CN102530936A - Method for producing graphene on silicon carbide (SiC) underlayer based on chlorine (Cl2) reaction - Google Patents
Method for producing graphene on silicon carbide (SiC) underlayer based on chlorine (Cl2) reaction Download PDFInfo
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- CN102530936A CN102530936A CN2012100073408A CN201210007340A CN102530936A CN 102530936 A CN102530936 A CN 102530936A CN 2012100073408 A CN2012100073408 A CN 2012100073408A CN 201210007340 A CN201210007340 A CN 201210007340A CN 102530936 A CN102530936 A CN 102530936A
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Abstract
The invention discloses a method for producing graphene on a silicon carbide (SiC) underlayer based on chlorine (Cl2) reaction, which mainly solves the problems of the rough surface and uneven layer numbers of the produced graphene in the prior art. The realization process of the method is that: a SiC sample piece is firstly cleaned standardly; the cleaned SiC sample piece is placed in a quartz tube, mixed gas of argon (Ar) gas and Cl2 is introduced into the quartz tube, and the SiC is reacted with the Cl2 for 3-8min under 700-1100 DEG C to produce a carbon film; and the produced carbon film is placed in the Ar gas, and is annealed under the temperature of 1000-1200 DEG C for 10-30min, so the graphene is produced. The method has a simple technology, high safety, produced graphenes with smooth surfaces and low porosity, and can be used for sealing gases and liquids.
Description
Technical field
The invention belongs to microelectronics technology, relate to semiconductor film material and preparation method thereof, specifically be based on Cl
2The method for preparing Graphene on the SiC substrate of reaction.
Technical background
It is in 2004 that Graphene appears in the laboratory, and at that time, two scientist An Delie Jim of Univ Manchester UK and the Ke Siteyanuowo Lip river husband that disappears found that they can obtain more and more thinner graphite flake with a kind of very simple method.They separate graphite flake from graphite, the two sides with thin slice is bonded on a kind of special adhesive tape then, tears adhesive tape, just can be divided into two graphite flake.Operation so constantly, last so thin slice is more and more thinner, they have obtained the thin slice that only is made up of one deck carbon atom, Here it is Graphene.After this, the novel method of preparation Graphene emerges in an endless stream.Present preparation method mainly contains two kinds:
1. arc process is used for preparing Graphene by people such as Rao CNR the earliest, and they use the mixed gas of hydrogen and helium as reaction gas.Use this method to prepare higher hydrogen pressure of Graphene needs and bigger discharging current, dangerous higher.
2. thermolysis SiC method: to remove Si through lip-deep SiC is decomposed, residual subsequently carbon forms Graphene with the monocrystal SiC heating.Yet the monocrystal SiC that uses in the SiC thermolysis is very expensive, and the Graphene that grows out is island and distributes, and hole is many, and the number of plies is inhomogeneous.
Existing preparation method of graphene; Like application number is " method of process for preparing graphenes by chemical vapour deposition " patent of 200810113596.0, and disclosed method is: at first prepare catalyzer, carry out high temperature chemical vapor deposition then; The substrate that will have catalyzer is put into anoxic reactor; Make substrate reach 500-1200 ℃, feed the carbon containing source of the gas again and carry out electroless plating and obtain Graphene, then to Graphene purify (being the evaporation down of s.t. or low pressure, high temperature) remove catalyzer.The main drawback of this method is: complex process, need the special catalyzer of removing, and energy consumption is big, and production cost is high.
Summary of the invention
The objective of the invention is to deficiency, propose a kind of based on Cl to above-mentioned prior art
2The method for preparing Graphene on the SiC substrate of reaction is to improve surface flatness, to reduce porosity.
For realizing above-mentioned purpose, preparation method of the present invention may further comprise the steps:
(1) the SiC print is cleaned, to remove surface contaminant;
(2) the SiC print after will cleaning places silica tube, is heated to 700-1100 ℃;
(3) in silica tube, feed Ar gas and Cl
2The mixed gas of gas, time length 3-8min makes Cl
2Generate carbon film with the 3C-SiC reaction;
(4) the carbon film print that generates being placed Ar gas is 1000-1200 ℃ of annealing 10-30min down in temperature, makes carbon film reconstitute Graphene.
The present invention compared with prior art has following advantage:
1. the method technology of the present invention's use is simple, and save energy is safe.
2. SiC and Cl among the present invention
2Can under lower temperature and normal pressure, react, and speed of reaction is fast.
3. the present invention is owing to utilize SiC and Cl
2Solid/liquid/gas reactions, thereby the Graphene smooth surface that generates, voidage is low, and thickness controls easily, can be used for the sealing to gas and liquid.
Description of drawings
Fig. 1 is the device synoptic diagram that the present invention prepares Graphene;
Fig. 2 is the schema that the present invention prepares Graphene.
Embodiment
With reference to Fig. 1, preparation equipment of the present invention mainly is made up of silica tube 1 and resistance furnace 2, and wherein silica tube 1 is provided with inlet mouth 3 and air outlet 4, and resistance furnace is 2 to be the ring-type hollow structure, and silica tube 1 is inserted in the resistance furnace 2.
With reference to Fig. 2, making method of the present invention provides following three kinds of embodiment.
Embodiment 1
Step 1: clean the 6H-SiC print, to remove surface contaminant.
(1.1) the 6H-SiC substrate base is used NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue;
(1.2) the 6H-SiC print that will remove behind the surperficial organic residue re-uses HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step 2: with the 6H-SiC print silica tube of packing into, and the exhaust heating.
(2.1) the 6H-SiC print after will cleaning is put into silica tube 1, places resistance furnace 2 to silica tube;
(2.2) to silica tube, feed the Ar gas that flow velocity is 80sccm from inlet mouth 3, silica tube was carried out emptying 10 minutes, air 4 discharges from the air outlet;
(2.3) open the resistance furnace power switch, silica tube is heated to 700 ℃.
Step 3: generate carbon film
Feed Ar gas and the Cl that flow velocity is respectively 98sccm and 2sccm to silica tube
2Gas, the time is 5 minutes, makes Cl
2Generate carbon film with the 6H-SiC reaction.
Step 4: the carbon film to generating reconstitutes Graphene
Resistance furnace temperature is risen to 1000 ℃, and in silica tube, feeding flow velocity is the Ar gas of 100sccm, the carbon film that generates is carried out 10 minutes annealing, to reconstitute Graphene.
Step 1: clean the 4H-SiC print, to remove surface contaminant.
The 4H-SiC substrate base is used NH earlier
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step 2: with the 4H-SiC print silica tube of packing into, and the exhaust heating.
4H-SiC print after cleaning is placed silica tube 1, place resistance furnace 2 to silica tube; To silica tube, feed the Ar gas that flow velocity is 80sccm from inlet mouth 3, silica tube was carried out emptying 10 minutes, with air 4 discharges from the air outlet; Open the resistance furnace power switch again, silica tube is heated to 1000 ℃.
Step 3: generate carbon film
Feed Ar gas and the Cl that flow velocity is respectively 97sccm and 3sccm to silica tube
2Gas, the time is 3 minutes, makes Cl
2Generate carbon film with the 4H-SiC reaction.
Step 4: the carbon film to generating reconstitutes Graphene
Resistance furnace temperature is risen to 1050 ℃, and in silica tube, feeding flow velocity is the Ar gas of 75sccm, the carbon film that generates is carried out 15 minutes annealing, to reconstitute Graphene.
Steps A: the 6H-SiC substrate base is carried out cleaning surfaces handle, promptly use NH earlier
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step B: the 6H-SiC print after will cleaning places silica tube 1, and places resistance furnace 2 to silica tube; To silica tube, feed the Ar gas that flow velocity is 80sccm from inlet mouth 3, silica tube was carried out emptying 10 minutes, with air 4 discharges from the air outlet; Open the resistance furnace power switch again, silica tube also is heated to 1100 ℃.
Step C: in silica tube, feed Ar gas and the Cl that flow velocity is respectively 95sccm and 5sccm
2Gas, the time is 8 minutes, makes Cl
2Generate carbon film with the 6H-SiC reaction.
Step D: resistance furnace temperature is risen to 1200 ℃, and in silica tube, feeding flow velocity is the Ar gas of 25sccm, the carbon film that generates is carried out 30 minutes annealing, to reconstitute Graphene.
Claims (5)
1. one kind based on Cl
2Prepare the method for Graphene on the SiC substrate of reaction, it is characterized in that the preparation method may further comprise the steps:
(1) the SiC print is cleaned, to remove surface contaminant;
(2) the SiC print after will cleaning places silica tube, is heated to 700-1100 ℃;
(3) in silica tube, feed Ar gas and Cl
2The mixed gas of gas, time length 3-8min makes Cl
2Generate carbon film with the 3C-SiC reaction;
(4) the carbon film print that generates being placed Ar gas is 1000-1200 ℃ of annealing 10-30min down in temperature, makes carbon film reconstitute Graphene.
2. according to claim 1 based on Cl
2Prepare the method for Graphene on the SiC substrate of reaction, it is characterized in that said step (1) cleans the SiC print, is use NH earlier
4OH+H
2O
2Reagent soaked the SiC print 10 minutes, took out the back oven dry, to remove print surface organic residue; Re-use HCl+H
2O
2Reagent soaked print 10 minutes, took out the back oven dry, to remove ionic contamination.
3. according to claim 1 based on Cl
2Prepare the method for Graphene on the SiC substrate of reaction, it is characterized in that the Ar gas and the Cl of the said feeding of step (3)
2Gas, its flow velocity is respectively 95-98sccm and 5-2sccm.
4. according to claim 1 based on Cl
2The method for preparing Graphene on the SiC substrate of reaction, the flow velocity of Ar gas is 25-100sccm when it is characterized in that said step (4) annealing.
5. according to claim 1 based on Cl
2The method for preparing Graphene on the SiC substrate of reaction is characterized in that the crystal formation of said SiC print adopts 4H-SiC or 6H-SiC.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936746A (en) * | 2012-10-29 | 2013-02-20 | 武汉理工大学 | Method for directly converting amorphous carbide into graphene under low-temperature and normal-pressure halogenation conditions |
| WO2013174139A1 (en) * | 2012-05-23 | 2013-11-28 | 西安电子科技大学 | METHOD FOR PREPARING STRUCTURED GRAPHENE ON SiC SUBSTRATE BASED ON CL2 REACTION |
| CN106744844A (en) * | 2016-12-23 | 2017-05-31 | 武汉理工大学 | A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline |
| US9691612B2 (en) | 2012-01-03 | 2017-06-27 | Xidian University | Process for preparing graphene on a SiC substrate based on metal film-assisted annealing |
| WO2019054563A1 (en) * | 2017-09-14 | 2019-03-21 | 김동호 | Mechanical seal |
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| CN1716522A (en) * | 2004-06-30 | 2006-01-04 | 齐卡博制陶业有限公司 | A method for the treatment of a surface of a metal-carbide substrate as well as such a metal-carbide substrate |
| CN101069264A (en) * | 2004-12-01 | 2007-11-07 | 应用材料股份有限公司 | Selective epitaxy process with alternating gas supply |
| CN101602503A (en) * | 2009-07-20 | 2009-12-16 | 西安电子科技大学 | The method of 4H-SiC silicon face extending and growing graphene |
| WO2010122928A1 (en) * | 2009-04-25 | 2010-10-28 | 国立大学法人九州工業大学 | Method for forming graphene film |
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2012
- 2012-01-03 CN CN2012100073408A patent/CN102530936A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1716522A (en) * | 2004-06-30 | 2006-01-04 | 齐卡博制陶业有限公司 | A method for the treatment of a surface of a metal-carbide substrate as well as such a metal-carbide substrate |
| CN101069264A (en) * | 2004-12-01 | 2007-11-07 | 应用材料股份有限公司 | Selective epitaxy process with alternating gas supply |
| WO2010122928A1 (en) * | 2009-04-25 | 2010-10-28 | 国立大学法人九州工業大学 | Method for forming graphene film |
| CN101602503A (en) * | 2009-07-20 | 2009-12-16 | 西安电子科技大学 | The method of 4H-SiC silicon face extending and growing graphene |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9691612B2 (en) | 2012-01-03 | 2017-06-27 | Xidian University | Process for preparing graphene on a SiC substrate based on metal film-assisted annealing |
| WO2013174139A1 (en) * | 2012-05-23 | 2013-11-28 | 西安电子科技大学 | METHOD FOR PREPARING STRUCTURED GRAPHENE ON SiC SUBSTRATE BASED ON CL2 REACTION |
| US9951418B2 (en) | 2012-05-23 | 2018-04-24 | Xidian University | Method for preparing structured graphene on SiC substrate based on Cl2 reaction |
| CN102936746A (en) * | 2012-10-29 | 2013-02-20 | 武汉理工大学 | Method for directly converting amorphous carbide into graphene under low-temperature and normal-pressure halogenation conditions |
| CN102936746B (en) * | 2012-10-29 | 2015-09-30 | 武汉理工大学 | Under low-temperature atmosphere-pressure and halogenation conditions, directly decolorizing carbon compound is converted into the method for Graphene |
| CN106744844A (en) * | 2016-12-23 | 2017-05-31 | 武汉理工大学 | A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline |
| WO2019054563A1 (en) * | 2017-09-14 | 2019-03-21 | 김동호 | Mechanical seal |
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