CN104962876A - Boron-doped diamond film material on surface of graphite and preparation method thereof - Google Patents
Boron-doped diamond film material on surface of graphite and preparation method thereof Download PDFInfo
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- CN104962876A CN104962876A CN201510320273.9A CN201510320273A CN104962876A CN 104962876 A CN104962876 A CN 104962876A CN 201510320273 A CN201510320273 A CN 201510320273A CN 104962876 A CN104962876 A CN 104962876A
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Abstract
The invention relates to a boron-doped diamond film material on the surface of graphite and a preparation method thereof. The boron-doped diamond film material on the surface of the graphite is formed in the mode that a metal tungsten film is formed on the surface of a graphite basal body through hot filament chemical vapor deposition to serve as a middle transition layer, and then a boron-doped diamond film is formed on the metal tungsten film through hot filament chemical vapor deposition. The preparation method includes the steps that the graphite basal body is placed in a hot filament plasma chemical vapor deposition reaction chamber, and a hot filament is powered on to be 1200-1400 DEG C after the reaction chamber is vacuumized; then, carbonyl tungsten steam is introduced, so that the metal tungsten film is discomposed and deposited from carbonyl tungsten steam molecules on the surface of the graphite basal body to serve as a middle layer; a filament power source is adjusted to increase the temperature of a filament to 2100-2300 DEG C, methane, borane and hydrogen are introduced in the reaction chamber, and a diamond film grows on the surface of the deposited tungsten layer. The graphite basal body does not need to be transferred and continuously grow in the original position in the same device. The method is efficient and simple, cost is low, and the high quality of prepared films can be guaranteed.
Description
Technical field
The present invention relates to the modification to conventional graphite electrochemical electrode material, by adopting special preparation method to obtain high performance graphite/metal/boron-doped diamond multilayer materials, significantly promoting the performance of graphite as electrochemical electrode.
Background technology
Along with developing rapidly of petrochemical complex, medicine, agricultural chemicals and dyestuffs industries, in trade effluent, the quantity of biodegradable organic compounds and kind grow with each passing day, particularly wherein contained high density aromatics, belong to " three cause " material, be difficult to direct removal with general physics, chemistry and biodegradation method.Electrochemical advanced oxidation method is removed in the intermediate product of water molecules electrolysis or target compound in electrode surface direct oxidation because of its oxidant source, the degraded of pollutent can be completed without the need to adding other reagent by regulating current potential, belong to Green Chemistry process, become the important directions of wastewater processing technology development.
The key of advanced electrochemical oxidation process is suitable electrode materials.Electrode materials for the electrochemical advanced oxidation process of high density, hardly degraded organic substance should have strong, the wide electromotive force window etc. of stable surface chemical property, excellent electrochemical catalysis performance, erosion resistance.Electrode materials conventional at present has graphite, metal and oxide electrode, and what with fastest developing speed, prospect was best is then b-doped diamond film (BDD) electrode.BDD electrode has the widest electrochemical potential window (> 3.5 V vs NHE), the highest overpotential for oxygen evolution (> 2.5 V vs NHE), extremely low background current (< 50 mA/cm
2), the feature such as extremely strong unreactiveness and antipollution poisoning capability, low-down surface adsorption characteristic and high electro catalytic activity, be ideal electro-chemical water process electrode materials in theory; And large quantity research all proves under all experiment conditions, compared to traditional electrode, rate of oxidation and the current efficiency of diamond electrode are the highest, have more excellent electrode performance.
B-doped diamond film (BDD) electrode mainly uses heavily doped silicon or metal as matrix at present, silicon is larger as its resistance of semiconductor material, after forming silicon/BDD combined electrode, electrochemical electrolysis treating processes middle impedance thermal value is large, add wastewater treatment energy consumption, also easily destroy the bonding force of diamond coatings and matrix simultaneously, send a telegraph pole global failure; In addition silicon substrate fragility is large, and physical strength is inadequate, is unfavorable for installing and using in engineer applied.Metallic matrix (as tungsten, molybdenum, niobium etc.) is although have good mechanical property and electric property, but due to very big with diamond thermal expansion coefficient difference, metal/BDD combined electrode the bonding force formed is weak, and use procedure easily occurs that diamond film comes off and causes electrode damage; These metal prices are expensive simultaneously, and use cost is high, are difficult to through engineering approaches application.Comparatively speaking, graphite then can solve above-mentioned difficulties as BDD combined electrode matrix comprehensively: graphite relative low price, processibility is good, machinery, electricity, thermal characteristics are excellent, particularly crucially its thermal expansivity and diamond are very close, if coating surface diamond coatings thermal stresses is little, substantially can ignore anchoring strength of coating impact, thus graphite is the optimal body material of BDD coated electrode in theory.
However, due to must hydrogen be used in chemical vapour deposition BDD coating procedure, the graphite of association during to etch away diamond film and amorphous carbon, if consequent impact is exactly as matrix with graphite, the high concentration of hydrogen used in diamond film acutely can etch graphite matrix equally, not only destroy basal body structure, and make diamond film atmosphere out of control, be difficult to form complete diamond film material on surface, although therefore many researchists carried out the increment study of graphite matrix surface diamond film so far, but not yet realize the product of diamond coated film on graphite matrix in practical application.And the application of this coated material is the most key sport technique segment to electrochemical wastewater process, directly decide the Effectiveness and benefit that advanced electrochemical oxidation process is applied in water treatment field.Therefore promote that for the application of electrochemical process in water treatment, the technology of preparing difficult problem solving high quality BDD coating on graphite matrix is extremely important key node for being used by BDD electrode.
The best method that theoretical and existing practice all proves to overcome above-mentioned difficulties be on graphite matrix, first deposit layer of metal (mainly carbide forming element is as tungsten, molybdenum, titanium, niobium etc.), growing diamond then can obtain continuous on graphite matrix, complete, high-quality diamond coatings thereon again.Metal intermediate layer not only avoids the violent hydrogen etching of graphite matrix, and carbide can be formed with the carbon source chemical combination in graphite matrix and diamond film atmosphere when diamond film under the effect of graphite matrix hot conditions, not only increase the bonding strength between graphite, transition layer, diamond film, and due to metallic carbide and graphite and adamantine thermal expansivity comparatively close, significantly can reduce growth and terminate the thermal stresses of rear existence, final security deposit's hard rock coating stable, firmly be present in graphite matrix surface.
But graphite matrix surface metal intermediate layer adopts physical gas phase deposition technology (as sputtering substantially, ion plating, electron beam evaporation plating) preparation, not only need the film deposition equipment outside diamond coatings growth, and complex procedures, after the growth of graphite matrix surface metal transition layer need being completed in physics vapour deposition system, take out again and put into the preparation that chemical gas-phase deposition system (mainly hot-wire chemical gas-phase deposition system) carries out diamond film, time cycle is long, complicated operation bothers, and matrix transfer process will be exposed to air, surface contamination also can affect the quality of subsequent deposition diamond thin to a certain extent.Therefore existing graphite matrix surface is prepared diamond coating technique and be there is obvious weakness and defect, strongly limit the application of this novel material as electrochemical electrode, is badly in need of improving perfect.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of efficient, easy, low cost is provided and high-quality graphite/metal/diamond coatings matrix material and preparation method thereof can be ensured.
Solution of the present invention is: a kind of graphite surface boron-doped diamond film material, be characterized in graphite matrix surface first hot-wire chemical gas-phase deposition layer of metal tungsten film as intermediate layer, hot-wire chemical gas-phase deposition boron-doped diamond film thereon again, wherein metal tungsten layer thickness is 0.2 ~ 2mm, and the thickness of diamond film is 0.5 ~ 10 mm.
Solution of the present invention is: the preparation method of graphite surface boron-doped diamond film material, is characterized in comprising the following steps:
A, graphite matrix to be positioned over heated filament plasma cvd reactor indoor, reaction chamber is evacuated to 1.0 ~ 3.0 Pa;
B, to the heated filament energising in reaction chamber, make filament temperature reach 1200 ° ~ 1400 ° C, then pass into the tungsten carbonyl steam of 50-70 ° of C water-bath thermostatically heating gasification, make tungsten carbonyl steam molecule deposit metal tungsten film as middle layer at graphite matrix Surface disintegration;
C, closedown tungsten carbonyl vapour line intake valve, regulate heater supply to raise filament temperature and reach 2100-2300 ° of C, then in reaction chamber, pass into methane, borine and hydrogen, the tungsten layer surface growth diamond film deposited.
In solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, the reactant gas source of its thermal filament chemical vapor deposition of diamond film is methane and hydrogen, and doped source is borine; Wherein methane accounts for volume of gas ratio is 0.5 ~ 4%, borine account for volume of gas ratio be 10-1000 1,000,000/, remaining gas is hydrogen, and general gas flow is per minute 200 ~ 400 milliliters.
In solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, its borine passed into is the borine of hydrogen dilution.
In solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, the method that boron-doped diamond film is prepared on its graphite matrix surface adopts the preparation of original position MOCVD (MOCVD) technology, namely same set of device is used, elder generation as middle layer at graphite matrix surface deposition metal tungsten film, closes tungsten carbonyl vapour line intake valve, then changes source of the gas and processing condition, pass into methane, borine and hydrogen, depositing diamond film.
Advantage of the present invention: the present invention adopts hot filament CVD, first utilize tungsten carbonyl thermal decomposed deposition layer of metal tungsten as intermediate layer on graphite matrix surface, change source of the gas immediately growth in situ boron-doped diamond film thereon again, different device growths is needed respectively unlike traditional method intermediate metal transition layer and diamond coatings, and graphite matrix does not need transfer yet, can grow continuously at same set of device situ, this method is efficient, easy, low cost and the high quality of film preparation can be ensured.
Accompanying drawing explanation
Fig. 1 is the preparation system structure iron that the present invention uses;
Fig. 2 is the Raman spectrum of the graphite matrix surface b-doped diamond film that foundation embodiment 1 and embodiment 2 are prepared.
In figure, 1 is water-bath (inside containing tungsten carbonyl container), and 2 is methane container, and 3 is hydrogen tank, and 4 is borine container, and 5 is heater supply, and 6 is inlet mouth, and 7 is heated filament, and 8 is graphite matrix, and 9 is water-cooled sample table, and 10 is sediment chamber, and 11 is vacuum pumping opening.
Embodiment
The embodiment of the present invention 1:
Open heating tungsten carbonyl thermostat water bath power supply in advance, regulate water-bath temperature to 50 ° C constant temperature; Be fixed on by graphite matrix in the water-cooled sample table of hot-wire chemical gas-phase deposition system, the vacuum of taking out sediment chamber is 2.0 Pa to vacuum tightness, and opens sample table water coolant; Start heater supply, boost source power reaches 1200 ° to hot-wire temperature; The metering pin valve 1/3rd opened in tungsten carbonyl gas circuit encloses, and passes into the tungsten carbonyl steam of pin valve opening manipulated variable in vacuum chamber; Above-mentioned condition maintains 1.5 hours, completes the growth of tungsten middle layer.Close the needle-valve in tungsten carbonyl gas circuit, increase heater supply power and reach 2200 ° to hot-wire temperature, pass into borine (i.e. borine and the hydrogen gas mixture of 200 SCCM hydrogen, 20SCCM methane, 20SCCM hydrogen dilution, borine volumetric concentration is ten thousand/), continuous deposition 3 hours, finally reduces the shutdown of heater power Slow cooling gradually.Wherein tungsten film thickness is 1 mm, and the thickness of boron-doped diamond film is 1.5mm, and Boron contents is 50ppm.
Embodiment 2:
Open heating tungsten carbonyl thermostat water bath power supply in advance, adjustment water-bath temperature to 50 ° C constant temperature; Be fixed on by graphite cathode in the water-cooled sample table of hot-wire chemical gas-phase deposition system, the vacuum of taking out sediment chamber is 2.0 Pa to vacuum tightness, and opens sample table water coolant; Start heater supply, boost source power reaches 1200 ° to hot-wire temperature; The metering pin valve 1/3rd opened in tungsten carbonyl gas circuit encloses, and passes into the tungsten carbonyl steam of pin valve opening manipulated variable in vacuum chamber; Above-mentioned condition maintains 2 hours, completes the growth of tungsten middle layer.Close the needle-valve in tungsten carbonyl gas circuit, increase heater supply power and reach 2200 ° to hot-wire temperature, pass into borine (i.e. borine and the hydrogen gas mixture of 300 SCCM hydrogen, 40SCCM methane, 50SCCM hydrogen dilution, borine volumetric concentration is ten thousand/), continuous deposition 5 hours, finally reduces the shutdown of heater power Slow cooling gradually.Wherein tungsten film thickness is 1.5 mm, and the thickness of boron-doped diamond film is 2.5mm, and Boron contents is 150ppm.
Fig. 2 is the Raman spectrum of the graphite matrix surface b-doped diamond film prepared.Wherein 1# is the Raman spectrum of embodiment 1, and 2# is the Raman spectrum of embodiment 2.At about 1332 cm in figure
-1all there is a sharp-pointed sp in place
3the single order Raman resonance peak of-C phase, and at 1350 cm
-1with 1580 cm
-1place, without obvious D peak and G peak, shows that the two is comparatively pure diamond film, does not almost have graphite and amorphous carbon dephasign.Simultaneously on spectrogram at about 1240 ~ 1218 cm
-1near all there is weak Raman resonance peak, this peak be due to boron mix diamond lattice after B-C key to increase and the crystal state of disarray caused increases shown characteristic peak, and along with the increase of B/C ratio in reactant gas source, the intensity at this Raman peak strengthens gradually, show the increase along with B/C ratio, in diamond film, the content of B increases thereupon, namely in embodiment 2 gained diamond film Boron contents higher than embodiment 1.
Claims (5)
1. a graphite surface boron-doped diamond film material, it is characterized in that at the first hot-wire chemical gas-phase deposition layer of metal tungsten film in graphite matrix surface as intermediate layer, hot-wire chemical gas-phase deposition boron-doped diamond film thereon again, wherein metal tungsten layer thickness is 0.2 ~ 2mm, and the thickness of diamond film is 0.5 ~ 10 mm.
2. a preparation method for graphite surface boron-doped diamond film material as claimed in claim 1, is characterized in that comprising the following steps:
A, graphite matrix to be positioned over heated filament plasma cvd reactor indoor, reaction chamber is evacuated to 1.0 ~ 3.0 Pa;
B, to the heated filament energising in reaction chamber, make filament temperature reach 1200 ° ~ 1400 ° C, then pass into the tungsten carbonyl steam of 50-70 ° of C water-bath thermostatically heating gasification, make tungsten carbonyl steam molecule deposit metal tungsten film as middle layer at graphite matrix Surface disintegration;
C, closedown tungsten carbonyl vapour line intake valve, regulate heater supply to raise filament temperature and reach 2100-2300 ° of C, then in reaction chamber, pass into methane, borine and hydrogen, the tungsten layer surface growth diamond film deposited.
3. the preparation method of graphite surface boron-doped diamond film material according to claim 2, it is characterized in that the reactant gas source of thermal filament chemical vapor deposition of diamond film is methane and hydrogen, doped source is borine; Wherein methane accounts for volume of gas ratio is 0.5 ~ 4%, and it is 1,000,000/10-1000 that borine accounts for volume of gas ratio, and remaining gas is hydrogen, and general gas flow is per minute 200 ~ 400 milliliters.
4. the preparation method of graphite surface boron-doped diamond film material according to claim 3, is characterized in that passed into borine is the borine of hydrogen dilution.
5. the preparation method of graphite surface boron-doped diamond film material according to claim 2, it is characterized in that method employing original position MOCVD (MOCVD) the technology preparation of boron-doped diamond film is prepared on graphite matrix surface, namely same set of device is used, first at graphite matrix surface deposition metal tungsten film as middle layer, close tungsten carbonyl vapour line intake valve, change source of the gas and processing condition again, pass into methane, borine and hydrogen, depositing diamond film.
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| CN106830205A (en) * | 2016-12-16 | 2017-06-13 | 大连理工大学 | A kind of preparation method of self-supporting boron-doped diamond catalysis material |
| CN107034467A (en) * | 2017-03-13 | 2017-08-11 | 深圳先进技术研究院 | A kind of hard alloy piece with diamond coatings and preparation method thereof |
| CN107545936A (en) * | 2017-08-22 | 2018-01-05 | 廊坊西波尔钻石技术有限公司 | Diamond film and graphite composite material |
| WO2018072367A1 (en) * | 2016-10-21 | 2018-04-26 | 中南大学 | Boron-doped diamond electrode and preparation method and application of same |
| CN109811328A (en) * | 2017-11-21 | 2019-05-28 | 深圳先进技术研究院 | A kind of preparation method of boron-doped diamond film |
| CN111254409A (en) * | 2018-12-03 | 2020-06-09 | 核工业西南物理研究院 | Preparation method of diamond film first wall facing to plasma |
| CN112763556A (en) * | 2020-12-07 | 2021-05-07 | 山东省科学院海洋仪器仪表研究所 | Ocean detector electrode with multilayer film structure and preparation method thereof |
| CN114751408A (en) * | 2022-03-25 | 2022-07-15 | 浙江工业大学 | Method for preparing diamond based on graphite under low pressure |
| CN115572962A (en) * | 2022-10-10 | 2023-01-06 | 松山湖材料实验室 | CVD equipment of curved surface chamber coating film |
| CN117187774A (en) * | 2023-09-19 | 2023-12-08 | 无锡松煜科技有限公司 | Boron diffusion method without coiling and diffusion and oxygen source deposition |
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| WO2018072367A1 (en) * | 2016-10-21 | 2018-04-26 | 中南大学 | Boron-doped diamond electrode and preparation method and application of same |
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| CN107034467A (en) * | 2017-03-13 | 2017-08-11 | 深圳先进技术研究院 | A kind of hard alloy piece with diamond coatings and preparation method thereof |
| CN107545936A (en) * | 2017-08-22 | 2018-01-05 | 廊坊西波尔钻石技术有限公司 | Diamond film and graphite composite material |
| CN109811328A (en) * | 2017-11-21 | 2019-05-28 | 深圳先进技术研究院 | A kind of preparation method of boron-doped diamond film |
| CN111254409A (en) * | 2018-12-03 | 2020-06-09 | 核工业西南物理研究院 | Preparation method of diamond film first wall facing to plasma |
| CN112763556A (en) * | 2020-12-07 | 2021-05-07 | 山东省科学院海洋仪器仪表研究所 | Ocean detector electrode with multilayer film structure and preparation method thereof |
| CN114751408A (en) * | 2022-03-25 | 2022-07-15 | 浙江工业大学 | Method for preparing diamond based on graphite under low pressure |
| CN114751408B (en) * | 2022-03-25 | 2023-09-05 | 浙江工业大学 | Method for preparing diamond based on graphite at low pressure |
| CN115572962A (en) * | 2022-10-10 | 2023-01-06 | 松山湖材料实验室 | CVD equipment of curved surface chamber coating film |
| CN117187774A (en) * | 2023-09-19 | 2023-12-08 | 无锡松煜科技有限公司 | Boron diffusion method without coiling and diffusion and oxygen source deposition |
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