CN103572237A - Preparation method of boron-doped diamond-like carbon film electrode - Google Patents
Preparation method of boron-doped diamond-like carbon film electrode Download PDFInfo
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- CN103572237A CN103572237A CN201310568131.5A CN201310568131A CN103572237A CN 103572237 A CN103572237 A CN 103572237A CN 201310568131 A CN201310568131 A CN 201310568131A CN 103572237 A CN103572237 A CN 103572237A
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Abstract
The invention provides a preparation method of a boron-doped diamond-like carbon film electrode. The preparation method is characterized in that boron is used as a doping element; a linear ion-source deposition technology and a magnetron sputtering deposition technology are combined; a boron target is used as a sputtering target; and a carbon-containing gas source is fed into the preparation system, a carbon film is deposited by the linear ion-source deposition technology and simultaneously, a boron element is subjected to sputtering deposition so that a boron-doped diamond-like carbon film is obtained, and the boron-doped diamond-like carbon film is connected to a lead so that the boron-doped diamond-like carbon film electrode is obtained. Compared with the prior art, the preparation method is green and environmentally friendly and has simple processes and a low cost. The boron-doped diamond-like carbon film electrode has good electrochemical properties and a good application prospect.
Description
Technical field
The present invention relates to diamond-like thin film electrode technical field, be specifically related to a kind of preparation method of boron doped diamond membrane electrode
Background technology
, as mercury electrode, noble metal electrode and carbon pole (as graphite, glass carbon, RESEARCH OF PYROCARBON etc.) have good application, but all there is certain defect in traditional electrode.For example, mercury electrode is poisonous and can not use at positive potential; Gold and platinum electrode easily detected liquid pollute, and biocompatibility is poor, is difficult to realize the online detection in body; The resistance to solution corrosion of carbon pole is poor, electrode poor repeatability, and limited electrochemical potential window has limited its sensing range; Boron-doped diamond film electrode has very strong anti-poisoning, contamination resistance, corrosion-resistant, and there is wide electromotive force window and low background current, but film-forming temperature high (conventionally more than 800 ℃), it is high that substrate temperature tolerance requires, surface irregularity porous, surface treatment and reproduce difficulty, and be difficult to prepare big area even thickness film, this has greatly limited its application.
Diamond like carbon film has the characteristic that is similar to diamond thin, as high hardness, wear resistance, thermal conductivity, insulativity, high optical transmission and light refractive index, good chemical stability, resistance to corrosion and biocompatibility etc., there is in addition the low film formation temperature (can at room temperature deposit) that is better than diamond thin, substrate is applied widely, is specially adapted to the preparation of microelectrode and broad-area electrode, so diamond like carbon film is extensive in a plurality of fields application prospect.But, still there is some problems as the application of electrode materials in diamond like carbon film, for example, diamond like carbon film prepared by energetic plasma exists higher internal stress (or claiming stress), more than its value can reach 10GPa, had a strong impact on the cohesive strength of film and substrate; The resistivity of diamond like carbon film, between metal and isolator, can reach 10
6more than Ω cm, limit to a certain extent the application of its semiconductor material as good conduction on device, and affected its current-responsive as electrode materials.
At present, generally adopt the method for mixing impurity element in diamond like carbon film to reduce the resistivity of film, adjust conductivity, and form new active site at film surface, increase it as the detection sensitivity of electrode.For example, publication number is in the Chinese patent of CN1963484A, to disclose a kind of preparation method of phosphorus doping amorphous diamond film electrode, the concrete phosphine gas that adopts is as doped source, while utilizing filtered cathodic vacuum arc depositing system to carry out carbon film deposition, carry out phosphorus doping and make phosphorus doping non-crystal diamond film, then connect wire, carry out electrochemical treatment, obtain phosphorus doping amorphous diamond film electrode.But this preparation method's Shortcomings is: (one) doped source phosphine gas is poisonous, had a strong impact on preparation personnel's health; (2) surfactivity of the electrode materials obtaining after phosphorus doping non-crystal diamond film connection wire is lower, therefore need to pass through electrochemical treatment, to remove the zone of oxidation of electrode material surface, thereby improve the active site of electrode materials, but this electrochemical treatment process has increased complexity prepared by electrode greatly.
Summary of the invention
Technical purpose of the present invention is the deficiency existing for above-mentioned diamond-like thin film electrode, and a kind of preparation method of boron doped diamond membrane electrode is provided, and the method is green non-poisonous, and technique is simple, and the electrode making has good chemical property.
The present invention realizes the technical scheme that above-mentioned technical purpose adopts: a kind of preparation method of boron doped diamond membrane electrode, select boron as doped element, the method preparation that adopts linear ion source deposition technique to combine with magnetron sputtered deposition technology, concrete preparation process is as follows:
Step 1, carry out surface etching treatment after will matrix cleaning;
Step 3: the matrix after step 2 is processed is connected with wire, then that its surrounding and back of the body surface is coated with epoxy resin, not coated film, as electrode surface, obtains boron doped diamond membrane electrode.
Described body material is not limit, and is preferably electro-conductive material, such as high conductive silicon chip, metal etc.
In described step 1, as preferably, ultrasonic cleaning is selected in the cleaning of matrix.
In described step 1, as preferably, the surface etch of matrix is ion etching, detailed process is preferably: matrix is put into cavity, cavity is vacuumized to processing, then pass into rare gas element, open linear ion source and bias voltage, utilize inert gas ion beam to carry out etching to matrix.Further preferably, substrate bias is-50V～-200V, linear ion source electric current 0.1A～0.3A, and etching time is 5min～40min.
In described step 2, carbon containing source of the gas includes but not limited to methane, acetylene etc.
In described step 2, as preferably, substrate bias is-100V, and linear ion source electric current is 0.2A, and the working current of sputtering target is 0.2A～1.5A, depositing time 20～30min.
In described step 3, as preferably, wire is connected to matrix back of the body surface.
In described step 3, as preferably, first at boron doped diamond film surface metallizing microelectrode, then on this metal microelectrode surface, connect wire.
Compare with the preparation method of the existing diamond like carbon film containing doped element, the present invention has following beneficial effect:
(1) select boron as doped element, and the preparation method who adopts linear ion source deposition technique to combine with magnetron sputtered deposition technology, because doped source is solid-state boron target, not having the toxicity of gaseous state, liquid doped source on the one hand, is a kind of preparation method of green health; The boron doped diamond film surface making is on the other hand smooth, and roughness is less, can save electrochemical treatment process, thereby has greatly simplified preparation technology, has reduced cost;
(2) the boron doped diamond film film surface making is smooth, and roughness is less, and its internal stress is little, good with the film-substrate cohesion of matrix;
(3) compare with phosphorus doping amorphous diamond film electrode, boron doped diamond membrane electrode does not need to carry out electrochemical treatment, simplified electrode preparation process, the boron doped diamond membrane electrode simultaneously making has good electrochemical activity, in sulphuric acid soln, there is very wide electromotive force window, its value is for more than 4.0V, and low background current; And electric transmission speed that this electrode reduces in reversible system at one-electron oxidation is fast, reversibility is good, repeatability and having good stability;
(4) in the deposition process of film, temperature is lower, and generally lower than 50 ℃, and sedimentation rate is very fast, therefore can realize the low temperature preparation of microelectrode and large area film electrode, and thickness is controlled to several microns from several nanometers.
Accompanying drawing explanation
Fig. 1 is the second ion mass spectroscopy figure of the boron doped diamond film that makes in the embodiment of the present invention 1;
Fig. 2 is that the boron doped diamond membrane electrode that makes in the embodiment of the present invention 1 is at 0.5M H
2sO
4electrochemical potential window and background current in solution;
Fig. 3 is that the boron doped diamond membrane electrode electrode that makes in the embodiment of the present invention 1 is at 10mMK
3fe (CN)
6with the cyclic voltammetry result figure in the mixing solutions of 1M KCl.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
In the present embodiment, the preparation method of diamond-like thin film electrode who mixes boron is as follows:
(1) matrix cleaning, surface ion etching:
Matrix is selected silicon chip, by silicon chip ultrasonic cleaning 15min, then dries up and puts into vacuum chamber, is fixed on work supporting block; Treat that cavity internal gas pressure is less than 2.0 * 10
-5after Torr, pass into 40sccm argon gas, open linear ion source and bias voltage, adjusting substrate bias is-100V that linear ion source electric current 0.2A, utilizes ar-ion beam to matrix etching 5min, after etching finishes, stops passing into argon gas, closes bias voltage and linear ion source;
(2) film preparation:
Open linear ion source, sputtering target power supply and bias voltage; Setting linear ion source electric current is 0.2A, passes into 20sccm acetylene; Sputtering target is boron target, and the working current of adjusting sputtering target is 0.2～1.5A, passes into 60sccm argon gas Boron Sputtered target; Setting silicon chip bias voltage is-100V, at silicon chip surface, carries out thin film deposition, and depositing time 20～30min, obtains boron doped diamond film.
The above-mentioned boron doped diamond film surface making is smooth.Adopt second ion mass spectroscopy to analyze this film, as shown in Figure 1, boron atom is effectively incorporated in film analytical results.
(3) electrode preparation
Silicon chip extracting after step (2) is processed, is cut into 1 * 1cm
2size, use conductive resin that wire is connected to its back side, surrounding and the back side are coated with epoxy resin, and the boron doped diamond film surface not being wrapped by exposing is the useful area of boron doped diamond membrane electrode, obtains boron doped diamond membrane electrode.
The above-mentioned boron doped diamond membrane electrode making is put into three-electrode electro Chemical test macro, at 0.5M H
2sO
4electrochemical potential window and the background current of in solution, measuring this electrode, measuring result as shown in Figure 2.As can be seen from Figure 2:
(1) potential range of this membrane electrode in sulphuric acid soln is-2.2V～2.17V, and its electrochemical potential window is about 4.4V, and wider than the gesture window result of existing open report, this membrane electrode has very wide electrochemical potential window in sulphuric acid soln; The electromotive force window of electrode is larger, the oxygen on anode and the hydrogen on negative electrode is more difficult separates out, thus be more conducive to adopt electrochemical method catalyzing oxidizing degrading organic pollutant;
(2) simultaneously, the background current of this membrane electrode in sulphuric acid soln is only 3 ± 2 μ A/cm
2, it has very low background current, therefore can significantly improve the signal to noise ratio of electrode, is conducive to improve the detection sensitivity of electrode when detecting micro substance.
The above-mentioned boron doped diamond membrane electrode making is put into three-electrode electro Chemical test macro, at 10mM K
3fe (CN)
6with in the mixing solutions of 1M KCl, measure the reversibility of this electrode, test result is as follows:
(1) when scanning speed is 50mV/s, circulate 10 times measuring result as shown in Figure 3, as can be seen from Figure 3, the redox peak potential difference of this membrane electrode is 92mV, electrode has very large current-responsive, electric transmission speed is fast; In solution, circulate 10 times, this measuring result has repeatability.
(2) scanning speed be respectively 20,50,80,110,140,170, during 200mV/s, increase along with scanning speed, redox peak current increases, and the square root of peak point current and scanning speed is directly proportional, illustrate that electrode kinetics is mainly subject to diffusion control, electrode shows as Quasi-reversible process.
Embodiment 2:
In the present embodiment, the preparation method of diamond-like thin film electrode who mixes impurity element is basic identical with embodiment 1, and difference is that step (3) is as follows,
Silicon chip extracting after step (2) is processed, is cut into 1 * 1cm
2size, is used conductive resin that wire is connected to its back side,
(3) by the silicon chip extracting after step (2) processing, be cut into 1 * 1cm
2size, first in film surface evaporation, plate layer of metal microelectrode, then use conductive resin that wire is connected on this metal microelectrode, then the surrounding of film and the back side are wrapped up with epoxy resin, the part of exposing is the useful area of boron doped diamond membrane electrode.
The above-mentioned boron doped diamond membrane electrode making is put into and three-electrode electro Chemical test macro identical described in embodiment 1, at 0.5M H
2sO
4electrochemical potential window and the background current of in solution, measuring this electrode, measuring result is similar to Figure 2, and this membrane electrode has very wide electrochemical potential window and low background current in sulphuric acid soln.
The above-mentioned boron doped diamond membrane electrode making is put into and three-electrode electro Chemical test macro identical described in embodiment 1, at 10mM K
3fe (CN)
6with in the mixing solutions of 1M KCl, measure the reversibility of this electrode, test result is similar to Figure 3, this electrode has very large current-responsive, electric transmission speed is fast, and electrode shows as Quasi-reversible process.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making within the scope of principle of the present invention, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a preparation method for boron doped diamond membrane electrode, is characterized in that: the method preparation that adopts linear ion source deposition technique to combine with magnetron sputtered deposition technology, and specifically preparation process is as follows:
Step 1, carry out surface etching treatment after will matrix cleaning;
Step 2, setting linear ion source electric current are 0.1A～0.3A, pass into carbon containing source of the gas; Sputtering target is boron target, and the working current of adjusting sputtering target is 0.2A～1.5A, passes into argon gas and carries out sputter; Setting substrate bias is-50V～-250V; Open linear ion source, sputtering target power supply and bias voltage, at matrix front surface, carry out thin film deposition, obtain boron doped diamond film;
Step 3: the matrix after step 2 is processed is connected with wire, then that its surrounding and back of the body surface is coated with epoxy resin, not coated film, as electrode surface, obtains boron doped diamond membrane electrode.
2. the preparation method of boron doped diamond membrane electrode according to claim 1, is characterized in that: in described step 1, matrix is conductor.
3. the preparation method of boron doped diamond membrane electrode according to claim 1, it is characterized in that: in described step 1, the surface etch of matrix is ion etching, detailed process is: matrix is put into cavity, cavity is vacuumized to processing, then pass into rare gas element, open linear ion source and bias voltage, utilize inert gas ion beam to carry out etching to matrix.
4. the preparation method of boron doped diamond membrane electrode according to claim 3, is characterized in that: in described step 1, substrate bias is-50V～-200V, linear ion source electric current 0.1A～0.3A, and etching time is 5min-40min.
5. the preparation method of boron doped diamond membrane electrode according to claim 1, is characterized in that: in described step 2, carbon containing source of the gas comprises methane and acetylene.
6. the preparation method of boron doped diamond membrane electrode according to claim 1, is characterized in that: in described step 2, substrate bias is-100V that linear ion source electric current is 0.2A, depositing time 20～30min.
7. the preparation method of boron doped diamond membrane electrode according to claim 1, is characterized in that: in described step 3, first at boron doped diamond film surface metallizing microelectrode, then on this metal microelectrode surface, connect wire.
8. the preparation method of boron doped diamond membrane electrode according to claim 1, is characterized in that: in described step 3, wire is connected to matrix back of the body surface.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294230A (en) * | 2014-10-09 | 2015-01-21 | 中国科学院宁波材料技术与工程研究所 | High-hardness and low-stress multi-element composite diamond-like coating and preparation method thereof |
| CN105241569A (en) * | 2015-09-21 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Metal-doped amorphous carbon film temperature-sensing element and preparation method therefor |
| CN107389217A (en) * | 2017-06-20 | 2017-11-24 | 西安交通大学 | A kind of temperature sensor chip based on ultra-high resistance temperature coefficient amorphous carbon film |
| CN107389215A (en) * | 2017-06-20 | 2017-11-24 | 西安交通大学 | A kind of superelevation linearity temperature sensor chip based on amorphous carbon-film |
| CN113897675A (en) * | 2021-09-15 | 2022-01-07 | 湖南新锋先进材料科技有限公司 | Diamond-doped particles and preparation method and application thereof |
| CN114380363A (en) * | 2022-03-23 | 2022-04-22 | 北京博大紫辉科技有限公司 | Boron-doped diamond electrode sewage treatment module and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192787A (en) * | 1995-06-07 | 1998-09-09 | 先进耐火技术公司 | Electrically tunable coatings |
| CN1963484A (en) * | 2006-11-22 | 2007-05-16 | 哈尔滨工业大学 | Phosphorus-doped amorphous diamond film electrode and preparation method of the same |
| JP2008045180A (en) * | 2006-08-18 | 2008-02-28 | Denso Corp | Method for depositing dlc film, and manufacturing apparatus of dlc film |
| TW201015623A (en) * | 2008-10-09 | 2010-04-16 | Univ Nat Taipei Technology | Manufacturing method for semiconductor diamond-like carbon film |
| CN101792898A (en) * | 2010-04-09 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Carbon film for improving abrasion resistance of magnesium alloy and preparation method thereof |
-
2013
- 2013-11-14 CN CN201310568131.5A patent/CN103572237B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192787A (en) * | 1995-06-07 | 1998-09-09 | 先进耐火技术公司 | Electrically tunable coatings |
| JP2008045180A (en) * | 2006-08-18 | 2008-02-28 | Denso Corp | Method for depositing dlc film, and manufacturing apparatus of dlc film |
| CN1963484A (en) * | 2006-11-22 | 2007-05-16 | 哈尔滨工业大学 | Phosphorus-doped amorphous diamond film electrode and preparation method of the same |
| TW201015623A (en) * | 2008-10-09 | 2010-04-16 | Univ Nat Taipei Technology | Manufacturing method for semiconductor diamond-like carbon film |
| CN101792898A (en) * | 2010-04-09 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Carbon film for improving abrasion resistance of magnesium alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郭延龙等: "非金属掺杂类金刚石膜的研究进展", 《激光与广电子学进展》, 30 April 2009 (2009-04-30), pages 33 - 37 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294230A (en) * | 2014-10-09 | 2015-01-21 | 中国科学院宁波材料技术与工程研究所 | High-hardness and low-stress multi-element composite diamond-like coating and preparation method thereof |
| CN105241569A (en) * | 2015-09-21 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Metal-doped amorphous carbon film temperature-sensing element and preparation method therefor |
| CN105241569B (en) * | 2015-09-21 | 2018-01-30 | 中国科学院宁波材料技术与工程研究所 | A kind of metal-doped amorphous carbon film temperature-sensing element and preparation method thereof |
| CN107389217A (en) * | 2017-06-20 | 2017-11-24 | 西安交通大学 | A kind of temperature sensor chip based on ultra-high resistance temperature coefficient amorphous carbon film |
| CN107389215A (en) * | 2017-06-20 | 2017-11-24 | 西安交通大学 | A kind of superelevation linearity temperature sensor chip based on amorphous carbon-film |
| CN113897675A (en) * | 2021-09-15 | 2022-01-07 | 湖南新锋先进材料科技有限公司 | Diamond-doped particles and preparation method and application thereof |
| CN114380363A (en) * | 2022-03-23 | 2022-04-22 | 北京博大紫辉科技有限公司 | Boron-doped diamond electrode sewage treatment module and manufacturing method thereof |
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