CN103145123B - A kind of method preparing grapheme material - Google Patents
A kind of method preparing grapheme material Download PDFInfo
- Publication number
- CN103145123B CN103145123B CN201310099793.2A CN201310099793A CN103145123B CN 103145123 B CN103145123 B CN 103145123B CN 201310099793 A CN201310099793 A CN 201310099793A CN 103145123 B CN103145123 B CN 103145123B
- Authority
- CN
- China
- Prior art keywords
- carbon source
- positive electrode
- negative potential
- voltage
- unbodied
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of method preparing grapheme material, belong to technical field prepared by material in microtronics and information electronic.The method concrete steps are: carbon nanotube or unbodied carbon source are inserted the centre of positive electrode and negative potential by (1), positive and negative electrode is close to each other and contact conducting, (2) electrode connected is inserted in vacuum chamber also fixing, turn off the voltage of external power source, the vacuum tightness of vacuum chamber is evacuated to 10
-4~ 10
-5pa scope; (3) carbon nanotube or unbodied carbon source are slowly heated; Apply a voltage pulse to positive and negative electrode again, carbon nanotube or unbodied carbon source are blown, the breaking part after ablation defines the material of a large amount of graphene-structured.Preparation equipment required for method of the present invention is simple, and temperature is low, and raw material is simple and easy to get, and the Graphene quality that it prepares is good, and output is more.
Description
Technical field
The present invention relates to a kind of method at room temperature preparing high quality, single-layer graphene material in a large number, belong to technical field prepared by material in microtronics and information electronic.
Background technology
Grapheme material is a kind of novel semiconductor material.It is that current intensity known is in the world maximum, and heat conductivility is best, the material that thickness is the thinnest.Its thickness only has 0.3nm, but intensity is 100 times of steel, and thermal conductivity is 100 times of silicon.Since being found from 2004, be the focus of academic circles at present and industrial community for the preparation of grapheme material and property Quality Research.
The method preparing Graphene is at first original mechanically peel method, and the Van der Waals force namely directly overcoming the interlayer of bulk graphite makes the carbon atomic layer of individual layer be stripped out, and becomes nominal grapheme material.Owing to having found the character of grapheme material excellence, investigator has been had to also been proposed other method subsequently, such as: the method for graphite oxide reduction, by the graphite material preparing individual layer after original graphite expansion again through reduction, i.e. Graphene; " the slide fastener method " that use carbon nanotube (CNT) to be raw material in addition in addition, namely adopts catalyzer to be cut open vertically by carbon nanotube, namely obtains graphene band after expansion; In addition, also have direct growth method, namely use the method for chemical vapor deposition (CVD) directly at the graphite of Grown single or multiple lift; And use the method for heating SiC substrate, heat SiC substrate in the high temperature high vacuum environment also namely more than 1300 degrees Celsius, due to the volatilization of Si atom, the graphite material of single or multiple lift can be formed on its surface.In above various preparation methods, use the method for mechanically peel can obtain top-quality grapheme material, but due to its output very low, so the research being only limitted to laboratory uses.The method of graphite oxide reduction can be a large amount of prepare grapheme material, but the Graphene defect obtained is too many, quality need to improve.Use " the slide fastener method " that CNT is raw material to be also the one belonging to chemical process, owing to it using the catalyzer such as metal, can have an impact to the character of the Graphene obtained, the performance of the Graphene therefore obtained is also to be improved.The method advantage that CVD method prepares Graphene is can big area preparation, can be mutually integrated with semi-conductor industry, but the performance of the Graphene obtained also is difficult to and comparing favourably of using mechanically peel method to prepare.For this reason, both output was high to find one, and the measured method preparing Graphene of matter is problem very urgent at present.
Summary of the invention
Based on above problem, the object of this invention is to provide a kind of electrothermal ablation technology that uses to prepare the method for grapheme material, the method uses CNT or unbodied carbon source to be raw material, by heating ablation processes under vacuum conditions, makes carbon source be converted into grapheme material.Its advantage had is that the quality of the product obtained is good, and has higher productive rate.
The method detailed process that the present invention prepares grapheme material is as follows:
Prepare a method for grapheme material, concrete steps are:
(1) carbon nanotube or unbodied carbon source are placed on positive electrode or negative potential, positive electrode connects the positive pole of external power source, negative potential connects the negative pole of external power source, and positive electrode is close to each other with negative potential and contact conducting by carbon nanotube or unbodied carbon source;
(2) positive electrode of conducting and negative potential are placed in vacuum chamber, turn off the voltage of external power source, the vacuum tightness of vacuum chamber is evacuated to 10
-4~ 10
-5pa scope;
(3) on positive electrode and negative potential, apply the volts DS of 2-3V, carbon nanotube or unbodied carbon source are slowly heated; After heating 5-20 minute, again a voltage pulse 0.2-1V is applied to positive electrode and negative potential, the voltage of this pulse exceedes the voltage that carbon nanotube or unbodied carbon source can bear, there are part carbon nanotube or unbodied carbon source by the ablation of big current institute, electric current is reduced to 0 very soon, carbon nanotube in the middle of positive electrode and negative potential or unbodied carbon source are burnt till two-section, and the breaking part after ablation defines the material of a large amount of graphene-structured.
Electrode materials wherein can be any conducting metal; Vacuum chamber can be various shape specification; Heating CNT uses other modes, such as Resistant heating etc.; The voltage pulse applied can be selected as the case may be.
Preparation equipment required for method of the present invention is simple, and temperature is low, and raw material is simple and easy to get.It is easy to operate, reproducible, and the Graphene quality utilizing the present invention to prepare is good, and output is more.
Accompanying drawing explanation
Fig. 1 is the setting drawing that the present invention prepares grapheme material and uses.
Fig. 2 is transmission electron microscope (TEM) picture and the curent change figure of ablation CNT in the past.
Fig. 3 (a), for after CNT rolls into a ball ablated disconnection, have found the TEM picture of a large amount of flake graphite alkene structured materials at rupture portion; What b () was Graphene chooses electron-diffraction diagram.
Fig. 4 is the TEM photo in an other ablated area, and (a), for having the graphite flake structure of double-deck and multilayer, the arrow on top indicates multi-layer graphene structure, the few layer graphene structure of arrow instruction below; B () is for there being the graphite flake structure of single layer structure at edge; Arrow indicates single-layer graphene structure.
Fig. 5 is the I-E characteristic figure testing the single-layer graphene material obtained.
Embodiment
The device of the present embodiment as shown in Figure 1, comprise vacuum chamber 1, positive electrode 2, negative potential 3, method steps is: pugil carbon nanotube 4 is inserted the centre of positive electrode 2 and negative potential 3 by (1), for connecting this two conductive electrodes, the diameter of carbon nanotube 4 is below 100 nanometers, length is not limit, and the material of positive and negative electrode can be that the electrode connecting carbon nanotube 4 is inserted in vacuum chamber 1 also fixing by the metal (2) that the fusing point such as tungsten, graphite is higher, and the vacuum of vacuum chamber 1 is evacuated to 10 by (3)
-4below Pa, (4) between positive electrode 2 and negative potential 3, pass into the voltage of 2-3V, wait for about 10 minutes, (5) voltage of 2-3V between two electrodes is kept, and pass into the voltage pulse of 0.2-1V, blown by carbon nanotube 4, (6) rupture portion after carbon nanotube 4 blows finds a large amount of single-layer graphene materials.
Be described further referring to accompanying drawing.
As shown in Figure 1, Figure 2, CNT is placed on positive and negative electrode, by positive and negative electrode near and contact conducting by CNT.Because CNT itself has good conduction property, electric current can be observed after the external voltage that therefore applying one is little and pass through.Turn off outside voltage, the vacuum tightness of system is evacuated to 10
-4~ 10
-5on positive and negative electrode, apply the volts DS of 2-3V after Pa scope, CNT is slowly heated.Comparatively slow owing to dispelling the heat in vacuum, relative to two metal electrode CNT, there is larger resistance, therefore just CNT can be heated to higher temperature at about 10 minutes.In heat-processed, its electric current has a process slowly increased, and this is because heating causes CNT to improve with contacting of electrode, and the defect of CNT itself reduces simultaneously, and conductivity improves.Generally after heating 5-20 minute, two electrodes apply the voltage of a 0.2-1V, now, due to the voltage that applied voltage can bear more than CNT, there is part CNT will by the ablation of big current institute, electric current will be reduced to 0 very soon as can see from Figure 2, and the CNT in the middle of two electrodes is burnt till two-section.And the disconnecting unit branch after ablation finds the material defining a large amount of graphene-structured.
TEM picture in Fig. 2 gives the CNT structure before ablation, can see that a lot of CNT is intertwined, wherein have single wall and the various dissimilar CNT of many walls from figure.Careful inspection does not find that there is graphite form.The metal catalyst be less than wherein is had to be mingled with.
Fig. 3 (a) gives after CNT rolls into a ball ablated disconnection, have found the TEM picture of a large amount of flake graphite alkene structured materials at rupture portion.Wherein most of lamella is of a size of 10-20nm.The obtained grapheme material for individual layer significantly can be seen at edge portions.Owing to being through the graphene film that pyroprocessing obtains, so its quality is very good.What b () figure gave Graphene chooses electron-diffraction diagram (SAED), can see clearly corresponding to the diffraction ring of graphite material from figure is, it should be noted that especially original belong to block graphite distinctive (
000l) diffraction ring disappearance, this illustrates the single-layer graphene material good for crystallization prepared.
Fig. 4 gives the TEM photo in an other ablated area.Wherein, the region that (a) figure shows has graphite flake structure that is double-deck and multilayer; B region that () figure shows is presented at edge single layer structure.Which floor graphite sheet structure of similar individual layer or minority can be observed in most of region of sample.This illustrates that the Graphene using this method to prepare has higher output.
Fig. 5 gives the I-E characteristic figure testing the single-layer graphene material obtained, and the illustration in the upper left corner is TEM photo.See from figure, Graphene has good conduction property.It defines good ohmic contact after contacting with CNT.This illustrates that the Graphene prepared by this method has good structure and physical properties.
Claims (3)
1. prepare a method for grapheme material, it is characterized in that, the concrete steps of the method are:
(1) be placed on positive electrode or negative potential by unbodied carbon source, positive electrode connects the positive pole of external power source, and negative potential connects the negative pole of external power source, and positive electrode is close to each other with negative potential and contact conducting by unbodied carbon source;
(2) positive electrode of conducting and negative potential are placed in vacuum chamber, turn off the voltage of external power source, the vacuum tightness of vacuum chamber is evacuated to 10
-4~ 10
-5pa scope;
(3) unbodied carbon source is slowly heated; Heat after 5-20 minute, again a voltage pulse is applied to positive electrode and negative potential, the voltage of this pulse exceedes the voltage that unbodied carbon source can bear, unbodied carbon source is by the ablation of big current institute, unbodied carbon source in the middle of positive electrode and negative potential is burnt till two-section, and the breaking part after ablation defines the material of a large amount of graphene-structured.
2. a kind of method preparing grapheme material according to claim 1, is characterized in that: in described step (3) by the method that unbodied carbon source slowly heats be: utilize Resistant heating or on positive electrode and negative potential, apply the volts DS of 2-3V.
3. a kind of method preparing grapheme material according to claim 1 and 2, is characterized in that: the voltage pulse in described step (3) is 0.2-1V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310099793.2A CN103145123B (en) | 2013-04-17 | 2013-04-17 | A kind of method preparing grapheme material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310099793.2A CN103145123B (en) | 2013-04-17 | 2013-04-17 | A kind of method preparing grapheme material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145123A CN103145123A (en) | 2013-06-12 |
| CN103145123B true CN103145123B (en) | 2015-11-18 |
Family
ID=48543512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310099793.2A Expired - Fee Related CN103145123B (en) | 2013-04-17 | 2013-04-17 | A kind of method preparing grapheme material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145123B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3847128A1 (en) * | 2018-09-05 | 2021-07-14 | William Marsh Rice University | Flash joule heating synthesis method and compositions thereof |
| KR20220088716A (en) * | 2019-10-11 | 2022-06-28 | 유니버셜 매터 아이엔씨. | Apparatus, method and carbon fill for synthesizing graphene |
| CN112607731B (en) * | 2020-12-24 | 2021-08-10 | 广东工业大学 | Device and method for preparing graphene powder |
| CN114289711B (en) * | 2021-12-30 | 2023-05-02 | 广东工业大学 | Preparation method and preparation system of graphene coated metal material |
| CN115108548A (en) * | 2022-07-01 | 2022-09-27 | 厦门工学院 | Method and device for preparing graphene at high temperature by electric pulse |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051651A (en) * | 2011-01-11 | 2011-05-11 | 湖南大学 | Preparation method of graphene film |
| CN103000669A (en) * | 2011-09-09 | 2013-03-27 | 中国科学院微电子研究所 | Source-drain buried graphene transistor device on diamond-like carbon substrate and manufacture method |
-
2013
- 2013-04-17 CN CN201310099793.2A patent/CN103145123B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051651A (en) * | 2011-01-11 | 2011-05-11 | 湖南大学 | Preparation method of graphene film |
| CN103000669A (en) * | 2011-09-09 | 2013-03-27 | 中国科学院微电子研究所 | Source-drain buried graphene transistor device on diamond-like carbon substrate and manufacture method |
Non-Patent Citations (1)
| Title |
|---|
| Electrical and Structural Feature of Monolayer Graphene Produced by Pulse Current Unzipping and Microwave Exfoliation of Carbon Nanotubes;Woo Sik Kim et al.;《Chem. Mater.》;20111231;第23卷(第4期);940－944 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145123A (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145123B (en) | A kind of method preparing grapheme material | |
| Jain et al. | Monolayer graphene/hexagonal boron nitride heterostructure | |
| Hattori et al. | Layer-by-layer dielectric breakdown of hexagonal boron nitride | |
| Lee et al. | Breakdown current density of CVD-grown multilayer graphene interconnects | |
| Hibino et al. | Growth and electronic transport properties of epitaxial graphene on SiC | |
| Chueh et al. | TaSi2 nanowires: a potential field emitter and interconnect | |
| Di Bartolomeo et al. | Observation of field emission from GeSn nanoparticles epitaxially grown on silicon nanopillar arrays | |
| Zhang et al. | Electrical breakdown of ZnO nanowires in metal-semiconductor-metal structure | |
| Jain et al. | Graphene interconnects fully encapsulated in layered insulator hexagonal boron nitride | |
| DE102014103429A1 (en) | Sensor and sensor technology | |
| JP5990145B2 (en) | Graphene production method | |
| Jain et al. | Graphene-based interconnects on hexagonal boron nitride substrate | |
| Daniels et al. | Evidences of electrochemical graphene functionalization and substrate dependence by Raman and scanning tunneling spectroscopies | |
| Huang et al. | Observing the evolution of graphene layers at high current density | |
| Lee et al. | Vertically well-aligned epitaxial Ni31Si12 nanowire arrays with excellent field emission properties | |
| Kawano et al. | Formation and characterization of silicon/carbon nanotube/silicon heterojunctions by local synthesis and assembly | |
| Zhuge et al. | Single-crystalline metal filament-based resistive switching in a nitrogen-doped carbon film containing conical nanopores | |
| KR101505471B1 (en) | Transfer and adhesion technology of nano thin film | |
| Thapa et al. | Self filling of Ni nanoparticles in amorphous AlN nanotubes and its field emission property | |
| Tsutsui et al. | Atomically controlled fabrications of subnanometer scale electrode gaps | |
| Wang et al. | Single-walled carbon nanotube thermionic electron emitters with dense, efficient and reproducible electron emission | |
| Xu et al. | Transmission electron microscopy assisted in-situ joule heat dissipation study of individual InAs nanowires | |
| Alam et al. | In situ TEM modification of individual silicon nanowires and their charge transport mechanisms | |
| Daon et al. | Electrically conductive thermal interface materials based on vertically aligned carbon nanotubes mats | |
| Dardona et al. | Gas adsorption and high-emission current induced degradation of field emission characteristics in solution-processed ZnO nanoneedles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151118 Termination date: 20210417 |