CN108658037A - A kind of graphene functionalized nanometer pinpoint and preparation method thereof - Google Patents
A kind of graphene functionalized nanometer pinpoint and preparation method thereof Download PDFInfo
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- CN108658037A CN108658037A CN201810395415.1A CN201810395415A CN108658037A CN 108658037 A CN108658037 A CN 108658037A CN 201810395415 A CN201810395415 A CN 201810395415A CN 108658037 A CN108658037 A CN 108658037A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B1/001—Devices without movable or flexible elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0019—Forming specific nanostructures without movable or flexible elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention provides a kind of graphene functionalized nanometer pinpoint, is the metal needle point that surface is covered with continuous graphite alkene layer, the tip diameter of the metal needle point is 10~500nm, and graphene and needle surface have good interfacial contact.The present invention also proposes the preparation method of the graphene functionalized nanometer pinpoint.Graphene functionalized nanometer pinpoint proposed by the present invention has excellent needle point pattern, and needle point tip is sharp, surfacing；The graphene that is formed in wide area is continuous and corrugationless.Since the excellent electric property of graphene itself and the good interface of graphene and needle surface contact, graphene functionalized nanometer pinpoint prepared by the method for the invention possesses the electric conductivity and durability that usual metal needle point cannot compare.In addition, the chemical stability of graphene itself, ensure that the inoxidizability for changing functionalized nano needle point.
Description
Technical field
The invention belongs to metal material functionalization fields, and in particular to a kind of needle point and its system with grapheme material modification
Standby method.
Background technology
With the rise of nano material and nanotechnology, the preparation of nano material functionalization needle point and its in different field
Using the broad interest for causing whole world researcher.Special construction based on nano material itself and property, these functions
Change nanometer pinpoint and usually possesses excellent mechanics and electric property.For example, Nano diamond needle point is because of its outstanding mechanical property
There is good application prospect [1,2] in nanoprocessing and tribology tester field with durability.Electric conductive oxidation Asia tungsten nanometer rods work(
Needle point can be changed and can be used as multiprobe atomic force microscope (AFM) probe, different materials are carried out on micron/nano scale flexible
Electrical measurement and mechanics evaluation [3,4].In addition, in terms of carbon nano tube modified pinpoint array can be used for neuron electrical measurement
And there is higher sensitivity and bio-compatibility[5]。
Graphene be there is atomic level thickness two dimensional crystal structure is formed by carbon hexatomic ring, came out from 2004 with
Come, has become the research hotspot of field of nanometer material technology.Graphene possesses the incomparable mechanics and electricity of many other materials
Property.The Young's modulus of single-layer graphene is 1Tpa, and electron mobility is at room temperature up to 105cm2V-1s-1, and be resistant to
Current density is 106 times of copper[6].Therefore, graphene functionalized needle point is widely believed that in nanoprocessing and electrical measurement field
With outstanding application potential.Duan et al. will utilize chemical vapor deposition (CVD) method system in advance using physical transfer method
Standby graphene film is adsorbed on silicon substrate afm tip surface, improves the stability and durability of needle point[7].However, physical absorption
Method cannot be guaranteed the good contact of graphene layer and needle surface, lack and the pattern of tip portion controlled.Therefore, in needle
Sharp surface, especially tip portion, growth in situ graphene become the trend in the field.CVD method is current graphene growth
A kind of main method, it usually needs the substrate surface strictly handled and very high growth temperature (~1000 DEG C)[8-10]。
Gimzewski and Liu et al. people attempt to grow graphite in the afm tip surface in situ for being coated with Cu and Au using CVD method respectively
Alkene[11,12].However, due to growing required long-time hot environment, the tip ruler of obtained graphene functionalized needle point
Very little other and cutting-edge structure in the micron-scale is uncontrollable.So far, researcher still can not prepare with nanotip size
And possess the graphene functionalized probe of controllable needle point structure.
Bibliography
[1]H.Bhaskaran,B.Gotsmann,A.Sebastian,U.Drechsler,M.A.Lantz,
M.Despont,P.Jaroenapibal,R.W.Carpick,Y.Chen,K.Sridharan,Nat Nanotechnol2010,
5,181.
[2]H.J.Kim,N.Moldovan,J.R.Felts,S.Somnath,Z.T.Dai,T.D.B.Jacobs,
R.W.Carpick,J.A.Carlisle,W.P.King,Nanotechnology 2012,23,495302.
[3]T.Nakayama,O.Kubo,Y.Shingaya,S.Higuchi,T.Hasegawa,C.S.Jiang,
T.Okuda,Y.Kuwahara,K.Takami,M.Aono,Adv Mater 2012,24,1675.
[4]O.Kubo,Y.Shingaya,M.Nakaya,M.Aono,T.Nakayama,Appl Phys Lett2006,
88,254101.
[5]E.W.Keefer,B.R.Botterman,M.I.Romero,A.F.Rossi,G.W.Gross,Nat
Nanotechnol 2008,3,434.
[6]K.S.Novoselov,V.I.Fal'ko,L.Colombo,P.R.Gellert,M.G.Schwab,K.Kim,
Nature 2012,490,192.
[7]M.Lanza,A.Bayerl,T.Gao,M.Porti,M.Nafria,G.Y.Jing,Y.F.Zhang,
Z.F.Liu,H.L.Duan,Adv Mater 2013,25,1440.
[8]Z.P.Chen,W.C.Ren,L.B.Gao,B.L.Liu,S.F.Pei,H.M.Cheng,Nat Mater 2011,
10,424.
[9]K.V.Emtsev,A.Bostwick,K.Horn,J.Jobst,G.L.Kellogg,L.Ley,
J.L.McChesney,T.Ohta,S.A.Reshanov,J.Rohrl,E.Rotenberg,A.K.Schmid,D.Waldmann,
H.B.Weber,T.Seyller,Nat Mater 2009,8,203.
[10]Y.B.Chen,J.Y.Sun,J.F.Gao,F.Du,Q.Han,Y.F.Nie,Z.Chen,A.Bachmatiuk,
M.K.Priydarshi,D.L.Ma,X.J.Song,X.S.Wu,C.Y.Xiong,M.H.Rummeli,F.Ding,Y.F.Zhang,
Z.F.Liu,Adv Mater 2015,27,7839.
[11]Y.G.Wen,J.Y.Chen,Y.L.Guo,B.Wu,G.Yu,Y.Q.Liu,Adv Mater2012,24,3482.
[12]C.Martin-Olmos,H.M.Rasool,B.H.Weiller,J.K.Gimzewski,Acs Nano
2013,7,4164.
Invention content
Place, one of the objects of the present invention are to provide a kind of graphene functionalized nanometer in view of the shortcomings of the prior art
Needle point.
It is another object of the present invention to propose the preparation method of the graphene functionalized nanometer pinpoint.
Realize that the technical solution of above-mentioned purpose of the present invention is：
A kind of graphene functionalized nanometer pinpoint is the metal needle point that surface is covered with continuous graphite alkene layer, the metal
The tip diameter of needle point is 10~500nm, and graphene and needle surface have good interfacial contact.
Further, the material of the metal needle point is the compound of one or both of Ni, Co, W, and compound mode is
Coating and base material are compound.The apex angle at needle point tip is 10~70 °.
Preferably, the graphene is single layer and multilayered structure, and for single layer, far from gradual mistake at tip at needle point tip
It crosses as multilayer；It is from 10~200 μm down of top that graphene, which covers needle point area,.
Based on existing microexamination condition, the graphene position of single layer structure is about in needle point tip 100nm models down
In enclosing, the graphene position of multilayered structure is about under needle point tip in the μ ms of 100nm~200.
A kind of preparation method of graphene functionalized nanometer pinpoint, includes the following steps：
1) metal needle point is contacted with carbon source, then by heat treatment, metal needle point surface is made to form carburization zone；The carbon source
For high purity graphite target or carbon-containing molecules；
2) under the conditions of gas shield, by way of electrified regulation or annealing, graphene is formed on metal needle point surface；
The electrified regulation mode is that the metal needle point with carburization zone is fixed on conductive carrier, is applied at conductive carrier both ends
Transient voltage makes immediate current generate Joule heat by conductive carrier, on heat transfer to metal needle point, in metal needle point surface shape
At graphene；The temperature of the annealing is 500~600 DEG C.
Wherein, the metal needle point contacts after overpickling removes oxide layer, water cleaning, drying with carbon source.
The preferred technical solution of the present invention is that the carbon source is high purity graphite target, and high purity graphite target passes through magnetron sputtering side
Carbon is evaporated to metal needle point surface by method, then forms carburization zone by annealing；Or, the carbon source is carbon-containing molecules, it will be golden
Belong to needle point to be placed in the carbon-containing molecules solution in reaction kettle, (reaction kettle is closed, and pressure is nature boosting, pressure for high-temperature closed
Less than 5.0MPa) under the conditions of, form carburization zone on metal needle point surface.
Wherein, in step 1), the carbon source is triethylene glycol, triethanolamine, resorcinol, one kind in glucose or more
The mixing of kind and sodium hydroxide, the carbon source are liquid or the solution for being configured to 0.01~5mol/L.
Optionally, the carbon source is one kind in triethylene glycol, triethanolamine, resorcinol, by volume 1：4~5
Ratio and the mixing of the NaOH solution or glucose solution of a concentration of 0.1~1mol/L.
It is highly preferred that in step 1), the metal needle point is immersed in carbon source and is heated together, it is described to be heated to be:With 2~8
DEG C/heating rate of min is heated to 200~250 DEG C, Temperature fall after being kept for 1~3 hour.
The gas shield condition can be one or more gas atmospheres in nitrogen, argon gas, neon.Protect gas
Body can static can also be flowing.
Wherein, in step 2), the material of the conductive carrier is metal or graphite, and conductive carrier shape is silk, band or boat；
A diameter of 0.05~0.5mm of the silk, the specification of band be long 10~100mm × wide 0.1~10mm × thickness 0.05~
The size of 0.2mm, boat are long 50~200mm × wide 5~15mm.
Wherein, the shape of band can curve U-shaped or V-type, and metal needle is fixed on U-shaped or V-type centre.
Wherein, in step 2), the electric current by the conductive carrier is 1~50A, and conduction time is 0.01~5 second.
Alive size and duration and the material (resistivity) and dimensions of the wire/band/boat it is close
Cut phase is closed.When the resistivity of metal material used is larger, thickness, width or diameter it is smaller under conditions of, institute's galvanization, that is, corresponding
Smaller, the duration is accordingly shorter；When metal material used is smaller, thickness, width or under conditions of being relatively large in diameter, institute's galvanization
I.e. corresponding larger, the duration is accordingly longer.The method of the invention and under the conditions of, institute's galvanization rises to target current from 0A
About 10 milliseconds the time required to value, metal needle point can be heated to a very high temperature to be more than the heating rate of 1000 DEG C/s
Degree (>1000℃).The ultrafast high annealing method can cause metal needle point surface to be rapidly achieved condition needed for graphene growth；
Meanwhile with optimal conditions, metal needle point in the duration of high temperature section within 2 seconds, you can moment drops to low temperature.This method
It ensure that the melting and oxidation that metal needle point tip is avoided while the graphene of metal needle point Surface Creation large area.This
The ultra-fast anneal process of invention solves CVD method and conventional anneal handles faced needle point passivation and cutting-edge structure is uncontrollable
The problem of.
Graphene functionalized nanometer pinpoint proposed by the present invention has excellent needle point pattern, and needle point tip is sharp, surface
It is smooth；The graphene that is formed in wide area is continuous and corrugationless.Due to the excellent electric property of graphene itself and
The good interface of graphene and needle surface contacts, and graphene functionalized nanometer pinpoint prepared by the method for the invention possesses logical
The electric conductivity and durability that normal metal needle point cannot compare.In addition, the chemical stability of graphene itself, ensure that and change work(
The inoxidizability of nanometer pinpoint can be changed.
Description of the drawings
The a of Fig. 1 is the device schematic diagram that electrochemical erosion method prepares original nickel needle, and the b of Fig. 1 is the TEM image for generating nickel needle.
Fig. 1 c correspond to the HR-TEM images of nickel needle tip, and the d of Fig. 1 is corresponding SAED styles (scale is 5 1/nm in Fig. 1 d).
In Fig. 2, a, b are two kinds of device schematic diagrams of TRANSIENT HIGH TEMPERATURE annealing fixed heat nickel needle used, respectively U-shaped Pt
Band and V-type Pt bands；When c is that setting electric current 10A is heated by Pt bands, the single pulse of oscillograph recording；D schemes and e figures are right respectively
The U-shaped Pt bands and V-type Pt band heating devices answered, when TRANSIENT HIGH TEMPERATURE heats, a series of photos of tip red heat.
Fig. 3 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.
Fig. 4 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.
Fig. 5 is saturating corresponding to a kind of typical graphene functionalized nanometer pinpoint prepared by the processing of usual tube annealing
Penetrate electromicroscopic photograph.
Fig. 6 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.
Specific implementation mode
The present invention is now illustrated with following most preferred embodiment, but is not limited to the scope of the present invention.
Embodiment 1：
Using electrochemical erosion method, be prepared tip diameter 30nm or so W metal needle point.The a electrifications of Fig. 1
The device schematic diagram that etch prepares original nickel needle is learned, is that nickel wire is connected to positive pole, Jin Huan connection power cathodes.Utilize golden ring
On the KCl liquid films of 1M gradually corrode Ni and finally obtain Ni needle points.The b of Fig. 1 is the TEM image for generating nickel needle, needle surface
It is smooth, tip size about 30nm.Fig. 1 c correspond to the HR-TEM images of nickel needle tip, and the d of Fig. 1 is corresponding SAED styles.Needle point
The apex angle at tip is about 30 °.
Ni needle points are rinsed with a large amount of water, are soaked in spirit of vinegar and are removed surface oxide layer, then are rinsed with a large amount of water, and nitrogen is blown
It is dry.Above-mentioned Ni needle points are fixed in autoclave vertically, the triethylene glycol solution that 100 μ L purity are 99% are added, simultaneously
The NaOH solution that 450 a concentration of 0.1mol/L of μ L are added mixes well.Be placed in autoclave is closed in Muffle furnace, with 5 DEG C/
The heating rate of min is heated to 220 DEG C, Temperature fall after being kept for 2 hours.
By above-mentioned Ni needle points take out, with a large amount of water rinse, nitrogen drying after, spot welding be fixed on long 25mm × wide 1.2mm ×
Among the Pt metal band of thick 0.05mm；Pt metal band jack-knife shape, two-end-point solid welding are scheduled on two electrode columns of ceramic electrode
(Fig. 2 b).Above-mentioned sample is fixed on two electrode columns on the electrode flange of high vacuum cavity, using molecular pump that cavity is true
Sky is evacuated to 10-5Pump is closed after Pa, is filled with high pure nitrogen.It is 10A using DC power supply one size of output, 1.5 seconds duration
Immediate current passes through Pt metal tapes；Pt metal tapes and the W metal needle point moment being fixed thereon reach red heat state, such as Fig. 2 e
It is shown.After sample cooling, metal needle point is taken out, graphene functionalized nanometer pinpoint as shown in Figure 3 is obtained.
In Fig. 2, a, b are two kinds of device schematic diagrams of TRANSIENT HIGH TEMPERATURE annealing fixed heat nickel needle used, respectively U-shaped Pt
Band and V-type Pt bands；When c is that setting electric current 10A is heated by Pt bands, the single pulse of oscillograph recording；D schemes and e figures are right respectively
The U-shaped Pt bands and V-type Pt band heating devices answered, in instantaneous (heating time is no more than 2S) high-temperature heating, the one of tip red heat
Serial-gram.
Fig. 3 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.By electric current 10A, heating time 1.5S, Pt bandwidth is 1.2mm.Fig. 3
Center electromicroscopic photograph shows that the nanometer pinpoint pointed shape that this condition annealing generates remains unchanged, and five-pointed star mark is white in figure
Frame region transmission electron microscope photo shows that needle surface generates graphene；Figure intermediate cam shape identifies white edge region high-resolution-ration transmission electric-lens
Photo shows that needle point tip end surface generates single-layer graphene；Hexagon mark white edge region high-resolution-ration transmission electric-lens photo is aobvious in figure
Show that needle point sidewall surfaces generate multi-layer graphene；Lower-left is corresponding Raman collection of illustrative plates.Based on existing microexamination condition, single layer
The graphene position of structure is about within the scope of needle point tip down 100nm, and the graphene position of multilayered structure is about in needle point
Under tip in the μ ms of 100nm~200.
Transmission electron microscope observing result is shown in Ni needle points tip size about 30nm, surfacing and the continuous single layer stone of covering
Black alkene；It is multilayered structure to go out graphene farther out from needle point tip.Microscopic Raman test result confirms the presence of graphene-structured,
About 50 μm far from needle point distance between two tips of graphene overlay area edge.
Embodiment 2
Using electrochemical erosion method, be prepared tip diameter 30nm or so W metal needle point.Ni needle points are with largely
Water rinses, and is soaked in spirit of vinegar and removes surface oxide layer, then is rinsed with a large amount of water, nitrogen drying.Above-mentioned Ni needle points is vertical
It is fixed in autoclave, the triethylene glycol solution that 100 μ L purity are 99% is added, while it is a concentration of that 450 μ L are added
The NaOH solution of 0.1mol/L mixes well.Aforesaid reaction vessel is placed in Muffle furnace, is heated to the heating rate of 5 DEG C/min
220 DEG C keep 2 hours after Temperature fall.
Above-mentioned Ni needle points are taken out, are rinsed with a large amount of water, after nitrogen drying, it is thick that spot welding is fixed on long 25mm* wide 0.85mm*
Among the Pt metal band of 0.05mm；Pt metal band curves U-shape, and two-end-point solid welding is scheduled on two electrode columns of ceramic electrode
(Fig. 2 a).Above-mentioned sample is fixed on two electrode columns on the electrode flange of high vacuum cavity, using molecular pump that cavity is true
Sky is evacuated to 10-5Pump is closed after Pa, is filled with high pure nitrogen.It is 10A using DC power supply one size of output, 0.75 second duration
Immediate current passes through Pt metal tapes；Pt metal tapes and the W metal needle point moment being fixed thereon reach red heat state, such as Fig. 2 d
It is shown.After sample cooling, metal needle point is taken out, graphene functionalized nanometer pinpoint as shown in Figure 4 is obtained.Transmission electron microscope is seen
It examines result and is shown in Ni needle points tip size about 100nm, surfacing and the continuous single-layer graphene of covering；From needle point tip compared with
It is multilayered structure far to go out graphene.Microscopic Raman test result confirms the presence of graphene-structured, graphene overlay area from
About 100 μm of needle point distance between two tips.
Fig. 4 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.By electric current 10A, heating time 0.75s, Pt bandwidth is 0.85mm.
The centers Fig. 4 electromicroscopic photograph shows that the nanometer pinpoint tip that this condition annealing generates is slightly molten, five-pointed star mark white edge region in figure
Transmission electron microscope photo shows that needle surface generates graphene；It is aobvious that figure intermediate cam shape identifies white edge region high-resolution-ration transmission electric-lens photo
Show that needle point tip end surface generates single-layer graphene；Hexagon mark white edge region high-resolution-ration transmission electric-lens photo shows needle point in figure
Sidewall surfaces generate multi-layer graphene；Lower-left is corresponding Raman collection of illustrative plates.
Embodiment 3
Using electrochemical erosion method, be prepared tip diameter 30nm or so W metal needle point.Ni needle points are with largely
Water rinses, and is soaked in spirit of vinegar and removes surface oxide layer, then is rinsed with a large amount of water, nitrogen drying.Above-mentioned Ni needle points is vertical
It is fixed in autoclave, the triethylene glycol solution that 100 μ L purity are 99% is added, while it is a concentration of that 450 μ L are added
The NaOH solution of 0.1mol/L mixes well.Aforesaid reaction vessel is placed in Muffle furnace, is heated to the heating rate of 5 DEG C/min
220 DEG C are held Temperature fall after 2 hours.
Above-mentioned Ni needle points are taken out, are rinsed with a large amount of water, after nitrogen drying, needle point tip is fixed on corundum needle holder upward
On, then needle holder is positioned over diamond heating region.Chamber vacuum is evacuated to 10 using molecular pump-5Pump is closed after Pa, is filled with high-purity
Nitrogen, with the heating rate of 5 DEG C/min be heated to 550 DEG C keep 0.5 hour after Temperature fall.After sample cooling, gold is taken out
Belong to needle point, obtains graphene functionalized nanometer pinpoint as shown in Figure 5.Transmission electron microscope observing result is shown in Ni needle points tip ruler
Very little about 100nm, surface major part region are aoxidized, and very small region covers single-layer graphene.
Fig. 5 is saturating corresponding to a kind of typical graphene functionalized nanometer pinpoint prepared by the processing of usual tube annealing
Penetrate electromicroscopic photograph.A schemes and b figures are static state N2Under atmosphere, the nanometer pinpoint of annealing；C and d figures are flowing N2Under atmosphere, annealing
The nanometer pinpoint of processing.In flowing N2Under atmosphere, more severe, the graphene region smaller of Surface Creation of nanometer pinpoint oxidation.
Embodiment 4
Using electrochemical erosion method, be prepared tip diameter 30nm or so W metal needle point.Ni needle points are with largely
Water rinses, and is soaked in spirit of vinegar and removes surface oxide layer, then is rinsed with a large amount of water, nitrogen drying.Above-mentioned Ni needle points is vertical
It is fixed in autoclave, the triethylene glycol solution that 100 μ L purity are 99% is added, while it is a concentration of that 450 μ L are added
The NaOH solution of 0.1mol/L mixes well.Aforesaid reaction vessel is placed in Muffle furnace, is heated to the heating rate of 5 DEG C/min
220 DEG C keep 2 hours after Temperature fall.
Above-mentioned Ni needle points are taken out, are rinsed with a large amount of water, after nitrogen drying, it is thick that solid welding is scheduled on long 25mm* wide 0.5mm*
The metal Ta bands of 0.05mm are intermediate；Metal Ta band jack-knife shapes, two-end-point solid welding are scheduled on two electrode columns of ceramic electrode
(Fig. 2 b).Above-mentioned sample is fixed on two electrode columns on the electrode flange of high vacuum cavity, using molecular pump that cavity is true
Sky is evacuated to 10-5Pump is closed after Pa, is filled with high-purity argon gas.It is 6A, the moment of 1 second duration to export a size using DC power supply
Electric current passes through Ta metal tapes；Ta metal tapes and the W metal needle point moment being fixed thereon reach red heat state, as shown in Figure 2 d.
After sample cooling, metal needle point is taken out, graphene functionalized nanometer pinpoint as shown in FIG. 6 is obtained.Transmission electron microscope observing knot
Fruit is shown in Ni needle points tip size about 30nm, surfacing and the continuous single-layer graphene of covering；Remotely from needle point tip
Graphene is multilayered structure.Microscopic Raman test result confirms the presence of graphene-structured, and graphene overlay area is from needle point
About 80 μm of distance between two tips.
Fig. 6 is a series of corresponding to a kind of typical graphene functionalized nanometer pinpoint of TRANSIENT HIGH TEMPERATURE annealing preparation
Transmission electron microscope photo and corresponding Raman collection of illustrative plates.By electric current 6A, heating time 1s, Ta bandwidth is 0.5mm.The a of Fig. 6
Transmission electron microscope photo shows that the nanometer pinpoint tip pattern that this condition annealing generates is kept, and b, c of Fig. 6 are respectively needle point point
End and the corresponding high-resolution-ration transmission electric-lens photo of side wall；The d of Fig. 6 is corresponding Raman collection of illustrative plates.
Above embodiment be only the preferred embodiment of the present invention is described, not to the scope of the present invention into
Row limits, under the premise of not departing from design spirit of the present invention, technical side of this field ordinary engineering and technical personnel to the present invention
The all variations and modifications that case is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of graphene functionalized nanometer pinpoint, which is characterized in that it is the metal needle point that surface is covered with continuous graphite alkene layer,
The tip diameter of the metal needle point is 10~500nm, and graphene and needle surface have good interfacial contact.
2. graphene functionalized nanometer pinpoint according to claim 1, which is characterized in that the material of the metal needle point is
One or both of Ni, Co, W's is compound, and compound mode is that coating and base material are compound, and the apex angle at needle point tip is 10~
70°。
3. graphene functionalized nanometer pinpoint according to claim 1, which is characterized in that the graphene is single layer and more
Layer structure, and be single layer at needle point tip, be multilayer far from gradual transition at tip；It is from top that graphene, which covers needle point area,
10~200 μm down.
4. a kind of preparation method of graphene functionalized nanometer pinpoint, which is characterized in that include the following steps：
1) metal needle point is contacted with carbon source, then by heat treatment, metal needle point surface is made to form carburization zone；The carbon source is height
Pure graphite target or carbon-containing molecules；
2) under the conditions of gas shield, by way of electrified regulation or annealing, graphene is formed on metal needle point surface；It is described
Electrified regulation mode is that the metal needle point with carburization zone is fixed on conductive carrier, applies moment at conductive carrier both ends
Voltage makes immediate current generate Joule heat by conductive carrier, and on heat transfer to metal needle point, stone is formed on metal needle point surface
Black alkene；The temperature of the annealing is 500~600 DEG C.
5. preparation method according to claim 4, which is characterized in that the metal needle point is the warp using wire as raw material
Electrochemical corrosion is made；Metal needle point contacts after overpickling removes oxide layer, water cleaning, drying with carbon source.
6. preparation method according to claim 4, which is characterized in that the carbon source is high purity graphite target, high purity graphite target
Carbon is evaporated to metal needle point surface by magnetically controlled sputter method, then carburization zone is formed by annealing；Or, the carbon source is
Metal needle point is placed in the carbon-containing molecules solution in reaction kettle by carbon-containing molecules, under the conditions of high-temperature closed, on metal needle point surface
Form carburization zone.
7. preparation method according to claim 6, which is characterized in that in step 1), the carbon source is triethylene glycol, three second
One or more and sodium hydroxide mixing in hydramine, resorcinol, glucose, the carbon source are liquid or are configured to
The solution of 0.01~5mol/L.
8. preparation method according to claim 7, which is characterized in that in step 1), the metal needle point is immersed in carbon source
In heat together, it is described to be heated to be:200~250 DEG C are heated to the heating rate of 2~8 DEG C/min, after being kept for 1~3 hour certainly
So cooling.
9. according to claim 4~8 any one of them preparation method, which is characterized in that in step 2), the conductive carrier
Material is metal or graphite, and conductive carrier shape is silk, band or boat；A diameter of 0.05~0.5mm of the silk, the specification ruler of band
Very little is long 10~100mm × wide 0.1~10mm × 0.05~0.2mm of thickness, and the size of boat is long 50~200mm × wide 5~15mm.
10. according to claim 4~8 any one of them preparation method, which is characterized in that in step 2), pass through the conduction
The electric current of carrier is 1~50A, and conduction time is 0.01~5 second.
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| CN112779517A (en) * | 2020-12-28 | 2021-05-11 | 吉林工程技术师范学院 | Preparation method of self-supporting nanocone diamond |
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| CN114217097A (en) * | 2021-11-19 | 2022-03-22 | 国家纳米科学中心 | Preparation method of graphene functionalized silicon-based probe |
| WO2022151349A1 (en) * | 2021-01-15 | 2022-07-21 | 国家纳米科学中心 | Functionalized carbon nanocone tip and preparation method therefor |
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