CN100595578C - Method for preparing platinum nano-perforated electrode by evaporation deposition - Google Patents
Method for preparing platinum nano-perforated electrode by evaporation deposition Download PDFInfo
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- CN100595578C CN100595578C CN200810039485A CN200810039485A CN100595578C CN 100595578 C CN100595578 C CN 100595578C CN 200810039485 A CN200810039485 A CN 200810039485A CN 200810039485 A CN200810039485 A CN 200810039485A CN 100595578 C CN100595578 C CN 100595578C
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Abstract
The invention discloses a method for preparing a poriferous nano platinum electrode which can be used for fuel batteries and non-enzyme glucose measuring through vapor depositing, and belongs to the technical field of material preparation, electrochemical batteries and electrochemical analysis. The method for preparing the poriferous nano platinum electrode uses an electron beam vapor depositing method for depositing a platinum alloy layer on a substrate, and uses an electrochemical and mechanical erosion method so as to implement dealloying, thus producing the poriferous nano platinum electrode. The method for preparing the poriferous nano platinum electrode has following advantages: the electron beam vapor depositing ensures the excellent repeatability of the components and the thicknessof platinum and silicon alloy films and consequently the excellent repeatability of poriferous nano platinum films, and the method is applicable to batch production.
Description
Technical field
The present invention relates to a kind of method with preparing platinum nano-perforated electrode by evaporation deposition, platinum nanometer perforated electrodes can be used for fuel cell and no enzyme detects glucose, belongs to the technical field of material preparation and electrochemical cell and electrochemical analysis.
Background technology
At present, platinum nanometer perforated electrodes has been applied to fuel cell and field of biosensors.The preparation method of research platinum nanometer perforated electrodes more and more is subjected to domestic and international researchist's attention.Can under neutrallty condition, detect glucose by no enzyme as the platinum nanometer perforated electrodes of making as template with liquid crystal (roughness is greater than 72) [1], also not be subjected to the interference of other interference element.But preparation method's complexity of electrode, time-consuming, poor repeatability are not suitable for producing in enormous quantities.
Summary of the invention
The objective of the invention is to overcome current platinum nanometer perforated electrodes preparation and go up the deficiency that exists,, be not suitable for producing in enormous quantities etc., propose a kind of method with preparing platinum nano-perforated electrode by evaporation deposition as preparation method's complexity, time-consuming, poor repeatability.
For achieving the above object, the present invention adopts following technical scheme: the deposited by electron beam evaporation deposition process deposits one deck platinum alloy on substrate, use the electrochemical etching method removal alloying then, makes platinum nanometer perforated electrodes.
Now describe technical scheme of the present invention in detail.A kind of method with preparing platinum nano-perforated electrode by evaporation deposition, need in the equipment of electric arc furnaces, electron-beam evaporation device, electrolytic cell and under the electrochemical workstation power supply, to implement, working electrode is installed in the electrolytic cell, to electrode, contrast electrode, it is characterized in that, working electrode is a silicon substrate, the concrete operations step:
First step surface treatment surface of silicon substrate
With the cleaning method in the standard microelectronics planar technology surface of silicon substrate is cleaned up, stand-by;
Second step preparation PtSi alloy
Take by weighing purity respectively and be 99.999% platinum and silicon 1.56g and 0.0562g, be smelted into the PtSi alloy in electric arc furnaces, melting three times makes the PtSi alloy, and chemical analysis shows that the atomic ratio of platinum and silicon is 8: 2;
The 3rd step hydatogenesis PtSi alloy film on silicon substrate
The PtSi alloy that titanium, platinum, second step are made places respectively in three crucibles of electron-beam evaporation device, silicon substrate is placed on the deposition table, with titanium, platinum and PtSi alloy hydatogenesis successively on silicon substrate, the average thickness of three kinds of films is respectively 1nm, 30nm and 150nm, the Ti film can strengthen sticking between silicon substrate and the platinum film, and platinum film is as the restraining barrier, stops that electroetching solution in the subsequent step is to the corrosion of silicon substrate;
The 4th step preparation Si electroetching solution
Draw 3.0ml hydrofluorite in the 100ml volumetric flask, be diluted with water to scale, make Si electroetching solution for later use;
Si in the 5th step electroetching etching off PtSi alloy film
After depositing the silicon substrate scribing of PtSi alloy film on the surface, be mounted to working electrode, insert Si electroetching solution with contrast electrode with to electrode, electrochemical workstation provides constant voltage for working electrode with to electrode, constant voltage is between the 200-500 millivolt, contrast electrode provides reference potential, reduce to zero to the etching electric current, make the platinum nanometer perforated electrodes crude product;
The 6th step preparation electrode cleaning solution
Draw the 5.4ml concentrated sulphuric acid in the 100ml volumetric flask, be diluted with water to scale, make the 1.0M sulfuric acid solution, i.e. the electrode cleaning solution;
The 7th step was removed the impurity that remains in platinum nanometer perforated electrodes crude product surface
With working electrode, contrast electrode, electrode cleaned up the back insert the electrode cleaning solution, electrochemical workstation provides+1.0 volts to-0.45 volt scanning voltages for working electrode with to electrode, contrast electrode provides reference potential, be scanned up to acquisition repeatably the volt-ampere cyclic curve till, so far, make platinum nanometer perforated electrodes, platinum nanometer perforated electrodes is exactly the silicon substrate that surface deposition has platinum nanometer perforated film.
Compare with background technology, the present invention has following advantage:
1, electron-beam evaporation guarantees that the component of platinum silicon alloy film and thickness have excellent repeatability, guarantees that then platinum nanometer perforated film has excellent repeatability;
2, be fit to produce in enormous quantities.
Description of drawings
Fig. 1 is the electro chemical etching apparatus synoptic diagram of preparation porous platinum electrode of the present invention.Among the figure, the 1st, electrochemical workstation, the 2nd, working electrode, the 3rd, contrast electrode, the 4th, to electrode, the 5th, electrolyte solution is respectively when different step: during Si in the electroetching etching off PtSi alloy film, electrolyte solution is silicon etching solution 5a; When removal remained in the impurity on platinum nanometer perforated electrodes crude product surface, electrolyte solution was electrode cleaning solution 5b; The 6th, electrolytic cell.
Fig. 2 is an electron-beam evaporation device synoptic diagram.21 is electron beam emissive sources among the figure; The 22nd, the electromagnetic control apparatus 23 of controlling electron beam direction of motion is the crucible that titanium is housed; The 24th, the crucible 25 that platinum is housed is crucibles that the platinum silicon alloy is housed; The 27th, vacuum chamber, 31 are mounted in the silicon substrate on the deposition platform.
Fig. 3,4 and 5 is synoptic diagram of platinum nanometer perforated electrodes preparation process.Among the figure, the 32nd, titanium adhesion layer 33 is platinum films; The 34th, the platinum silicon alloy film; The 35th, through the platinum nanometer perforated film of electroetching removal alloying formation.
Fig. 6 is the image through the scanning electron microscope of the platinum nanometer perforated film of electroetching removal alloying formation.
Embodiment
Now describe technical scheme of the present invention in conjunction with the accompanying drawings and embodiments in detail.All embodiment all operate according to above-mentioned preparation method's concrete operations step, and each embodiment is only enumerated crucial technical data.
In the 5th step, the constant voltage that electrochemical workstation 1 provides is 200 millivolts.
In the 5th step, the constant voltage that electrochemical workstation 1 provides is 350 millivolts.
In the 5th step, the constant voltage that electrochemical workstation 1 provides is 500 millivolts.
The platinum nanometer perforated electrodes of method preparation of the present invention is particularly suitable for being used for the electrode in fuel cell and the no enzyme detection glucose.
List of references
[1]Sejin?Park，Taek?Dong?Chung，Hee?Chan?Kim，Nonenzymatic?GlucoseDetection?Using?Mesoporous?Platinum，Anal.Chem.2003，75，3046-3049
Claims (1)
1, a kind of method with preparing platinum nano-perforated electrode by evaporation deposition, need in the equipment of electric arc furnaces, electron-beam evaporation device, electrolytic cell and under the electrochemical workstation power supply, to implement, working electrode is installed in the electrolytic cell, to electrode, contrast electrode, it is characterized in that, working electrode is a silicon substrate, the concrete operations step:
First step surface treatment surface of silicon substrate
With the cleaning method in the standard microelectronics planar technology surface of silicon substrate is cleaned up, stand-by;
Second step preparation PtSi alloy
Take by weighing purity respectively and be 99.999% platinum and silicon 1.56g and 0.0562g, be smelted into the PtSi alloy in electric arc furnaces, melting three times makes the PtSi alloy, and chemical analysis shows that the atomic ratio of platinum and silicon is 8: 2;
The 3rd step hydatogenesis PtSi alloy film on silicon substrate
The PtSi alloy that titanium, platinum, second step are made places respectively in three crucibles of electron-beam evaporation device, silicon substrate is placed on the deposition table, with titanium, platinum and PtSi alloy hydatogenesis successively on silicon substrate, the average thickness of three kinds of films is respectively 1nm, 30nm and 150nm, the Ti film can strengthen sticking between silicon substrate and the platinum film, and platinum film is as the restraining barrier, stops that electroetching solution in the subsequent step is to the corrosion of silicon substrate;
The 4th step preparation Si electroetching solution
Draw 3.0ml hydrofluorite in the 100ml volumetric flask, be diluted with water to scale, make Si electroetching solution for later use;
Si in the 5th step electroetching etching off PtSi alloy film
After depositing the silicon substrate scribing of PtSi alloy film on the surface, be mounted to working electrode, insert Si electroetching solution with contrast electrode with to electrode, electrochemical workstation provides constant voltage for working electrode with to electrode, constant voltage is between the 200-500 millivolt, contrast electrode provides reference potential, reduce to zero to the etching electric current, make the platinum nanometer perforated electrodes crude product;
The 6th step preparation electrode cleaning solution
Draw the 5.4ml concentrated sulphuric acid in the 100ml volumetric flask, be diluted with water to scale, make the 1.0M sulfuric acid solution, i.e. the electrode cleaning solution;
The 7th step was removed the impurity that remains in platinum nanometer perforated electrodes crude product surface
With working electrode, contrast electrode, electrode cleaned up the back insert the electrode cleaning solution, electrochemical workstation provides+1.0 volts to-0.45 volt scanning voltages for working electrode with to electrode, contrast electrode provides reference potential, be scanned up to acquisition repeatably the volt-ampere cyclic curve till, so far, make platinum nanometer perforated electrodes, platinum nanometer perforated electrodes is exactly the silicon substrate that surface deposition has platinum nanometer perforated film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017206447A1 (en) * | 2016-05-28 | 2017-12-07 | 惠州市力道电子材料有限公司 | Porous metal surface-modified interdigitated electrodes, manufacturing method thereof, and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105869990B (en) * | 2015-01-22 | 2020-02-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing silicon-based nano graphic array structure |
| CN106093121A (en) * | 2016-05-28 | 2016-11-09 | 惠州市力道电子材料有限公司 | A kind of surface is provided with the matrix of nano-porous gold, its preparation method and application |
| CN107422012B (en) * | 2017-06-09 | 2020-04-03 | 清华大学 | Electrochemical biosensor electrode, sensor and preparation method thereof |
| CN107422015B (en) * | 2017-07-19 | 2020-03-27 | 清华大学 | Gold film electrode, electrochemical biosensor electrode, sensor and preparation method thereof |
| US10040948B1 (en) * | 2017-11-21 | 2018-08-07 | Uxn Co., Ltd. | Method of making a colloid and nanoporous layer |
| CN108018531B (en) * | 2017-11-27 | 2020-04-17 | 天津大学 | Method for preparing nano porous metal material |
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Non-Patent Citations (3)
| Title |
|---|
| A nonenzymatic glucose sensor using nanoporous platinumelectrodes prepared by electrochemical alloying/dealloying ina water-insensitive zinc chloride-1-ethyl-3-methylimidazoliumchloride ionic liquid. Chou CH，etal.Electroanalysis,Vol.20 No.7. 2008 |
| A nonenzymatic glucose sensor using nanoporous platinumelectrodes prepared by electrochemical alloying/dealloying ina water-insensitive zinc chloride-1-ethyl-3-methylimidazoliumchloride ionic liquid. Chou CH,etal.Electroanalysis,Vol.20 No.7. 2008 * |
| Nonenzymaticglucosedetectionbyusingathree-dimensionallyordered macroporous platinum template. Song YY，etal.Chemistry-A European Journal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206447A1 (en) * | 2016-05-28 | 2017-12-07 | 惠州市力道电子材料有限公司 | Porous metal surface-modified interdigitated electrodes, manufacturing method thereof, and application |
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