CN108658037B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- -1 graphite alkene Chemical class 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000969 carrier Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N Triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[[email protected]]1OC(O)[[email protected]](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[[email protected]]1O[C@@H](O)[[email protected]](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N Diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005485 electric heating Methods 0.000 claims 1
- 238000006056 electrooxidation reaction Methods 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000875 corresponding Effects 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 18
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000002356 single layer Substances 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- 230000001052 transient Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 230000003628 erosive Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000052 vinegar Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKCLAHRGFNTMAS-UHFFFAOYSA-N 1-[3-[2-[[2-(7-azido-4-methyl-2-oxochromen-3-yl)acetyl]amino]ethylsulfanyl]propanethioyloxy]-2,5-dioxopyrrolidine-3-sulfonic acid Chemical compound O=C1OC=2C=C(N=[N+]=[N-])C=CC=2C(C)=C1CC(=O)NCCSCCC(=S)ON1C(=O)CC(S(O)(=O)=O)C1=O OKCLAHRGFNTMAS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 230000003068 static Effects 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon(0) Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 210000002569 neurons Anatomy 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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, and 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 good interface of the excellent electric property of graphene itself and graphene and needle surface contacts, the graphene functionalized nanometer pinpoint of the method for the invention preparation 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 technique
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 and property based on nano material itself, 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 in nanoprocessing and tribology tester field with durability[1,2].Electric conductive oxidation Asia tungsten nanometer rods function
Changing needle point can be used as multiprobe atomic force microscope (AFM) probe, carry out on micron/nano scale to different materials 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 having
There are 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 using physical transfer method in advance
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 long-time hot environment required for growing, 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.
Summary of the invention
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 the technical solution of above-mentioned purpose of the present invention are as follows:
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 substrate are compound.The apex angle at needle point tip is 10~70 °.
Preferably, the graphene is single layer and multilayered structure, and is single layer at needle point tip, far from gradually mistake at 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 model down
In enclosing, the graphene position of multilayered structure is about under needle point tip in the μ m of 100nm~200.
A kind of preparation method of graphene functionalized nanometer pinpoint, comprising 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, carburization zone is formed on metal needle point surface.
Wherein, in step 1), the carbon source is one of triethylene glycol, triethanolamine, resorcinol, 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 of triethylene glycol, triethanolamine, resorcinol, by volume 1:4~5
The NaOH solution or glucose solution mixing that ratio and concentration are 0.1~1mol/L.
It is highly preferred that the metal needle point is immersed in carbon source and is heated together in step 1), the heating are as follows: 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 of nitrogen, argon gas, neon or a variety of gas atmospheres.Protect gas
Body, which can be, 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；
The diameter of the silk is 0.05~0.5mm, the specification of band be long 10~100mm × wide 0.1~10mm × thickness 0.05~
0.2mm, the size of 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 wire/band/boat material (resistivity) and dimensions it is close
Cut phase is closed.When the resistivity of metal material used is larger, thickness, width or diameter it is lesser under the 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 with the heating rate greater than 1000 DEG C/s
It spends (> 1000 DEG C).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 can drop to low temperature in the duration of high temperature section within 2 seconds moment.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, and to handle faced needle point passivation and cutting-edge structure 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 contact of the good interface of graphene and needle surface, the graphene functionalized nanometer pinpoint of the method for the invention preparation possess 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 function
The inoxidizability of nanometer pinpoint can be changed.
Detailed description of the invention
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 corresponds to the HR-TEM image of nickel needle tip, and the d of Fig. 1 is corresponding SAED style (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 band；When c is that setting electric current 10A is heated by Pt band, the single pulse of oscillograph recording；D figure and e figure are right respectively
The U-shaped Pt band and V-type Pt band heating device answered, in TRANSIENT HIGH TEMPERATURE heating, 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 map.
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 map.
Fig. 5 is saturating corresponding to a kind of typical graphene functionalized nanometer pinpoint of usual tube annealing processing preparation
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 map.
Specific embodiment
The present invention is now illustrated with following most preferred embodiment, but is not intended to limit the scope of the invention.
Embodiment 1:
Using electrochemical erosion method, tip diameter is prepared in the W metal needle point of 30nm or so.The a electrification 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 cathode.Utilize golden ring
On the KCl liquid film of 1M gradually corrode Ni and finally obtain Ni needle point.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 corresponds to the HR-TEM image of nickel needle tip, and the d of Fig. 1 is corresponding SAED style.Needle point
The apex angle at tip is about 30 °.
Ni needle point is rinsed with a large amount of water, is soaked in spirit of vinegar and is removed surface oxide layer, then is rinsed with a large amount of water, and nitrogen is blown
It is dry.Above-mentioned Ni needle point is fixed in a high pressure reaction kettle vertically, the triethylene glycol solution that 100 μ L purity are 99% is added, simultaneously
The NaOH solution that 450 μ L concentration are 0.1mol/L is added to mix 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 point take out, with a large amount of water rinse, after being dried with nitrogen, 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
Empty pump is to 10-5Pump is closed after Pa, is filled with high pure nitrogen.Exporting a size using DC power supply is 10A, the duration 1.5 seconds
Immediate current passes through Pt metal tape；Pt metal tape and the W metal needle point moment being fixed thereon reach red heat state, such as Fig. 2 e
It is shown.After sample is 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 band；When c is that setting electric current 10A is heated by Pt band, the single pulse of oscillograph recording；D figure and e figure are right respectively
The U-shaped Pt band and V-type Pt band heating device 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 map.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 map.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 m of 100nm~200.
Transmission electron microscope observing is as the result is shown in Ni needle point tip size about 30nm, surfacing and the continuous single layer stone of covering
Black alkene；Going out graphene farther out from needle point tip is multilayered structure.Microscopic Raman test result confirms the presence of graphene-structured,
Graphene overlay area edge is far from about 50 μm of needle point distance between two tips.
Embodiment 2
Using electrochemical erosion method, tip diameter is prepared in the W metal needle point of 30nm or so.Ni needle point is 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, is dried with nitrogen.Above-mentioned Ni needle point is vertical
It is fixed that the triethylene glycol solution that 100 μ L purity are 99% is added in a high pressure reaction kettle, while 450 μ L concentration are added and are
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 point is taken out, is rinsed with a large amount of water, after being dried with nitrogen, 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
Empty pump is to 10-5Pump is closed after Pa, is filled with high pure nitrogen.Exporting a size using DC power supply is 10A, the duration 0.75 second
Immediate current passes through Pt metal tape；Pt metal tape and the W metal needle point moment being fixed thereon reach red heat state, such as Fig. 2 d
It is shown.After sample is 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 as the result is shown in Ni needle point tip size about 100nm, surfacing and the continuous single-layer graphene of covering；From needle point tip compared with
Far going out graphene is multilayered structure.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 map.By electric current 10A, heating time 0.75s, Pt bandwidth is 0.85mm.
The center Fig. 4 electromicroscopic photograph shows that the nanometer pinpoint tip that this condition annealing generates is slightly molten, and five-pointed star identifies 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 map.
Embodiment 3
Using electrochemical erosion method, tip diameter is prepared in the W metal needle point of 30nm or so.Ni needle point is 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, is dried with nitrogen.Above-mentioned Ni needle point is vertical
It is fixed that the triethylene glycol solution that 100 μ L purity are 99% is added in a high pressure reaction kettle, while 450 μ L concentration are added and are
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 point is taken out, is rinsed with a large amount of water, after being dried with nitrogen, needle point tip is fixed on corundum needle holder upward
On, then needle holder is placed in diamond heating region.Chamber vacuum is evacuated to 10 using molecular pump-5Pump is closed after Pa, is filled with high-purity
Nitrogen, Temperature fall after being heated to 550 DEG C of holdings 0.5 hour with the heating rate of 5 DEG C/min.After sample is cooling, gold is taken out
Belong to needle point, obtains graphene functionalized nanometer pinpoint as shown in Figure 5.Transmission electron microscope observing is as the result is shown in Ni needle point tip ruler
Very little about 100nm, surface major part region are oxidized, and very small region covers single-layer graphene.
Fig. 5 is saturating corresponding to a kind of typical graphene functionalized nanometer pinpoint of usual tube annealing processing preparation
Penetrate electromicroscopic photograph.A figure and b figure are static state N2Under atmosphere, the nanometer pinpoint of annealing；C and d figure is flowing N2Under atmosphere, annealing
The nanometer pinpoint of processing.In flowing N2Under atmosphere, nanometer pinpoint is aoxidized more severe, and the graphene region of Surface Creation is smaller.
Embodiment 4
Using electrochemical erosion method, tip diameter is prepared in the W metal needle point of 30nm or so.Ni needle point is 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, is dried with nitrogen.Above-mentioned Ni needle point is vertical
It is fixed that the triethylene glycol solution that 100 μ L purity are 99% is added in a high pressure reaction kettle, while 450 μ L concentration are added and are
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 point is taken out, is rinsed with a large amount of water, after being dried with nitrogen, it is thick that solid welding is scheduled on long 25mm* wide 0.5mm*
The metal Ta band of 0.05mm is intermediate；Metal Ta 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
Empty pump is to 10-5Pump is closed after Pa, is filled with high-purity argon gas.Exporting a size using DC power supply is 6A, the duration 1 second moment
Electric current passes through Ta metal tape；Ta metal tape and the W metal needle point moment being fixed thereon reach red heat state, as shown in Figure 2 d.
After sample is 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 point 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 map.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 is 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 map.
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (6)
1. a kind of preparation method of graphene functionalized nanometer pinpoint, which comprises 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 solution；
2) under the conditions of gas shield, in such a way that electrified regulation is annealed, graphene is formed on metal needle point surface；It is described logical
Electric heating is that the metal needle point with carburization zone is fixed on conductive carrier, applies moment electricity at conductive carrier both ends
Pressure makes immediate current generate Joule heat by conductive carrier, on heat transfer to metal needle point, in metal needle point surface formation graphite
Alkene；The temperature of the annealing is 500~600 DEG C；It is 1~50A by the electric current of the conductive carrier, conduction time is 0.01~
5 seconds；The material of the conductive carrier is metal or graphite, and conductive carrier shape is silk, band or boat；The diameter of the silk is 0.05
~0.5mm, the specification of band are 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.
2. preparation method according to claim 1, 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.
3. preparation method according to claim 1, 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, under the conditions of high-temperature closed, in metal needle point by carbon-containing molecules solution
Surface forms carburization zone.
4. preparation method according to claim 3, which is characterized in that in step 1), the carbon source is triethylene glycol, three second
One of hydramine, resorcinol, glucose or a variety of and sodium hydroxide mixing, the carbon source are the molten of 0.01~5mol/L
Liquid.
5. the preparation method according to claim 4, which is characterized in that in step 1), the metal needle point is immersed in carbon source
In heat together, the heating are as follows: be heated to 200~250 DEG C with the heating rate of 2~8 DEG C/min, after being kept for 1~3 hour from
So cooling.
6. the graphene functionalized nanometer pinpoint that any one of Claims 1 to 5 the method is prepared.
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| CN104360107A (en) * | 2014-11-12 | 2015-02-18 | 苏州大学 | Graphene-clad atomic force microscope probe and manufacturing method and application thereof |
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