CN107416808A - A kind of preparation method of graphene carbon nano-tube nano composite construction - Google Patents
A kind of preparation method of graphene carbon nano-tube nano composite construction Download PDFInfo
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- CN107416808A CN107416808A CN201710729825.0A CN201710729825A CN107416808A CN 107416808 A CN107416808 A CN 107416808A CN 201710729825 A CN201710729825 A CN 201710729825A CN 107416808 A CN107416808 A CN 107416808A
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Abstract
The present invention relates to a kind of method that a step prepares graphene-carbon nano tube nano composite structure.This method is based on plasma enhanced chemical vapor deposition principle, the direct growth CNT on the metal containing catalytic elements or Semiconductor substrate, the direct extending and growing graphene on CNT wall simultaneously, forms the graphene film composite construction using CNT as matrix；In the case where growth conditions is met, the size of CNT and graphene film can increase simultaneously；Graphene, with C-C bond combination, forms ohmic contact characteristic with carbon nanotube interface.The inventive method is simple, and a step grows while realizing graphene and CNT, and this new carbon nano composite structure has important application in the devices such as electron emission, energy conversion, energy stores.
Description
Technical field
The present invention relates to nanostructured preparation method, in particular it relates to the one-dimensional carbon nano-structured tow -dimensions atom for base
Crystal structure self-assembling growth method, belongs to nano material and field of electronic materials.
Technical background
It is carbon nano-structured to be closed extensively in fields such as electronic information, the energy with its unique physical characteristic and chemical characteristic
Note.How to play different carbon nano-structured each characteristic advantages and obtain high performance structures and material to cooperate with, to promoting carbon nanometer
Material is realized extensively using significant.
Graphene is with sp by carbon atom2The individual layer atomic structure material of hybridized orbit composition hexagonal honeycomb lattice arrangement,
The outstanding and unique physicochemical characteristics of the characteristics such as its high electron mobility, high thermal conductivity super capacitor, field emitting electronic source,
Using the innovation that will likely can bring device performance in the photoelectric devices such as solar cell.Such as upright graphene, in its structure
With, with high electron mobility and high thermal conductivity feature, it makees in the sophisticated and big surface area feature of monatomic state, its characteristic
It is beneficial to obtain high current emission characteristics for Electron field emitters.
Field Electron Emission (referred to as Flied emission) refers to that body surface barrier width narrows under electric field action, height becomes
Low, interior of articles penetration of electrons surface potential barrier enters the physical process of vacuum, and it is a kind of quick, efficient acquisition electron emission
Method.Emitting facet can be brought very due to the ratio of height to diameter of its especially high numerical value using CNT as the one-dimensional nano structure of representative
Strong electric-field enhancing amount, so as to show electron emission characteristic under existing fringing field and be used in field emission cold-cathode electronic source.
How the nanostructared emitters of existing fringing field and high current emissivities characteristic are realizedThe present invention propose using composite construction come
Play the respective characteristic advantage of one-dimensional nano structure and two nanostructureds, collaboration obtains existing fringing field high current emissivities characteristic
The thinking of nanostructared emitters, and realized on graphene-carbon nano tube nano composite structure.Specifically, graphite
Alkene-carbon nanotube composite construction is integrated with graphene film and carbon nano-tube emitter, and electron emission is simultaneously from carbon nanometer
End surfaces and graphene film end face；Interface contacts for ohm property between the two for graphene film and CNT, there is provided good
Electron propagation ducts and the Joule heat for reducing interface；The abundant surface area of graphene film so that dissipated in its emission process on the scene
The passage of heat greatly increases, and improves the resistance to properties of flow of electric current.Such composite construction equally will also apply to as energy storage device etc.
Electrode material.
The content of the invention
The present invention provides a kind of method of one-step synthesis graphene-carbon nano tube nano composite structure, while provides one
Nanostructured of the kind with high current electron emissivity.The technical scheme of the invention is as follows：
A kind of preparation method of graphene-carbon nano tube nano composite structure, it is to be based on PECVD
Deposition principle in the Grown CNT with catalytic elements, the direct extending and growing graphene on CNT wall,
Form the graphene film composite construction using CNT as matrix.
Preferably, the method for the growth graphene-carbon nano tube nano composite structure comprises the following steps：
A) metal of selection carbon nanotubes growth catalytic elements composition or semiconductor are as backing material；
B) in the presence of low temperature plasma, substrate is reduced heating, and in the substrate surface shape selected by step a)
Into the nano particle with catalytic activity；
C) using plasma enhancing chemical gaseous phase depositing process closes on the substrate of the nano particle with catalytic activity
Into growth CNT, while the direct extending and growing graphene on CNT wall.
D) certain growth time is maintained, growth forms laminated structure to graphene at a certain angle on CNT wall.
Preferably, the plasma enhanced chemical vapor deposition method synthesis growth graphene-carbon nano tube nanometer is answered
Between the reaction temperature for closing structure is 500 DEG C~950 DEG C, carbon atom is in a manner of ordered structure from CNT wall direct growth stone
Black alkene.
Preferably, in the carbon nano composite structure of the synthesis growth, chemical bond is relied between graphene and CNT
Mode combines, and forms the connection of ohmic contact characteristic.
Preferably, the catalytic elements include chromium, iron, manganese, the oxide or its solid solution of nickel.
Preferably, the substrate includes the metal and Semiconductor substrate that various methods introduce catalytic elements, the catalysis member
The introducing method of element includes magnetically controlled sputter method, vapor deposition method.
The inventive method is simple, and a step grows while realizing graphene and CNT, and this new carbon nanometer is answered
Close structure has important application in the devices such as electron emission, energy conversion, energy stores.
Brief description of the drawings
Fig. 1 is the schematic diagram of Grown graphene-carbon nano tube nano composite structure, wherein 1 represents substrate, 2 generations
Table CNT, 3 represent graphene；
Fig. 2 is the shape appearance figure of graphene-carbon nano tube, Fig. 2 a and 2b sets forth graphene-carbon nano tube film and
The scanning electron microscope image of pattern at the top of single nanostructured, Fig. 2 c sets forth graphene and carbon nanotube interface
High power transmission electron microscope image, Fig. 2 d give the atomic arrangement image that interface inverse-Fourier transform obtains；
Fig. 3 is that the electrology characteristic of single graphene-carbon nano tube nano composite structure characterizes, and Fig. 3 a are that graphene is received with carbon
The interface conductivity test schematic diagram of mitron, Fig. 3 b are I-V characteristic curve.Fig. 3 c are the Flied emission of single graphene-carbon nano tube
Characteristic test schematic diagram, Fig. 3 d are I-V characteristic curve.
In Figure of abstract：1 represents substrate, and 2 represent CNT, and 3 represent graphene.
Embodiment
Present disclosure and technical scheme are further illustrated below with specific embodiment, but should not be construed as to this hair
Bright limitation.In the case of without departing substantially from inventive concept, the simple modification made to the inventive method, step or condition or replace
Change, belong to the scope of the present invention.Unless otherwise specified, technological means used in embodiment is ripe for those skilled in the art
The conventional meanses known.
The specific implementation flow of the present invention is as follows：
Step 1：The cleaning of substrate.The stainless steel of carbon nanotubes growth catalytic elements composition is selected as backing material,
And stainless steel lining bottom is cleaned by ultrasonic with acetone, ethanol, deionized water successively, each more than 10min.
Step 2：The preparation of growing environment.Using microwave plasma enhanced chemical vapor depsotition equipment, after cleaning
Substrate is placed on sample stage close to the position of microwave source, and equipment vacuum degree is extracted into below 10Pa.
Step 3：Substrate H2Pretreatment.After vacuum is extracted into below 10Pa, 100sccm H is passed through2Gas, and maintain air pressure
220Pa, opens the microwave source that power is 500W, and substrate bias adds to 100V, excited gas, produces low temperature plasma, this mistake
Cheng Chixu 20min, remove the oxide of substrate surface and other pollutants, and underlayer temperature is increased to 400 DEG C or so.
Step 4：The growth of nano composite structure.After step 3 continues 20min, cut-out microwave source biases with growth, is passed through
7sccm CH4Gas, air pressure is maintained 220Pa, be again turned on the microwave source that micropower is 500W, bias adds to 200V, excited
H2, CH4Gas, carbon containing active group is produced, this process continues 30min.In such carbon containing low temperature plasma atmosphere,
Shorter CNT can be grown on stainless steel lining bottom in the early stage；Then, graphene is nucleated simultaneously in CNT wall fault location
Epitaxial growth；In the case of carbon source supply sufficiently, it is big that the size of graphene and CNT increases over time same time-varying,
It is final to obtain graphene-carbon nano tube nano composite structure.
Step 5：Microwave source, growth bias and source of the gas are cut off, below 10Pa is evacuated to, is cooled to room temperature, takes out afterwards
Sample.
Received below by the interface topography structure and electrical characterization of graphene and CNT, and single graphene-carbon
The sign of the field emission characteristic of mitron nano composite structure, to illustrate the exploitativeness of technical scheme.
Sample topography and interface are analyzed using SEM and high-resolution-ration transmission electric-lens.Fig. 2 a and Fig. 2 b
It sets forth the pattern of the top area of graphene-carbon nano tube film and single graphene-carbon nano tube.Single graphite
Alkene-CNT shows tree and is distributed independently of each other.Fig. 2 c give graphene in nano composite structure and received with carbon
The distribution of mitron interface crystal lattice striped, the fringe spacing of CNT is 0.35nm；Inversefouriertransform point is done to interface zone
Analysis, obtains graphene and carbon nanotube interface atomic arrangement Fig. 2 d, and both interfaces are connected in a manner of carbon carbon chemical bond, implies
Carbon atom bonding of the carbon atom with CNT at the defects of CNT wall, realizes graphene in the outer of CNT wall
Epitaxial growth.
To the field of the conductive characteristic and single graphene-carbon nano tube nano composite structure of graphene and carbon nanotube interface
Emission characteristics is characterized.Two nano-probes are contacted with graphene and CNT respectively, such as Fig. 3 a, use model
Keithley 6487 carries the device that the pico-ampere table of voltage source characterizes as record I-V characteristic, and test system is evacuated to 1 ×
10-4Pa or so can making alive record its I-V characteristic.As shown in Figure 3 b, the I-V characteristic between graphene and CNT is obtained
Curve is straight line, illustrates to be combined together in a manner of Ohmic contact between graphene and CNT, there is provided good
Electron propagation ducts.In addition, in order to characterize its field emission characteristic, visited testing sample as field emission cold-cathode, tungsten nanometer
For pin as test anode, negative and positive die opening is fixed on 1 μm, such as Fig. 3 c, equally using model Keithley 6487 from voltage
The device that the pico-ampere table in source characterizes as record I-V characteristic.Fig. 3 d are that single graphene-carbon nano tube sample undergoes 8 I-V wheels
Return, obtained 8 I-V curves and corresponding F-N curves.The maximum field emission current for obtaining single graphene-carbon nano tube is
90.65μA。
To sum up, the present invention provide it is a kind of based on plasma enhanced chemical vapor deposition principle in the gold with catalytic elements
The method of graphene-carbon nano tube nano composite structure is grown on category or Semiconductor substrate.Carbon atom in a manner of ordered structure
Arranged at the defects of CNT wall, so as to realize epitaxial growth of the graphene on CNT wall.The present invention's is main excellent
Point includes：First, preparation method is simple, grown while realizing CNT and graphene without any pretreatment and post processing；
Second, this carbon nano composite structure is the high current hair for the integral structure that nanoscale tip and atomic-level thickness tip integrate
Beam, and be that ohm property contact enhances conductive capability between the two and reduces the joule at both interfaces between the two
Heat；Third, in this carbon nano composite structure, graphene film has abundant surface area so that its emission process or electronics on the scene
Heat dissipation channel greatly increases in transport process, improves resistance to properties of flow.
Claims (6)
- A kind of 1. preparation method of graphene-carbon nano tube nano composite structure, it is characterised in that：Based on plasma enhancing Vapour deposition principle is learned, CNT is grown on the metal with catalytic elements or Semiconductor substrate, while in CNT Direct extending and growing graphene on wall.
- 2. a kind of preparation method of graphene-carbon nano tube nano composite structure according to claim 1, its feature exist In：It the described method comprises the following steps：A) substrate of carbon nanotubes growth catalytic elements composition is selected；B) in the presence of low temperature plasma, substrate is reduced heating, and forms tool in the substrate surface selected by step a) There is the nano particle of catalytic activity；C) using plasma enhancing chemical gaseous phase depositing process synthesizes life on the substrate of the nano particle with catalytic activity Long CNT, while in CNT wall Epitaxial growth graphene；D) the certain growth time is kept, graphene grows at a certain angle on CNT wall, and forms laminated structure.
- 3. a kind of preparation method of graphene-carbon nano tube nano composite structure according to claim 2, its feature exist In：Between the reaction temperature of the thermal chemical vapor deposition method synthesis growth CNT is 500 DEG C~950 DEG C, carbon atom From CNT wall extending and growing graphene in a manner of ordered structure.
- 4. a kind of preparation method of graphene-carbon nano tube nano composite structure according to claim 2, its feature exist In：Combined between the graphene and CNT of the synthesis growth by chemical bond mode, form the company of ohmic contact characteristic Connect.
- 5. a kind of preparation method of graphene-carbon nano tube nano composite structure according to claim 2, its feature exist In：The catalytic elements include chromium, iron, manganese, the oxide or its solid solution of nickel.
- 6. a kind of preparation method of graphene-carbon nano tube nano composite structure according to claim 2, its feature exist In：The substrate includes the metal and semiconductive material substrate that various methods introduce catalytic elements, the introducing of the catalytic elements Method includes magnetically controlled sputter method, vapor deposition method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970289A (en) * | 2018-10-01 | 2020-04-07 | 三星电子株式会社 | Method of forming graphene |
| CN111092155A (en) * | 2019-10-28 | 2020-05-01 | 温州大学 | Metal nanoparticle-containing single-walled carbon nanotube intramolecular junction and preparation method and application thereof |
| CN111607763A (en) * | 2020-06-17 | 2020-09-01 | 武汉纺织大学 | Method for rapidly growing metal single atom on carbon-based carrier by microwave-induced metal discharge and application thereof |
| CN110970289B (en) * | 2018-10-01 | 2024-04-05 | 三星电子株式会社 | Method for forming graphene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048509A (en) * | 1999-07-29 | 2001-02-20 | Ricoh Co Ltd | Cnt and cnt assembly, field emission type cold cathode electron emission element, its production and display device using the same electron emission element |
| CN103436854A (en) * | 2013-09-05 | 2013-12-11 | 吉林大学 | Preparation method of graphene and carbon nanotube composite material |
| CN103824704A (en) * | 2014-02-24 | 2014-05-28 | 哈尔滨工业大学 | Method for preparing composite electrode material of carbon nano-tube-graphene supercapacitor |
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| CN103050346B (en) * | 2013-01-06 | 2015-09-30 | 电子科技大学 | The preparation method of field emission electron source and carbon nano-tube graphene composite structure thereof |
| CN105244249A (en) * | 2015-10-20 | 2016-01-13 | 天津师范大学 | Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof |
| KR20170028233A (en) * | 2015-12-04 | 2017-03-13 | 주식회사 이엠코리아 | A environmental-friendly surface finishing additives of buildings, surface finishing composition comprising the same and environmental-friendly surface finishing of buildings |
-
2017
- 2017-08-23 CN CN201710729825.0A patent/CN107416808B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048509A (en) * | 1999-07-29 | 2001-02-20 | Ricoh Co Ltd | Cnt and cnt assembly, field emission type cold cathode electron emission element, its production and display device using the same electron emission element |
| CN103050346B (en) * | 2013-01-06 | 2015-09-30 | 电子科技大学 | The preparation method of field emission electron source and carbon nano-tube graphene composite structure thereof |
| CN103436854A (en) * | 2013-09-05 | 2013-12-11 | 吉林大学 | Preparation method of graphene and carbon nanotube composite material |
| CN103824704A (en) * | 2014-02-24 | 2014-05-28 | 哈尔滨工业大学 | Method for preparing composite electrode material of carbon nano-tube-graphene supercapacitor |
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| CN105244249A (en) * | 2015-10-20 | 2016-01-13 | 天津师范大学 | Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof |
| KR20170028233A (en) * | 2015-12-04 | 2017-03-13 | 주식회사 이엠코리아 | A environmental-friendly surface finishing additives of buildings, surface finishing composition comprising the same and environmental-friendly surface finishing of buildings |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970289A (en) * | 2018-10-01 | 2020-04-07 | 三星电子株式会社 | Method of forming graphene |
| CN110970289B (en) * | 2018-10-01 | 2024-04-05 | 三星电子株式会社 | Method for forming graphene |
| CN111092155A (en) * | 2019-10-28 | 2020-05-01 | 温州大学 | Metal nanoparticle-containing single-walled carbon nanotube intramolecular junction and preparation method and application thereof |
| CN111092155B (en) * | 2019-10-28 | 2023-01-17 | 温州大学 | Metal nanoparticle-containing single-walled carbon nanotube intramolecular junction and preparation method and application thereof |
| CN111607763A (en) * | 2020-06-17 | 2020-09-01 | 武汉纺织大学 | Method for rapidly growing metal single atom on carbon-based carrier by microwave-induced metal discharge and application thereof |
| CN111607763B (en) * | 2020-06-17 | 2022-02-11 | 武汉纺织大学 | Method for rapidly growing metal single atom on carbon-based carrier by microwave-induced metal discharge and application thereof |
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