CN104962876B - Graphite surface boron-doped diamond film material and preparation method thereof - Google Patents
Graphite surface boron-doped diamond film material and preparation method thereof Download PDFInfo
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- CN104962876B CN104962876B CN201510320273.9A CN201510320273A CN104962876B CN 104962876 B CN104962876 B CN 104962876B CN 201510320273 A CN201510320273 A CN 201510320273A CN 104962876 B CN104962876 B CN 104962876B
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Abstract
The present invention relates to a kind of graphite surface boron-doped diamond film material and preparation method thereof.Graphite surface boron-doped diamond film material is as intermediate layer, then in hot-wire chemical gas-phase deposition boron-doped diamond film thereon in graphite matrix surface elder generation hot-wire chemical gas-phase deposition layer of metal tungsten film.Preparation method is that graphite matrix is positioned in heated filament plasma cvd reactor room, reative cell is vacuumized rear heated filament and is powered and reaches 1200 ° ~ 1400 °C, tungsten carbonyl steam is passed through again, tungsten carbonyl steam molecule is decomposed on graphite matrix surface and is deposited metal tungsten film as intermediate layer；Then adjust filament supply rise filament temperature and reach 2,100 2300 °C, methane, borine and hydrogen are passed through into reative cell, in the tungsten layer superficial growth diamond film deposited.Graphite matrix of the present invention is not required to shift, and can continuously be grown in same covering device situ, this method efficiently, easy, low cost and can guarantee that the high quality of film preparation.
Description
Technical field
The present invention relates to the modification to conventional graphite electrochemical electrode material, and high property is obtained by using special preparation method
Graphite/metal/boron-doped diamond multilayer materials of energy, significantly lift performance of the graphite as electrochemical electrode.
Background technology
With developing rapidly for petrochemical industry, medicine, agricultural chemicals and dye industry, biodegradable organic compoundses in industrial wastewater
Quantity and species high concentration aromatic compound growing day by day, particularly contained therein, category " three cause " material, use in general
Physics, chemistry and biodegradation method are difficult to directly remove.Electrochemical advanced oxidation method is because its oxidant source is in hydrone electricity
The intermediate product or object of solution remove in electrode surface direct oxidation, by adjusting current potential without adding other reagents
The degraded of pollutant is completed, belongs to Green Chemistry process, turns into the important directions of wastewater processing technology development.
The key of advanced electrochemical oxidation process is suitable electrode material.For high concentration, the electricity of hardly degraded organic substance
The electrode material of chemical advanced oxidation processing should have stable surface chemical property, excellent electrochemical catalysis performance, corrosion resistant
Corrosion is strong, wide potential window etc..Currently used electrode material has graphite, metal and oxide electrode, and with fastest developing speed, preceding
Scape it is best be then b-doped diamond film（BDD）Electrode.BDD electrodes have most wide electrochemical potential window（> 3.5 V vs
NHE）, highest overpotential for oxygen evolution（> 2.5 V vs NHE）, extremely low background current（< 50 mA/cm2）, extremely strong chemistry
The features such as inertia and antipollution poisoning capability, low-down adsorption characteristic and high electro catalytic activity, theoretically most
Electrode material is handled for preferable electro-chemical water；And numerous studies are proved under all experiment conditions, compared to traditional electricity
For pole, the oxidation rate and current efficiency highest of diamond electrode, there is more excellent electrode performance.
B-doped diamond film（BDD）The silicon of heavy doping is currently mainly used in electrode or metal is used as half as matrix, silicon
Its resistance of conductor material is larger, and electrochemical electrolysis processing procedure middle impedance caloric value is big after forming silicon/BDD combination electrodes, increase
Wastewater treatment energy consumption, while it is also easy to destroy the adhesion of diamond coatings and matrix, send a telegraph pole global failure；In addition silicon substrate
Body fragility is big, and mechanical strength is inadequate, is unfavorable for installing and using in engineer applied.Metallic matrix（Such as tungsten, molybdenum, niobium）Although have
Good mechanical performance and electric property, but due to very big with diamond thermal expansion coefficient difference, metal/BDD of formation is compound
Electrode adhesion is weak, easily occurs diamond film using process and come off to cause electrode damage；These metal prices are expensive simultaneously, make
With cost height, it is difficult to engineering application.Comparatively speaking, graphite then can be above-mentioned tired with comprehensively solve as BDD combination electrodes matrix
It is difficult：Graphite relative low price, processability is good, and machinery, electricity, hot property are excellent, and particularly critical is its thermal coefficient of expansion and gold
Hard rock is veryed close, if coating surface diamond coatings thermal stress is small, anchoring strength of coating is influenceed to ignore substantially, thus
Graphite is theoretically the optimal matrix material of BDD coated electrodes.
Nevertheless, due to hydrogen must be used in chemical vapor deposition BDD coating procedures, to etch away diamond film
When association graphite and amorphous carbon, if the thing followed influences to be exactly the height that uses in diamond film by the use of graphite as matrix
Concentration hydrogen equally can not only break up basal body structure to the violent etching of graphite matrix, and make diamond film atmosphere out of control,
It is difficult to complete diamond membrane material is formed on surface, although therefore many researchers carried out graphite matrix surface Buddha's warrior attendant so far
The increment study of stone film, but the product of diamond coated film on graphite matrix is not yet realized in practical application.And this coating material
The application of material is again the most key sport technique segment to electrochemical wastewater processing, directly decides that advanced electrochemical oxidation process exists
The effect and benefit of water treatment field application.Therefore for using promote electrochemical process in water process to answer by BDD electrodes
For, the technology of preparing problem for solving high quality BDD coatings on graphite matrix is extremely important key node.
It is theoretical and put into practice that to prove to overcome the best methods of above-mentioned difficulties be that one layer of gold is first deposited on graphite matrix
Category (mainly carbide former such as tungsten, molybdenum, titanium, niobium etc.), graphite matrix can be obtained if growing diamond thereon again
Upper continuous, the complete, diamond coatings of high quality.Metal intermediate layer not only avoids the violent hydrogen of graphite matrix from etching, and
And can in diamond film graphite matrix hot conditions effect under with the carbon source in graphite matrix and diamond film atmosphere
Chemical combination forms carbide, not only increases the bond strength between graphite, transition zone, diamond film, and due to metal carbides
It is closer to the thermal coefficient of expansion of graphite and diamond, existing thermal stress after growth terminates can be greatly lowered, finally
Ensure diamond coating stable, be firmly present in graphite matrix surface.
But graphite matrix surface metal intermediate layer uses physical gas phase deposition technology substantially（As sputtering, ion plating,
Electron beam evaporation plating）Prepare, not only need the film deposition equipment outside diamond coatings growth, and complex procedures, need to be in physics
After the growth that graphite matrix surface metal transition zone is completed in gas-phase deposition system, further take out and be put into chemical gas-phase deposition system
（Mainly hot-wire chemical gas-phase deposition system）The middle preparation for carrying out diamond film, time cycle length, complex operation trouble, and
Matrix transfer process will be exposed to air, and surface contamination can also influence the quality of subsequent deposition diamond thin to a certain extent.
Therefore existing graphite matrix surface prepares diamond coating technique and obvious weakness and defect be present, strongly limit this green wood
Expect the application as electrochemical electrode, need to improve perfect.
The content of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of efficient, easy, low cost and energy
Ensure graphite/metal/diamond coatings composite of high quality and preparation method thereof.
The present invention solution be：A kind of graphite surface boron-doped diamond film material, is characterized in graphite-based
Body surface face elder generation hot-wire chemical gas-phase deposition layer of metal tungsten film as intermediate layer, then thereon, mix by hot-wire chemical gas-phase deposition
Boron diamond film, wherein metal tungsten layer thickness are 0.2~2mm, and the thickness of diamond film is 0.5~10 mm.
The present invention solution be：The preparation method of graphite surface boron-doped diamond film material, is characterized in including
Following steps：
A, graphite matrix is positioned in heated filament plasma cvd reactor room, reative cell is evacuated to
1.0 ~ 3.0 Pa；
B, it is powered to the heated filament in reative cell, filament temperature is reached 1200 ° ~ 1400 °C, then be passed through 50-70 °C of water-bath
The tungsten carbonyl steam of pot heated at constant temperature gasification, tungsten carbonyl steam molecule is decomposed on graphite matrix surface and deposit metal tungsten film work
For intermediate layer；
C, tungsten carbonyl steam pipework intake valve is closed, regulation filament supply rise filament temperature reaches 2100-2300 °C, so
Methane, borine and hydrogen are passed through in backward reative cell, in the tungsten layer superficial growth diamond film deposited.
In the solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, its hot-wire chemical gas
The reactant gas source of phase depositing diamond film is methane and hydrogen, and doped source is borine；Wherein methane accounts for volume of gas ratio and is
0.5 ~ 4%, borine account for volume of gas ratio for 10-1000 million/, remaining gas is hydrogen, and general gas flow is every point
200 ~ 400 milliliters of clock.
In the solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, its boron being passed through
Alkane is the borine of hydrogen dilution.
In the solution of the present invention, the preparation method of graphite surface boron-doped diamond film material, its graphite-based body surface
The method that face prepares boron-doped diamond film is prepared using MOCVD in situ (MOCVD) technology, i.e.,
Using same covering device, first tungsten carbonyl steam pipework air inlet is closed as intermediate layer in graphite matrix surface deposited metal tungsten film
Valve, then change source of the gas and process conditions, it is passed through methane, borine and hydrogen, depositing diamond film.
Advantages of the present invention：The present invention uses hot filament CVD, on graphite matrix surface first with tungsten carbonyl
Thermal decomposed deposition layer of metal tungsten is as intermediate layer, then changes source of the gas in immediately growth in situ boron-doped diamond film thereon,
Unlike conventional method intermetallic metal transition zone and diamond coatings are respectively necessary for different device growths, and graphite matrix is not yet
Need to shift, can continuously be grown in same covering device situ, this method efficiently, easy, low cost and can guarantee that film preparation
High quality.
Brief description of the drawings
Fig. 1 is the preparation system structure chart that the present invention uses；
Fig. 2 is the Raman light for the graphite matrix surface b-doped diamond film prepared according to embodiment 1 and embodiment 2
Spectrum.
In figure, 1 is water-bath（Inside contain tungsten carbonyl container）, 2 be methane container, and 3 be hydrogen tank, and 4 be borine container,
5 be heater supply, and 6 be air inlet, and 7 be heated filament, and 8 be graphite matrix, and 9 be water cooling sample stage, and 10 be settling chamber, and 11 take out for vacuum
Gas port.
Embodiment
The embodiment of the present invention 1：
Heating tungsten carbonyl thermostat water bath power supply, regulation water-bath pot temperature to 50 °C of constant temperature are opened in advance；By graphite matrix
It is fixed on the water cooling sample stage of hot-wire chemical gas-phase deposition system, vacuum to the vacuum for taking out settling chamber is 2.0 Pa, and is beaten
Open sample stage cooling water；Start heater supply, boost source power to hot-wire temperature is up to 1200 °；Open in tungsten carbonyl gas circuit
Metering pin valve 1/3rd encloses, toward vacuum chamber in be passed through the tungsten carbonyl steam of pin valve opening controlled quentity controlled variable；Above-mentioned condition maintenance 1.5 is small
When the time, complete the growth of tungsten intermediate layer.The needle-valve closed in tungsten carbonyl gas circuit, increase heater supply power to hot-wire temperature reach
2200 °, it is passed through 200 SCCM hydrogen, 20SCCM methane, the borine of 20SCCM hydrogen dilutions（That is borine and hydrogen gas mixture, boron
Alkane volumetric concentration is a ten thousandth）, continuous deposition 3 hours, last gradually reduction heater power Slow cooling shutdown.Wherein metal
W film thickness is 1 mm, and the thickness of boron-doped diamond film is 1.5mm, Boron contents 50ppm.
Embodiment 2：
Heating tungsten carbonyl thermostat water bath power supply, adjustment water-bath pot temperature to 50 °C of constant temperature are opened in advance；By graphite cathode
It is fixed on the water cooling sample stage of hot-wire chemical gas-phase deposition system, vacuum to the vacuum for taking out settling chamber is 2.0 Pa, and is beaten
Open sample stage cooling water；Start heater supply, boost source power to hot-wire temperature is up to 1200 °；Open in tungsten carbonyl gas circuit
Metering pin valve 1/3rd encloses, toward vacuum chamber in be passed through the tungsten carbonyl steam of pin valve opening controlled quentity controlled variable；Above-mentioned condition maintains 2 hours
Time, complete the growth of tungsten intermediate layer.The needle-valve closed in tungsten carbonyl gas circuit, increase heater supply power to hot-wire temperature reach
2200 °, it is passed through 300 SCCM hydrogen, 40SCCM methane, the borine of 50SCCM hydrogen dilutions（That is borine and hydrogen gas mixture, boron
Alkane volumetric concentration is a ten thousandth）, continuous deposition 5 hours, last gradually reduction heater power Slow cooling shutdown.Wherein metal
W film thickness is 1.5 mm, and the thickness of boron-doped diamond film is 2.5mm, Boron contents 150ppm.
Fig. 2 is the Raman spectrum for the graphite matrix surface b-doped diamond film prepared.Wherein 1# is embodiment 1
Raman spectrum, 2# are the Raman spectrum of embodiment 2.In about 1332 cm in figure-1There is a sharp sp in place3- C phases
Single order Raman formants, and in 1350 cm-1With 1580 cm-1Place shows both at more without obvious D peaks and G peaks
Pure diamond film, almost without graphite and amorphous carbon dephasign.Simultaneously in about 1240 ~ 1218 cm on spectrogram-1Nearby go out
Existing weak Raman formants, the peak be due to after boron incorporation diamond lattice B-C keys increase caused by crystal disordered state increase
Shown characteristic peaks more, and with reactant gas source B/C than increase, the intensity at the Raman peaks gradually strengthens, show with
B/C than increase, B content increases therewith in diamond film, i.e., Boron contents are higher than implementing in the gained diamond film of embodiment 2
Example 1.
Claims (3)
1. a kind of preparation method of graphite surface b-doped diamond film, it is characterised in that in graphite matrix surface elder generation hot-wire chemical
Layer of metal tungsten film be vapor-deposited as intermediate layer, then in the boron-doped diamond film of Hot Filament Chemical Vapor's successive sedimentation thereon,
So as to realize the in-situ chemical vapor deposition of intermediate metal and b-doped diamond film.
A kind of 2. preparation method of graphite surface b-doped diamond film as claimed in claim 1, it is characterised in that including with
Lower step：
A, graphite matrix is positioned in heated filament plasma cvd reactor room, reative cell is evacuated to 1.0 ~
3.0 Pa；
B, it is powered to the heated filament in reative cell, filament temperature is reached 1200 ~ 1400 DEG C, then be passed through 50-70 DEG C of water-bath constant temperature
The tungsten carbonyl steam of heating and gasifying, tungsten carbonyl steam molecule is decomposed on graphite matrix surface and deposit among the conduct of metal tungsten film
Layer；
C, tungsten carbonyl steam pipework intake valve is closed, regulation filament supply rise filament temperature reaches 2100-2300 DEG C, Ran Houxiang
Methane, borine and hydrogen are passed through in reative cell, in the tungsten layer superficial growth diamond film deposited.
3. the preparation method of graphite surface b-doped diamond film according to claim 1, it is characterised in that graphite matrix
The method that surface prepares boron-doped diamond film is prepared using MOCVD in situ (MOCVD) technology,
Same set of hot-wire chemical gas-phase deposition device is used, is first closed in graphite matrix surface deposited metal tungsten film as intermediate layer
Tungsten carbonyl steam pipework intake valve, then change source of the gas and process conditions, it is passed through methane, borine and hydrogen, depositing diamond film.
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| US11603594B2 (en) | 2016-10-21 | 2023-03-14 | Nanjing Daimonte Technology Co., Ltd. | Boron doped diamond electrode and preparation method and applications thereof |
| CN106830205B (en) * | 2016-12-16 | 2020-08-21 | 大连理工大学 | Preparation method of self-supporting boron-doped diamond catalytic material |
| CN107034467B (en) * | 2017-03-13 | 2019-12-03 | 深圳先进技术研究院 | A kind of hard alloy piece and preparation method thereof with diamond coatings |
| 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 |
| CN109811328B (en) * | 2017-11-21 | 2021-04-09 | 深圳先进技术研究院 | 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 |
| CN112763556B (en) * | 2020-12-07 | 2022-12-02 | 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 |
| 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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