CN101811690B - Method for forming carbon composite structure by using carbon nano tube and graphene - Google Patents
Method for forming carbon composite structure by using carbon nano tube and graphene Download PDFInfo
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- CN101811690B CN101811690B CN200910078292XA CN200910078292A CN101811690B CN 101811690 B CN101811690 B CN 101811690B CN 200910078292X A CN200910078292X A CN 200910078292XA CN 200910078292 A CN200910078292 A CN 200910078292A CN 101811690 B CN101811690 B CN 101811690B
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Abstract
The invention relates to a method for forming a carbon composite structure by using carbon nano tube and graphene, which comprises the following steps: plating an aluminum film and an iron film in turn on a cleaned silicon substrate; putting the treated silicon substrate into a conventional chemical vapor deposition device, and depositing and growing a carbon nano tube array, wherein the height of the carbon nano tube array is 10 to 300 microns, the diameter of the multi-wall carbon nano-tube is 10 to 20 nanometers and the density is 1,010 to 1,011cm<-2>; taking a graphite substrate, fixing the back of the graphite substrateon a plane, and splitting a flat upper surface; and reversely clasping the prepared multi-wall carbon nano tube array on the surface of the flat graphite, contacting the upper surface of the carbon nano tube array and the surface of the graphite, pressing the carbon nano tube array and the graphite, dragging a silicon substrate along the direction parallel to the surface of the graphite, and taking up the silicon substrate along the direction vertical to the surface of the graphite after the silicon substrate is dragged for 5 to 10 centimeters. Several to hundreds of graphene sheet layers are attached to the surface of the carbon nano tube so as to obtain the carbon composite structure. The method of the invention has the advantages of simple preparation, few required apparatus, high success rate, low cost and high speed.
Description
Technical field
The invention belongs to the nanometer field of new, particularly relate to a kind of with preparing the method that carbon nanotube and Graphene form the carbon complex structure body.
Background technology
Carbon class material shows as the soccerballene of zero-dimension structural, the carbon nanotube of one-dimentional structure, the Graphene of two-dirnentional structure and the variforms such as diamond of three-dimensional structure according to the difference of carbon atom key form.
Single-layer graphene (graphene) is sp between the carbon atom
2Hydridization Cheng Jian is arranged in the monoatomic layer flat crystal of bi-dimensional cellular shape lattice.Common material--graphite is piled up by Graphene lamella from level to level exactly and is formed.Electronics in the single-layer graphene is followed the linear dispersion relation near dirac point, the dirac fermion of the similar no quality of behavior makes some theories of quantum electrodynamics can study through experiment first.Discover that in early days the current carrier of Graphene can be regulated continuously between electronics and hole, and its mobility is still very high under general external environment and high carrier concentration situation.It is not bad that (Novoselov, K.S.etal.Nature 438,197-200 (2005)) research recently calculates its hardness ratio diamond.Contrast other two dimensional crystal materials, the electricity mechanical property that Graphene is excellent at each extensive applications potential, has caused scientist's very big interest.
Carbon nanotube is (S.Iijima, Nature 354,56 (1991)) that from the thomel that arc process is produced, found in 1991.It is a kind of tubular carbon molecule, and each carbon atom is taked SP on the pipe
2Hydridization combines with carbon-to-carbon σ key each other, forms the polynuclear plane be made up of the hexagon skeleton as carbon nanotube; The length-to-diameter ratio of carbon nanotube is generally more than 1000: 1, and strength ratio is high 100 times with the intensity of volume steel, and weight but has only the latter's 1/6 to 1/7; Hardness and diamond are suitable, but have good snappiness, are the ideal high tensile strength fibrous materials, thereby are claimed " super fiber ".Because the structure of carbon nanotube is identical with the laminated structure of graphite, so have good electric property.Theoretical prediction is when caliber during less than 6nm, and carbon nanotube can be regarded as the One-dimensional Quantum lead with excellent conductive performance.Through suitable orientation, carbon nanotube can synthesize the heat conducting material of high anisotropy.Carbon nanotube also has other good performances such as optics and Chu Qing.These good character make carbon nanotube be considered to the ideal One-dimensional Quantum material of huge applications potentiality.
Aspect the Nano Carbon structure, mostly research concentrates on the aspect that combines of metallic particles, organic molecule and carbon nanotube or Graphene.Be equivalent to the doping research of one dimension, zero dimension carbon material.The complex body that forms between the carbon class material mainly concentrates in the carbon nano-tube process, produced simultaneously other carbon allotropes.Research has zero dimension and unidimensional complex structure body---the nanometer beanpod of finding (Smith, B.W.etal.Nature 396,323 (1998)) in 1998 more widely.Up in March, 2008, Fujitsu Research Institute " in the 34th the comprehensive symposial of fullerene nanotube, is delivering it in the success that obtains aspect the novel nano carbon complex structure body of self-organization formation joint carbon nanotube and Graphene.Fujitsu Research Institute utilizes the chemical vapour deposition flop-in method, under 510 ℃ temperature, on the multi-walled carbon nano-tubes that neatly generates in vertical direction with respect to base plate, has formed the complex structure body that is formed to the graphite self-organization of tens layers by which floor.This is the bonded structure of non-atomic structure of Graphene vertical engagement of realizing carbon nanotube and the two-dirnentional structure of one-dimentional structure first.
Summary of the invention
The objective of the invention is to: a kind of mechanical property of utilizing carbon nanotube itself is provided; Through the most direct machinery scraping and pressing mode; Effectively be formed on the one dimension array of multi-walled carbon nanotubes perpendicular to the growth of silicon substrate direction, in conjunction with the preparation method of the carbon complex structure body of going up two-dimentional Graphene.The sample area that this method preparation technology is simple, cost is low and obtain is big.
The objective of the invention is to realize like this.
A kind of being employed in perpendicular on the silicon substrate direction carbon nanometer tube array growing provided by the invention arrived the tens layers graphene film in conjunction with which floor is gone up, thereby formed the method for the carbon complex structure body of one dimension carbon nanotube and two-dimentional Graphene, may further comprise the steps:
1). the prepared silicon substrate is also done coating film treatment: the silicon substrate of the surfacing that selection cleans up, adopt coating process on silicon substrate, order plates thick aluminium film of 8-12nm and the thick iron film of 0.8-3nm;
2). the silicon substrate that step 1) is handled well is put into the conventional chemical vapor phase growing apparatus; Adopt conventional chemical gas-phase deposition growth array of multi-walled carbon nanotubes; Wherein the carbon nano pipe array height is at the 10-300 micron, and the multi-walled carbon nano-tubes diameter is at 10-20nm, and array density is 10
10-10
11Cm
-2
3). handle graphite material: get a highly oriented pyrolytic graphite or natural graphite, the graphite back side is fixed on the plane, and cleavage goes out smooth upper surface, remove the top layer graphite of flat surface again, expose new clean surface;
4). the legal system of directly swiping is equipped with sample: with step 2) array of multi-walled carbon nanotubes for preparing; Tip upside down on the graphite surface that step 3) obtains, the array of multi-walled carbon nanotubes upper surface contacts with graphite surface, pushes the back side of the silicon substrate of the array of multi-walled carbon nanotubes of having grown; Make pressure between graphite and array of multi-walled carbon nanotubes at 0.5-3kg; Reduce pressure then, pull silicon substrate along parallel graphite surface direction, pull the 5-10cm distance after; Pick up silicon substrate along vertical graphite surface direction; Obtain on, which floor is enclosed, form the carbon complex structure body of one dimension multi-walled carbon nano-tubes and two-dimentional Graphene to the tens layers graphene film perpendicular to silicon substrate direction carbon nanometer tube array growing.
In technique scheme, wherein said silicon substrate is silicon single crystal flake or SOI substrate.
In above-mentioned technical scheme, described conventional low-pressure chemical vapor deposition (low pressure chemical vapor deposition) technology carbon nano tube array grows processing condition are following: the silicon substrate that step 1) is handled well is put into container, be heated to 400-500 ℃, kept ten minutes; Then container is vacuumized, make internal pressure less than 10mTorr; Vessel temp is raised to 700-1000 ℃, and behind the constant temperature, with the flow feeding shielding gas of PM 100-300 milliliter, the flow with PM 50-200 milliliter feeds carbon source gas, Pintsch process 10-20 minute simultaneously; Afterwards, stop heating and close carbon source gas, continue logical shielding gas and make it to be cooled to room temperature.The first carbon pipeline section of growth, the direction of growth at random, the carbon pipeline section of continued growth is afterwards fitly grown along vertical si substrate direction.Have crooked winding arrangement thereby obtain upper surface, the array of multi-walled carbon nanotubes of main body trunk vertical si substrate proper alignment is grown on the silicon substrate to firm attachment.
In above-mentioned technical scheme, the specification of described carbon nano pipe array is relevant with reaction times and pressure, and the carbon nano pipe array height is at the 10-300 micron, and carbon pipe diameter is at 10-20nm, and density is 10
10-10
11Cm
-2(can be referring to synoptic diagram 3, the array that adopts the growth of conventional low-pressure chemical vapor deposition (low pressure chemical vapor deposition) technology to obtain can both be used for preparing carbon complex structure body of the present invention).
In above-mentioned technical scheme, described shielding gas is rare gas elementes commonly used such as argon gas or nitrogen.
In above-mentioned technical scheme, described carbon source gas is volume ratio blended hydrogen and the acetylene with 1: 1.
In above-mentioned technical scheme, the carbon complex structure body with step 4) obtains can also blow its surface about 1 minute with the nitrogen gun of medium gas flow rate, removes possible chip.
The carbon complex that the present invention prepares characterizes: use opticmicroscope (OM) observation sample surface, preliminary observation is picked out thin layer graphite flake layer zone; Observe the pattern of carbon nanotube and the carbon complex structure body of thin layer Graphene formation with sem (SEM), as shown in Figure 4.
Compared with present technology the preparation method of carbon complex structure body provided by the invention has following advantage:
1. preparation method provided by the invention, the little step of pressure is simple, is easy to carry out, and required plant and instrument is few, and success ratio is high, and cost is low, and speed is fast.
2. preparation method provided by the invention, key have utilized the array surface of growth to have winding arrangement.Discover, because the winding arrangement of array surface makes the side of the many multi-walled carbon nano-tubes of array upper surface be able to closely contact with graphite surface.In the case, tangentially the adhesive power between (parallel surfaces direction) two surfaces is very big, and little along normal direction (vertical surface direction) adhesive power, is prone to break away from.(referring to Fig. 2, document: Liangti Qu et al.Science 322,239 (2008))
3. the present invention makes is on perpendicular to silicon substrate direction carbon nanometer tube array growing; In conjunction with which floor being gone up to the tens layers graphene film; Thereby form the carbon composite structure body structure of one dimension carbon nanotube and two-dimentional Graphene, but not the direct joint of atomic structure is different with existing material; Because the effect of pressure in conjunction with closely, forms unique composite structure, is beneficial to follow-up study, is expected to obtain particular performances.
4. the carbon complex structure body that makes of the present invention, appended graphene film number of layers cross over that scope is wide, and macroscopic view is inhomogeneous, and microcosmic (1 micron) is even; Also can obtain the Nano Carbon structure that Graphene lamella and carbon nanotube by nanometer scale form.
Description of drawings
Fig. 1 the present invention adopts low-pressure chemical vapor deposition to prepare the device synoptic diagram of carbon nano pipe array.
Fig. 2 the present invention utilizes the character of special construction array, and directly scraping prepares the method process schematic representation of carbon complex structure body.
The electron scanning micrograph of the carbon nano pipe array of Fig. 3 embodiment of the invention 1 preparation.
The electron scanning micrograph of the carbon complex structure body that Fig. 4 embodiment of the invention 1 is prepared.
The drawing explanation:
1-electric tube furnace 2-silica tube 3-silicon substrate
4-programmed temperature control instrument 5-inlet mouth 6-vacuumometer
7-graphite 8-growth has the silicon substrate of carbon nano pipe array
Through accompanying drawing and embodiment the method that forms the carbon complex structure body with carbon nanotube and Graphene is further described below.
Embodiment
Embodiment 1
With reference to figure 1,2, specify the technical process that direct scraping legal system of the present invention is equipped with the carbon complex structure body.
As shown in Figure 1, the present invention is used to prepare the device employing popular response equipment of carbon nano pipe array, mainly is made up of reactor drum, gas distributing system, temperature controlling system, pumped vacuum systems four parts.Wherein, 1) reactor drum: form by silica tube 2 and electric tube furnace 1; Silica tube 2 is as reaction vessel, and substrate 3 is placed on the inside; 2) gas distributing system: form by gas circuit and mass-flow gas meter, can control flow, ratio and the kind of carrier gas.Feed in the silica tube by inlet mouth 5; 3) temperature controlling system: form by programmed temperature control instrument 4; 4) pumped vacuum systems: form by vacuum pump and vacuumometer 6, silica tube is vacuumized and measuring its internal pressure.
The preparation process of present embodiment is following:
1). preparing substrate is also done coating film treatment: select silicon (111) single-chip of the 4mm * 4mm of surfacing to do substrate; With conventional vacuum thermal evaporation plating method, with the speed of 5 dust per seconds, the aluminium film that plating 10nm is thick earlier is in order to increase the bonding force of carbon nano pipe array and silicon chip; Speed with 1 dust per second plates the thick iron film of 3nm as catalyzer again;
2). in conventional equipment shown in Figure 1, adopt conventional low pressure chemical vapor deposition (chemical vapour deposition) method carbon nano tube array grows: the substrate 3 that step 1) is handled well is put into silica tube as shown in Figure 12 middle parts; Through temperature controller 4, electric furnace 1 temperature is risen to 450 ℃, kept ten minutes; Then silica tube 2 is vacuumized, measure, make internal pressure be low to moderate 8mTorr through vacuumometer 6; Regulate electric furnace 1 temperature, make it to be raised to 750 ℃; Behind the constant temperature, in silica tube 2, feed argon gas or nitrogen, feed hydrogen and feed acetylene gas with the flow of 90 milliliters of PMs simultaneously with the flow of 100 milliliters of PMs during growth with the flow of 200 milliliters of PMs by inlet mouth 5; Keeping feeding under this mixed gas Pintsch process 15 minutes; Afterwards, stop heating and close hydrogen and acetylene gas, continue logical argon gas or nitrogen until cool to room temperature; Take out substrate, obtain in array of multi-walled carbon nanotubes perpendicular to the growth of substrate direction;
3). the array of multi-walled carbon nanotubes that obtains is observed with sem.As shown in Figure 3, the arrangement of neatly growing of the main body trunk vertical substrates of array of multi-walled carbon nanotubes, the beginning part direction of growth of multi-walled carbon nano-tubes is mixed and disorderly, thereby makes the array upper surface demonstrate crooked winding arrangement.The array of multi-walled carbon nanotubes of present embodiment, diameter are at 10-15nm, and about 150 microns, array density is 10 for carbon length of tube (being the array height)
10-10
11Cm
-2
Substrate is grown that face of array over against a vertical sheet glass of placing, push, make substrate stick on the sheet glass from substrate back.Be stained with cord at substrate back, spur silicon chip along parallel substrate direction, recording with ergometer needs the 2kg pulling force can let silicon chip break away from sheet glass approximately; Then only need the 0.4kg pulling force along the vertical substrates direction; The array of multi-walled carbon nanotubes that present embodiment growth is described securely apposition growth on substrate;
4). get the block A level highly oriented pyrolytic graphite (HOPG) of a 10cmX10cmX2mm size, the graphite back side is sticked on the clean slide with double sticky tape; Cut out smooth upper surface with the sharp sword cleavage, with the sticking top layer graphite that removes flat surface of scotch tape, expose new clean (0001) face again;
5). the legal system of directly swiping is equipped with sample: referring to Fig. 2, with the array of multi-walled carbon nanotubes for preparing, silicon substrate makes progress, and back-off is placed on the graphite surface gently, and the array upper surface contacts with graphite surface.Push the silicon substrate back side slightly, make pressure between graphite and array, keep pressure relief after 5 seconds at 0.5kg; (when the time with the pressure of 1.5kg, 3.5kg or 5kg; Can suitably reduce the time of pressurization; For example can 4,3; Those skilled in the art can be implemented), it is all passable to pull advance 5cm, 7cm or 10cm of silicon substrate along parallel graphite surface direction gently, picks up silicon substrate along vertical graphite surface direction again.Thereby make one dimension multi-walled carbon nano-tubes top layer combine to go up two-dimentional Graphene lamella, obtain the carbon complex structure body.
Also comprise step 6). to the carbon complex structure body in the step 5), blew its surface 1 minute, remove possible chip with the nitrogen gun of medium gas flow rate.
Also comprise step 7). with opticmicroscope finished product is observed selection, through colouring discrimination, preliminary screening goes out the zone of attachment coating graphite flake layer.
Also comprise step 8). take pictures with the sem mirror, obtain the pattern and the distribution situation of thin layer graphite flake, thereby obtain the situation of carbon complex structure body.
Like Fig. 4 is that being combined in of preparing of present embodiment is perpendicular to only counting layer graphenes, the carbon complex structure body electron scanning micrograph of formation on the array of multi-walled carbon nanotubes of substrate direction growth.
Embodiment 2
Concrete steps just change used graphite into natural flake graphite with embodiment 1; Substrate adopts the SOI substrate (to be coated with 100nmSiO
2The silicon chip of layer).
Embodiment 3
Concrete steps are with embodiment 1, and just the Pintsch process time that carbon nano tube array grows is used is reduced to 5 minutes, the array of multi-walled carbon nanotubes that obtains, and diameter Distribution is identical, and height is about 100 microns.
Embodiment 4
Concrete steps are with embodiment 1, and just the parameter that carbon nano tube array grows is used is changed slightly, and hydrogen and acetylene all feed with the flow of 80 milliliters of PMs, and the array character and the embodiment 1 that obtain are similar.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and modification according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (5)
1. one kind forms the method for carbon complex structure body with carbon nanotube and Graphene, may further comprise the steps:
1). the prepared silicon substrate is also done coating film treatment: the silicon substrate of the surfacing that selection cleans up, adopt coating process on silicon substrate, order plates thick aluminium film of 8-12nm and the thick iron film of 0.8-3nm;
2). the silicon substrate that step 1) is handled well is put into the conventional chemical vapor phase growing apparatus; Adopt conventional chemical gas-phase deposition growth array of multi-walled carbon nanotubes; Wherein the carbon nano pipe array height is at the 10-300 micron, and the multi-walled carbon nano-tubes diameter is at 10-20nm, and array density is 10
10-10
11Cm
-2
3). handle graphite material: get a highly oriented pyrolytic graphite or natural graphite, the graphite back side is fixed on the plane, and cleavage goes out smooth upper surface, remove the top layer graphite of flat surface again, expose new clean surface;
4). the legal system of directly swiping is equipped with sample: with step 2) array of multi-walled carbon nanotubes for preparing; Tip upside down on the graphite surface that step 3) obtains, the array of multi-walled carbon nanotubes upper surface contacts with graphite surface, pushes the back side of the silicon substrate of the array of multi-walled carbon nanotubes of having grown; Make pressure between graphite and array of multi-walled carbon nanotubes at 0.5-3kg; Reduce pressure then, pull silicon substrate along parallel graphite surface direction, pull the 5-10cm distance after; Pick up silicon substrate along vertical graphite surface direction; Obtain on, which floor is enclosed, form the carbon complex structure body of one dimension multi-walled carbon nano-tubes and two-dimentional Graphene to the tens layers graphene film perpendicular to silicon substrate direction carbon nanometer tube array growing.
2. the method with carbon nanotube and Graphene formation carbon complex structure body according to claim 1 is characterized in that described silicon substrate is silicon single crystal flake or SOI substrate.
3. the method that forms the carbon complex structure body with carbon nanotube and Graphene according to claim 1; It is characterized in that; Described step 2) condition of growth array of multi-walled carbon nanotubes is following: the silicon substrate that step 1) is handled well is put into container, be heated to 400-500 ℃, kept ten minutes; Then container is vacuumized, make internal pressure less than 10mTorr; Vessel temp is raised to 700-1000 ℃, and behind the constant temperature, with the flow feeding shielding gas of PM 100-300 milliliter, the flow with PM 50-200 milliliter feeds carbon source gas, Pintsch process 10-20 minute simultaneously; Afterwards, stop heating and close carbon source gas, continue logical shielding gas and make it to be cooled to room temperature.
4. the method with carbon nanotube and Graphene formation carbon complex structure body according to claim 3 is characterized in that described shielding gas is argon gas or nitrogen rare gas element.
5. the method with carbon nanotube and Graphene formation carbon complex structure body according to claim 3 is characterized in that described carbon source gas is volume ratio blended hydrogen and the acetylene with 1: 1.
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| US9475921B2 (en) | 2011-06-23 | 2016-10-25 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| US9997785B2 (en) | 2011-06-23 | 2018-06-12 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
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Cited By (2)
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| US9997785B2 (en) | 2011-06-23 | 2018-06-12 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
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