CN107119263A - A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode - Google Patents
A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, it is related to novel electron material technology technology, boron-doped diamond is prepared using electron assistant hot-wire chemical gas-phase deposition method, then catalytic materials are used as by gold, the method for spraying chemical vapor deposition in Boron-doped diamond surface using plasma grows graphene, so as to obtain vertical graphene/boron-doped diamond sensing electrode.It is an advantage of the invention that：The high-quality boron-doped diamond film and graphene layer prepared ensure that the quality of vertical graphene/boron-doped diamond compounded film, and the complex thin film structure is close, it is difficult for drop-off, the combination of vertical graphene and boron-doped diamond can give full play to the advantage and synergy of the two, the graphene of vertical-growth has bigger effective ratio area compared to the graphene of tiling, and the vertical graphene/boron-doped diamond compounded film for choosing appropriate size can be directly used for the detection of biomolecule as sensing electrode.
Description
Technical field
The present invention relates to the preparation of vertical graphene and boron-doped diamond film, more particularly to a kind of vertical graphene/mix
The preparation method of boron diamond sensing electrode.
Technical background
In recent years, grapheme material and boron-doped diamond material are respectively freed from itself excellent characteristic and ground extensively
Study carefully.
Grapheme material has extensive use in terms of sensor, and compared to conventional electrode materials, grapheme material has
High specific surface area and biocompatibility, absorption material to be detected that can be rapidly and efficiently；Also, graphene has at room temperature
Very high electron mobility, therefore with high catalytic performance, and then shorten the reaction time.
The graphene prepared compared to oxide-reduction method, the graphene defect prepared by chemical vapour deposition technique is few,
Electrical conductivity is big, and closer to preferable graphene state, and the graphene is perpendicular to substrate grown, with bigger ratio surface
Long-pending, more electro catalytic activity sites, the contact with determinand is more abundant, this will be advantageous to improve electron transfer speed,
Accelerate catalytic reaction.
Diamond has hardness big, the physical property such as antiacid caustic corrosion.Diamond is carried out after boron doping, in crystal structure
Part carbon atom is replaced by boron atom, and forms hole, beneficial to electron transfer.Therefore, the suitable boron of ratio is carried out to diamond
Doping obtains boron-doped diamond, can also make it that itself is conductive while the good characteristic of most of diamond in itself is retained
Rate is improved, closer to semiconductor.Boron-doped diamond has low background current, and wide potential window feature is being used as sensing electrode
In use, the wide potential window of boron-doped diamond can detect the higher material of oxidizing potential scope, low background current can
Reduce interference, and then improve sensitivity.
In the prior art for the preparation of graphene sensing electrode, grapheme material is such as allowed to attached by drop coating method
In similar approach such as glass-carbon electrodes, the potential scope of application (vs. saturated calomel electrodes) of wherein glass-carbon electrode is about -1~1V,
And the potential window of the boron-doped diamond electrode of excellent quality is wider, therefore it can detect oxidizing potential outside the above range
Material；By graphene growth and tantalum, it can also use, compared to the metalloid, be mixed directly as sensing electrode on the metal such as titanium
Boron diamond has higher carrier concentration, therefore Detection results are more preferable when as sensing electrode.
Vertical graphene/boron-doped diamond compound film is prepared as sensing electrode, effectively original technology can be changed
Enter, vertical graphene/boron-doped diamond compound film has the advantage and cooperative effect of the two, can not only improve original graphene
System has graphene vertical-growth to impart more catalytic sites in diamond the detectability of material, to be measured
The selectivity of thing is also improved.
At present, the method for preparing boron-doped diamond of comparative maturity is chemical vapour deposition technique, the boron-doped diamond of preparation
It is best in quality, and be adapted to grow for a long time than larger area.The preparation method of graphene mainly has mechanical stripping method, and oxidation is also
Former method and chemical vapour deposition technique, chemical vapour deposition technique can prepare vertical orientated graphene, excellent in actual applications
Gesture becomes apparent.Chemical vapour deposition technique is to be most widely used at present and be adapted to fairly large industrially prepared such thin-film material
Method.
The content of the invention
It is an object of the invention to improve detectability of the graphene sensing electrode to biomolecule, vertical stone is made full use of
The advantage and cooperative effect of black alkene and boron-doped diamond, vertical graphene/boron-doped diamond sensing electrode of preparation are ensureing to hang down
While the detectability of straight graphene, the background current of Graphene electrodes is effectively reduced, increases its potential window, therefore, makes
Obtain its detection range more extensive.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, utilizes electron assistant Hot Filament Chemical Vapor
Depositing device prepares high-quality boron-doped diamond film, and catalysis is used as in the Boron-doped diamond surface combination metallic gold of preparation
Thing, using plasma injection chemical vapour deposition technique grows vertical graphene on Boron-doped diamond surface, and then obtains
Vertical graphene/boron-doped diamond sensing electrode.Comprise the following steps that：
1) its surface is polished and pre-processed as substrate by selection tantalum piece or molybdenum sheet with fine sandpaper, is removed surface impurity and is beaten
Grind the uniform and consistent cut in direction；By the substrate after processing, each ultrasound is clear in ultra-pure water, absolute ethyl alcohol, ultra-pure water successively
Wash 6min-10min；
2) substrate after cleaning is put into the suspension of diamond micro-nano powder, ultrasonic grinding 40min-60min makes base
The abundant forming core in piece surface；Substrate after forming core is handled is cleaned by ultrasonic 5min-10min in ultra-pure water, and with nitrogen by substrate
The moisture drying on surface；Wherein, the suspension of diamond micro-nano powder is diamond micro-nano powder and acetone, absolute ethyl alcohol or super
Pure water is mixed, and diamond micro-nano content of powder is about 1 milligram every milliliter in suspension；
3) substrate after drying is put on the sample stage in the chamber of electron assistant hot-filament chemical vapor deposition equipment, opened
Equipment is opened, the preparation of boron-doped diamond film is carried out；
Methane and hydrogen that purity is 99.999%, the two flow are passed through when preparing boron-doped diamond film, in chamber
Than being about 6mL/min:300mL/min；Boron source is trimethyl borate, and trimethylborate, the volume of the two are dissolved with absolute ethyl alcohol
Than for 3：1, boron source is inputted in reaction chamber by hydrogen, and the hydrogen flowing quantity for carrying boron source is about 25mL/min；Chamber room pressure is
4700-5300Pa；The temperature for growing boron-doped diamond is 900-1000 DEG C；Growth time at least 24 hours.
4) electron assistant hot-filament chemical vapor deposition equipment is closed, boron-doped diamond film is taken out；
5) ion sputtering equipment is used, in gold of the number of plies magnitude of Boron-doped diamond surface uniform fold one for Nano grade
Granulosa is used as the catalyst for growing graphene；
6) boron-doped diamond film combined after catalytic materials is positioned over into DC plasma jet chemical vapor deposition to set
On sample stage in standby chamber, equipment is opened, is combined in boron-doped diamond film and grows graphene on catalysis object plane；
When growing graphene, it is that 99.999% ratio is 2 Standard Liters per Minutes to be passed through purity：1.5 Standard Liters per Minute
Hydrogen and argon gas, chamber inner pressure maintains by force 3000Pa, and arc power is 4600-5200W；Open arc power controlling switch
And after timing 2-3min, the methane gas that purity is 99.999% is passed through, start to pass through golden catalytic materials in Boron-doped diamond surface
Effect carry out the growth of graphene, growth time is at least 15min, and the temperature in graphene growth face is about at 850 degrees Celsius；
7) pass hull closure, obtains vertical graphene/boron-doped diamond compound film, cuts the size of needs as sensing electricity
Pole.
It is an advantage of the invention that：
The high-quality boron-doped diamond film and graphene prepared ensure that vertical graphene/boron-doped diamond compounded
The quality of film, and the structure of composite membrane is close, is difficult layering and comes off.The combination of vertical graphene and boron-doped diamond can fill
The advantage and synergy of the two are waved in distribution, and the graphene of vertical-growth has bigger effective ratio table compared to the graphene of tiling
Area, as that can effectively improve detectability during sensing electrode, is used as the boron-doped diamond sheet of vertical graphene growth substrate
The characteristic of body causes the composite membrane to be reduced compared to the background current for the Graphene electrodes for being grown on metallic substrates, and potential window increases
Plus.Vertical graphene/boron-doped diamond compounded the film for cutting appropriate size from obtained composite membrane can be straight as sensing electrode
Connect the detection for biomolecule.
Brief description of the drawings
Fig. 1 gives the Boron-doped diamond surface and profile scanning figure of the preparation of embodiment 1,
Fig. 2 gives embodiment 2 and prepares vertical graphenic surface and side scanning figure (a), and vertical graphene/boron-doping gold
Hard rock composite membrane profile scanning figure (b),
Fig. 3 gives embodiment 3 and detects that dopamine biomolecule is obtained by vertical graphene/boron-doped diamond sensing electrode
The differential pulse voltammetry curve arrived.
Embodiment
Then the present invention passes through golden catalytic materials using electron assistant hot-wire chemical gas-phase deposition method growth boron-doped diamond
Effect, using DC electric arc plasma chemical vapor deposition equipment in Boron-doped diamond surface vertical-growth graphene, from
And realize that the combination of two kinds of elite clones of boron-doped diamond and graphene obtains vertical graphene/boron-doped diamond sensing electrode,
And then material impact is produced to boron-doped diamond actual application related to graphene.Below will be to preparing vertical graphene/mix
The most preferred embodiment of boron diamond sensing electrode is described in detail.
Embodiment 1：
A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, the preparation process of boron-doped diamond is as follows：
1) its surface is polished and pre-processed, polished metallic luster and polish uniform and square as substrate by selection molybdenum sheet
To consistent cut；Then by the molybdenum sheet after polishing successively each ultrasonic cleaning 6min in ultra-pure water, absolute ethyl alcohol, ultra-pure water；
2) molybdenum sheet after cleaning is put into well-mixed acetone：Diamond micro-nano powder (1：1) in suspension, ultrasound is ground
40min is ground, makes the abundant forming core in molybdenum sheet surface；Molybdenum sheet after then forming core is handled is cleaned by ultrasonic 5min in ultra-pure water, is used in combination
Nitrogen dries up the moisture on molybdenum sheet surface；
3) molybdenum sheet after drying is put on the sample stage in the chamber of electron assistant hot-filament chemical vapor deposition equipment, entered
The preparation of row boron-doped diamond film；The parameter for preparing boron-doped diamond film is as follows：It is 99.999% to be passed through chamber purity
Methane gas：Hydrogen flowing quantity ratio is 6mL/min:300mL/min, boron source is trimethyl borate：Absolute ethyl alcohol volume ratio is 3：1
Mixed solution, by boron source and to be passed through the hydrogen flowing quantity that the purity of chamber is 99.999% be 20mL/min；Chamber room pressure
About 5000Pa；The temperature on tantalum piece surface is about 950 DEG C；Growth time is 48 hours, and pass hull closure is obtained by mechanical means
Boron-doped diamond electrode, electron micrograph such as Fig. 1；
Embodiment 2：
A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, step is as follows：
1) its surface is polished and pre-processed, polished metallic luster and polish uniform and square as substrate by selection tantalum piece
To consistent cut；Then by the tantalum piece after polishing successively each ultrasonic cleaning 10min in ultra-pure water, absolute ethyl alcohol, ultra-pure water；
2) tantalum piece after cleaning is put into well-mixed absolute ethyl alcohol：Diamond micro-nano powder (1：1) in suspension, surpass
Sound grinds 60min, makes the abundant forming core in tantalum piece surface；Tantalum piece after then forming core is handled is cleaned by ultrasonic 10min in ultra-pure water,
And dried up the moisture on tantalum piece surface with nitrogen；
3) tantalum piece after drying is put on the sample stage in the chamber of electron assistant hot-filament chemical vapor deposition equipment, entered
The preparation of row boron-doped diamond film；The parameter for preparing boron-doped diamond film is as follows：It is 99.999% to be passed through chamber purity
Methane gas：Hydrogen flowing quantity ratio is 6mL/min:300mL/min, boron source is trimethyl borate：Absolute ethyl alcohol volume ratio is 3：1
Mixed solution, by boron source and to be passed through the hydrogen flowing quantity that the purity of chamber is 99.999% be 25mL/min；Chamber room pressure
About 5000Pa；The temperature on tantalum piece surface is about 950 DEG C；Growth time is 70 hours, and pass hull closure is obtained by mechanical means
Boron-doped diamond；
4) by model HFC-1600 metal-spraying equipment, one layer of fine and close gold is sprayed in the aufwuchsplate of the boron-doped diamond thin
Film, injecting time is 60 seconds, thickness nanometer scale；
5) boron-doped diamond film after metal spraying is positioned over DC plasma jet chemical vapor depsotition equipment chamber
In sample stage on, the vertical-growth graphene on the metal spraying face of boron-doped diamond film；The parameter for growing graphene is as follows：It is logical
Enter that purity is 99.999% hydrogen and the flow of argon gas is 1.5L/min, when chamber inner pressure maintains by force 3000Pa or so
Afterwards, arc power controlling switch and timing 3min are opened, now arc power is about 5000W；After timing 3min, being passed through purity is
99.999% methane gas flow is 200mL/min, starts to carry out the growth of graphene in the metal spraying face of boron-doped diamond, raw
It is for a long time 15min, the temperature in graphene growth face is at 800 DEG C or so；Grow after 15min, pass hull closure, system is taken out after cooling
Standby obtained vertical graphene/boron-doped diamond compounded film；Electron micrograph such as Fig. 2；
Embodiment 3：
A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, and to detect dopamine, step is such as
Under:1) compound concentration is 0.1 mole every liter of sodium dihydrogen phosphate and disodium phosphate soln mixed preparing is that the PBS that pH is 7 delays
Solution is rushed, and deoxygenation processing is carried out by nitrogen gas generator, is respectively then 10 with the PBS solution compound concentration-3mol/L、5*
10-4mol/L、10-4mol/L、5*10-5mol/L、10-5Mol/L dopamine solution；2) using obtaining vertical stone in embodiment 2
Black alkene/boron-doped diamond compounded film, it is about 0.2 square centimeter as sensing electrode to cut size；Utilize electrochemical workstation
Testing procedure 1) in biomolecules of dopamine in various concentrations solution, three-electrode system is used during test, wherein, working electrode
It is platinum plate electrode to electrode, reference electrode is saturated calomel electrode for the vertical graphene/boron-doped diamond sensing electrode；Inspection
Survey mode is differential pulse voltammetry, obtains peak curve such as Fig. 3；
It is pointed out that proposed by the present invention be used as catalytic materials in Boron-doped diamond surface growth of vertical by gold grain
Graphene obtains the technical scheme of vertical graphene/boron-doped diamond compounded film, is acted on by other suitable catalytic materials
Under can also realize.In particular, to prepare graphene/boron-doped diamond multiple for all similar replacements and change
Closing the method for film should be deemed to be included in spirit, scope and the content of the present invention.
Claims (6)
1. a kind of preparation method of vertical graphene/boron-doped diamond sensing electrode, it is characterised in that use electron assistant heated filament
Chemical vapor depsotition equipment prepares boron-doped diamond film, by golden catalytic materials act on Boron-doped diamond surface using etc. from
Chemical vapour deposition technique growth of vertical graphene is sprayed in daughter, and step is as follows：
1) its surface is polished and pre-processed as substrate by selection tantalum piece or molybdenum sheet with fine sandpaper, is removed surface impurity and is polished
The uniform and consistent cut in direction；By the substrate after processing successively each ultrasonic cleaning 6- in ultra-pure water, absolute ethyl alcohol, ultra-pure water
10min；
2) substrate after cleaning is put into the suspension of diamond micro-nano powder, ultrasonic grinding 40min-60min makes substrate table
The abundant forming core in face；Substrate after forming core is handled is cleaned by ultrasonic 5min-10min in ultra-pure water, and with nitrogen by substrate surface
Moisture drying；
3) substrate after drying is put on the sample stage in the chamber of electron assistant hot-filament chemical vapor deposition equipment, unlatching is set
It is standby, carry out the preparation of boron-doped diamond film；
4) electron assistant hot-filament chemical vapor deposition equipment is closed, boron-doped diamond film is obtained by mechanical means；
5) catalytic materials are used as in one layer of gold thin film of Boron-doped diamond surface uniform fold；
6) boron-doped diamond film combined after catalytic materials is positioned over DC plasma jet chemical vapor depsotition equipment chamber
On sample stage in room, equipment is opened, is combined in boron-doped diamond film and grows graphene on catalysis object plane；
7) pass hull closure, obtains vertical graphene/boron-doped diamond compound film, cuts the size of needs as sensing electrode.
2. the preparation method of vertical graphene/boron-doped diamond sensing electrode according to claim 1, it is characterised in that：
Step 2) described in diamond micro-nano powder suspension be diamond micro-nano powder and acetone, absolute ethyl alcohol or ultra-pure water prepare
Form, diamond micro-nano content of powder is 1 milligram every milliliter in suspension.
3. the preparation method of vertical graphene according to claim 1/boron-doped diamond compounded film, it is characterised in that：
Step 3) described in electron assistant hot-filament chemical vapor deposition equipment by water circulation system, chamber, filament supply and grid bias power supply
Composition, water circulation system prevents that filament frame part temperature is too high in chamber and chamber, and filament supply provides electric current to filament
With voltage, filament is a diameter of 0.6 millimeter of tantalum wire, and grid bias power supply provides potential between filament and substrate, guides carbon atom
In deposition on substrate.
4. the preparation method of vertical graphene/boron-doped diamond sensing electrode according to claim 1, it is characterised in that：
Step 3) in, the methane gas that the purity that flow-rate ratio is 2% is 99.999% is passed through when preparing boron-doped diamond film, in chamber
Body：Hydrogen, boron source is trimethyl borate：Absolute ethyl alcohol volume ratio is 3：1 mixed solution, by boron source and is passed through the pure of chamber
The hydrogen flowing quantity that degree is 99.999% is that 25 standard milliliters are per minute；Chamber room pressure is 4700-5300Pa；Substrate grows boron-doping
The temperature on the surface of diamond is 900-1000 DEG C；Growth time at least 24 hours.
5. the preparation method of vertical graphene/boron-doped diamond sensing electrode according to claim 1, it is characterised in that：
Step 5) in catalytic materials be metallic gold, golden thickness spray by metal-spraying equipment in Boron-doped diamond surface is nanometer scale.
6. the preparation method of vertical graphene/boron-doped diamond sensing electrode according to claim 1, it is characterised in that：
Step 6) in, during growth graphene, it is that 99.999% ratio is 1 to be passed through purity：1 hydrogen and argon gas, chamber inner pressure is tieed up by force
Hold in 3000Pa, arc power is 4600-5200W；Open after arc power controlling switch and timing 2-3min, being passed through purity is
99.999% methane gas, starts to carry out the growth of graphene by the effect of golden catalytic materials in Boron-doped diamond surface, raw
It is at least 10min for a long time, the temperature in graphene growth face is at 850-950 degrees Celsius.
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| CN111517305A (en) * | 2020-04-08 | 2020-08-11 | 北京科技大学 | Preparation method of graphene/diamond composite structure with high carrier concentration |
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| CN111517305A (en) * | 2020-04-08 | 2020-08-11 | 北京科技大学 | Preparation method of graphene/diamond composite structure with high carrier concentration |
| CN111562297A (en) * | 2020-05-11 | 2020-08-21 | 中南大学 | Non-enzymatic biosensor based on carbon material/boron-doped diamond composite electrode and preparation method and application thereof |
| 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 |
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| CN113881929A (en) * | 2021-09-15 | 2022-01-04 | 湖南新锋先进材料科技有限公司 | Diamond-graphene film with double-sided structure and preparation method and application thereof |
| CN113881929B (en) * | 2021-09-15 | 2024-04-02 | 湖南新锋先进材料科技有限公司 | Diamond-graphene film with double-sided structure, and preparation method and application thereof |
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