能研究;林伟 等;《材料科学与工艺》;20101031;第18卷(第5期);719-723,728 * |
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Inventor after: Bojeev Farabi Inventor after: Azel Akinogu Inventor after: Feng Ke Inventor after: Jin Mingliang Inventor after: Michael Gilson Inventor before: Bojeev Farabi Inventor before: Azel Akinogu Inventor before: Feng Ke Inventor before: Jin Mingliang Inventor before: Michael Gilsey |
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