CN110331367A - A kind of preparation method of wolframic acid stannous film - Google Patents
A kind of preparation method of wolframic acid stannous film Download PDFInfo
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- CN110331367A CN110331367A CN201910740581.5A CN201910740581A CN110331367A CN 110331367 A CN110331367 A CN 110331367A CN 201910740581 A CN201910740581 A CN 201910740581A CN 110331367 A CN110331367 A CN 110331367A
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- Prior art keywords
- wolframic acid
- acid stannous
- preparation
- partial pressure
- 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 conductive oxide film technical fields, specifically disclose a kind of preparation method of wolframic acid stannous film.The present invention utilizes radio frequency cosputtering method, is 4 ~ 7x10 in vacuum degree‑4In the reaction chamber of Pa, it is passed through the mixed gas of oxygen and argon gas, applies the power of 80 ~ 150W to tin target and tungsten target respectively by radio-frequency power supply, forms plasma, the partial pressure of argon gas is 0.9Pa, O2Partial pressure is 0 to 0.42Pa, and sedimentation time is 30 seconds to 10 minutes, after the completion of deposition, at vacuum annealing 20 minutes at 600 DEG C.Wolframic acid stannous film has been prepared using radio frequency cosputtering method in the present invention, makes the reduction of its optical band gap, and hydrolyze and adapt to light, can preferably it be applied in light hydrolysis, such as in evolving hydrogen reaction, furthermore, it is easy to operate using radio frequency cosputtering method, it can be realized large-scale Commercialization application.
Description
Technical field
The invention belongs to conductive oxide film technical fields, and in particular to a kind of preparation method of wolframic acid stannous film.
Background technique
Ternary oxide causes extensive concern on producing oxygen reaction (OER), anti-this considerably increases can be used for producing oxygen
Answer the range of material.In past 10 years, the best material of performance is BiVO in ternary compound4, band gap is 2.5 ~ 2.7 eV
, its maximum photoelectric current is up to 6.9 mA*cm-2, maximum liberation of hydrogen efficiency (STH) be up to 8%.But due to the band of the material
Gap is excessive, causes its STH efficiency still very low, so, its band gap is reduced by suitable method and proposes STH efficiency
Height is necessary.Wolframic acid stannous α-SnWO4Electronic band cross over water decomposition oxidation-reduction potential conduction band and valence band, such as
Its bandgap range can be adjusted to lesser range by fruit, this reacts highly beneficial to water decomposition.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention proposes a kind of preparation methods of wolframic acid stannous film.
The present invention prepares wolframic acid stannous film using radio frequency reaction (RF) magnetron cosputtering method, and control film at
Point.
The technical scheme adopted by the invention is that:
A kind of preparation method of wolframic acid stannous film is 4 ~ 7x10 in vacuum degree using radio frequency cosputtering method-4The reaction chamber of Pa
It is interior, it is passed through the mixed gas of oxygen and argon gas, applies the power of 80 ~ 150W, shape to tin target and tungsten target respectively by radio-frequency power supply
At plasma, the partial pressure of argon gas is 0.9Pa, and oxygen partial pressure is 0 to 0.42Pa, and sedimentation time is 30 seconds to 10 minutes, deposition
After the completion, at vacuum annealing 20 minutes at 600 DEG C.
In order to realize that efficient photooxidation process, the band gap of photoelectric material have to, best band bigger than light hydrolysis energy 1.23V
Gap is between 1.5 ~ 1.7 eV.In order to reach this bandgap range, it is necessary to change the ingredient of film.
This patent is to prepare wolframic acid tin thin film by changing the condition of magnetron co-sputtering.
Preferably, oxygen partial pressure is 0.15 Pa.
Due to the deposition rate of influence of oxygen content Sn and W, so that the content of Sn and W in film is influenced, therefore, tune of the present invention
Whole partial pressure of oxygen obtains the stannotungstic acid salt film of optimum chemical metering ratio, to obtain the good film of performance.
Compared with prior art, the beneficial effects of the present invention are:
Wolframic acid stannous film has been prepared using radio frequency cosputtering method in the present invention, makes the reduction of its optical band gap, and hydrolyze with light
It adapts to, can preferably be applied in light hydrolysis, such as in evolving hydrogen reaction, in addition, energy easy to operate using radio frequency cosputtering method
Enough realize large-scale Commercialization application.
Detailed description of the invention
Fig. 1 is film deposition process schematic diagram of the present invention.
Fig. 2 is method for manufacturing thin film schematic diagram of the present invention.
Fig. 3 is 100 W of tin and tungsten power in radio frequency cosputtering method, stannotungstic acid salt film tin/tungsten in 600 DEG C of crystallizations
Ingredient is with O2The changing rule figure of partial pressure.
Fig. 4 is the optical band gap at 600 DEG C in vacuum after crystallization of wolframic acid stannous film with O2The variation diagram of partial pressure.
Specific embodiment
A specific embodiment of the invention and attached drawing are described further below.It should be noted that for this
The explanation of a little embodiments is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, disclosed below
Technical characteristic involved in each embodiment of the present invention can be combined with each other as long as they do not conflict with each other.
Embodiment 1
Operating procedure is as follows:
1, FTO the and Si piece of wash clean is placed on sample stage.
2, the vacuum degree of reaction chamber is extracted into 4*10-4Pa(4 ~ 7*10-4Pa reaches above range vacuum degree).
3, it is passed through O2And Ar.
4, by radio-frequency power supply respectively to Sn(99.99%) and W(99.95%) target apply 100W power.
Detailed process is as follows:
Wolframic acid stannous film is prepared at room temperature, and the vacuum degree of reaction chamber is extracted into 4-7x10-4After Pa, it is passed through O2With mixing for Ar
Gas is closed, by radio-frequency power supply respectively to Sn(99.99%) and W(99.95%) prepared by power that target applies 100W.When on target
When having electric current to pass through, plasma will be formed in the front of target, to sputter the atom of target.
The thickness of film is controlled by changing sedimentation time.For example, increased to 8 minutes between when deposited from 30 seconds, it is thin
Film thickness increases to 350 nm from 50 nm.
In order to control the ratio of Sn and W, Ar partial pressure is fixed as 0.9Pa, changes O2Partial pressure, make its 0 to 0.42Pa it
Between change.And by sample at 600 DEG C in Muffle furnace vacuum annealing 20 minutes.Fig. 2 is the step of preparing film.Work as O2Partial pressure
When being reduced to 0 from 0.42 Pa, tin concentration increases, and film color should become brown from yellow.
O is studied by studying influence of the different partial to Sn or W film thickness2Partial pressure is to wolframic acid tin thin film ingredient
It influences.The thickness (Fig. 3) of film is measured with quartz crystal microbalance (QCM).When by O2Partial pressure from 0 increase to 0.24Pa when,
It will increase the deposition rate of W, relative thickness increases by 13%.This is because O2Bombardment W target increases its sputter rate.When by O2
When partial pressure increases to 0.42Pa, relative thickness reduces 22%, this is because O2Sputtered atom is by additional O2Obstruction.Sn target
Also there is same phenomenon.Relative thickness increases by 9% when partial pressure of oxygen is 0.12Pa, and when partial pressure of oxygen is 0.42Pa, relative thickness subtracts
Few 40%.Due to Sn(232 DEG C) fusing point be significantly lower than W(3422 DEG C), so that Sn sputter rate is significantly higher than the sputter rate of W.
The optical band gap of wolframic acid stannous film narrows down to 1.57 eV from 1.87 eV, it means that the increase of Sn concentration makes it
Additional energy level (Fig. 4) is generated in band gap.When by O2When differential pressure drop is as low as 0.075 Pa, Sn/W ratio is reduced to 0.7, causes
The optical absorption of material reduces and its band gap increases to 1.89 eV.Work as O2When partial pressure is 0.15 Pa, the sputtering rate of Sn is more
Fastly, to be conducive to SnWO4Formation.So no matter partial pressure of oxygen is higher or lower than 0.15Pa, it can all lead to the reduction of Sn concentration,
To form non-stoichiometry stannotungstic acid salt film, it is made to generate defect, the reason is that: when material group becomes non-stoichiometric
When, material internal can generate vacancy or gap energy defect, and cause material band gap bigger than normal, so that device for Optical Properties of Materials is reduced, shadow
Ring catalysis and other effects.
Above the embodiments of the present invention are described in detail, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.
Claims (7)
1. a kind of preparation method of wolframic acid stannous film, which is characterized in that utilize radio frequency cosputtering method, be 4 ~ 7x10 in vacuum degree-4In the reaction chamber of Pa, it is passed through the mixed gas of oxygen and argon gas, 80 is applied to tin target and tungsten target respectively by radio-frequency power supply ~
The power of 150W forms plasma, and the partial pressure of argon gas is 0.9Pa, and oxygen partial pressure is 0 to 0.42Pa, and sedimentation time is 30 seconds
By 10 minutes, after the completion of deposition, at vacuum annealing 20 ~ 40 minutes at 400 ~ 600 DEG C.
2. the preparation method of wolframic acid stannous film according to claim 1, which is characterized in that O2Partial pressure is 0.15 Pa.
3. the preparation method of wolframic acid stannous film according to claim 1, which is characterized in that by radio-frequency power supply respectively to tin
Target and tungsten target apply the power of 100W.
4. the preparation method of wolframic acid stannous film according to claim 1, which is characterized in that the purity of tin target is 99.99%.
5. the preparation method of wolframic acid stannous film according to claim 1, which is characterized in that the purity of tungsten target is 99.95%.
6. the wolframic acid stannous film that the preparation method of wolframic acid stannous film described in a kind of claim 1 obtains.
7. a kind of application of the wolframic acid stannous film described in claim 6 in light hydrolysis evolving hydrogen reaction.
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| CN201910740581.5A CN110331367B (en) | 2019-08-12 | 2019-08-12 | Preparation method of stannous tungstate film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021027381A1 (en) * | 2019-08-12 | 2021-02-18 | 肇庆市华师大光电产业研究院 | Preparation method for stannous tungstate film for achieving continuous photolysis of water |
| WO2021103478A1 (en) * | 2019-11-28 | 2021-06-03 | 肇庆市华师大光电产业研究院 | Preparation method for bismuth acid copper film |
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2019
- 2019-08-12 CN CN201910740581.5A patent/CN110331367B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021027381A1 (en) * | 2019-08-12 | 2021-02-18 | 肇庆市华师大光电产业研究院 | Preparation method for stannous tungstate film for achieving continuous photolysis of water |
| WO2021103478A1 (en) * | 2019-11-28 | 2021-06-03 | 肇庆市华师大光电产业研究院 | Preparation method for bismuth acid copper film |
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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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