CN102602923A - Method for preparing graphene based on SiC as substrate - Google Patents
Method for preparing graphene based on SiC as substrate Download PDFInfo
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- CN102602923A CN102602923A CN2012101031845A CN201210103184A CN102602923A CN 102602923 A CN102602923 A CN 102602923A CN 2012101031845 A CN2012101031845 A CN 2012101031845A CN 201210103184 A CN201210103184 A CN 201210103184A CN 102602923 A CN102602923 A CN 102602923A
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Abstract
The invention discloses a method for preparing graphene based on SiC as substrate, mainly solving the problems that the graphene prepared in the prior art is not smooth in surface and not uniform in number of layers. The method comprises the steps of firstly carrying out standard washing on a SiC sample slice; placing the washed SiC sample slice in a quartz tube; carrying CC14 steam by utilizing Ar gas into the quartz tube, reacting the SiC with gaseous CC14 at a temperature of 800-1100 DEG C to generate a double-layer carbon film; and annealing the generated double-layer carbon film sample slice for 10-30minutes in the Ar gas at a temperature of 1000-1200 DEG C to ensure that the double-layer carbon film is reconstructed to obtain the double-layer graphene. The method disclosed by the invention is simple in process and high in safety; the obtained double-layer graphene has the advantages of smooth surface and low porosity and can be used for the sealing of gases and liquids.
Description
Technical field
The invention belongs to microelectronics technology, relate to a kind of semiconductor film material and preparation method thereof, specifically is the graphene preparation method of substrate with SiC.
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.From now on, the novel method of preparation Graphene emerges in an endless stream, but uses maximum mainly contain following 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 is " method of process for preparing graphenes by chemical vapour deposition " patent of 200810113596.0 like application number, 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, makes substrate reach 500-1200 ℃, feeds the carbon containing source of the gas again and carries out electroless plating and obtain Graphene; Then Graphene is purified, i.e. s.t. or low pressure, high temperature evaporation are down removed 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 the deficiency to above-mentioned prior art, proposing a kind of is the graphene preparation method of substrate with SiC, to improve the Graphene 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 carried out standard cleaning, promptly use NH earlier
4OH+H
2O
2Reagent soaked print 10 minutes, took out the back oven dry, re-used HCl+H
2O
2Reagent soaked print 10 minutes;
(2) the SiC print after will cleaning places silica tube, is heated to 800-1100 ℃;
(3) to CCl is housed
4The there-necked flask of liquid is heated to 65-80 ℃, utilizes Ar gas to carry CCl
4Steam gets in the silica tube and reacts with SiC, generates double-deck carbon film, and the reaction times is 20-120min;
The double-deck carbon film print that (4) will generate places Ar gas to be 1000-1200 ℃ in temperature and annealed 10-30 minute down, reconstitutes double-layer graphite alkene.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. the present invention is owing to utilize SiC and CCl
4Gas reaction, thereby the double-layer graphite alkene smooth surface that generates, porosity is low, 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 is mainly by three-way valve 3, there-necked flask 10, and water-bath 11, silica tube 5, resistance furnace 6 is formed; Three-way valve 3 links to each other with silica tube 5 through first channel 1, link to each other with the left side mouth of there-necked flask 10 through second passage 2, and the right side mouth of there-necked flask 10 links to each other with silica tube 5, and CCl is housed in the there-necked flask
4Liquid, and it is placed in the water-bath 11, and silica tube 5 is placed in the resistance furnace 6.
With reference to Fig. 2, making method of the present invention provides following three kinds of embodiment.
Embodiment 1
Step 1: remove the sample surfaces pollutent.
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 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 5, and places resistance furnace 6 to silica tube;
(2.2) resistance to air loss of the whole preparation equipment of inspection, feeding flow velocitys from inlet mouth 4 is the Ar gas of 80ml/min, and utilizes three-way valve 3 control Ar gas to get into from first channel 1 silica tube was carried out emptying 30 minutes, and air in the silica tube 7 is discharged from the air outlet;
(2.3) open the resistance furnace power switch, silica tube is warming up to 800 ℃.
Step 3: the double-deck carbon film of growing.
(3.1) bath 11 power supplys of fetching boiling water are to being equipped with CCl
4The there-necked flask 10 of liquid is heated to 65 ℃;
(3.2) after resistance furnace reaches 800 ℃ of setting, the swivel tee valve, making flow velocity is that the Ar gas of 50ml/min flows into there-necked flasks from second passage 2, and carries CCl
4Steam gets into silica tube, makes gaseous state CCl
4React in silica tube with 6H-SiC, generate double-deck carbon film, the reaction times is 20 minutes.
Step 4: the double-deck carbon film of generation reconstitutes double-layer graphite alkene.
(4.1) after reaction finished, the swivel tee valve made Ar gas turn to first channel to get into silica tube rapidly, and the flow velocity of Ar gas is adjusted into 25ml/min from 50ml/min;
(4.2) resistance furnace temperature is risen to 1000 ℃ rapidly, the double-deck carbon film of generation was annealed 30 minutes, reconstitute double-layer graphite alkene; Close resistance furnace power supply and water-bath power supply then, make double-layer graphite alkene under the Ar gas shiled, be cooled to room temperature, and the bath water port 9 of fetching boiling water, behind the hot water of draining, introduce cold water from water-in 8, make CCl
4The liquid fast cooling.
Embodiment 2
Step 1: remove the sample surfaces pollutent.
The 4H-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 2: with the 4H-SiC print silica tube of packing into, and the exhaust heating.
4H-SiC print after cleaning is placed silica tube 5, and place resistance furnace 6 to silica tube; Check the resistance to air loss of whole preparation equipment, feeding flow velocity from inlet mouth 4 is the Ar gas of 80ml/min, and utilizes three-way valve 3 control Ar gas to get into from first channel 1 silica tube was carried out emptying 30 minutes, makes air 7 discharges from the air outlet in the silica tube; Open the resistance furnace power switch, silica tube is warming up to 900 ℃.
Step 3: the double-deck carbon film of growing.
Step 4: the double-deck carbon film of generation reconstitutes double-layer graphite alkene.
After reaction finished, the swivel tee valve made Ar gas turn to first channel to get into silica tube rapidly, and the flow velocity of Ar gas is adjusted into 80ml/min from 60ml/min; Resistance furnace temperature is risen to 1050 ℃ rapidly, the double-deck carbon film of generation was annealed 15 minutes, reconstitute double-layer graphite alkene; Close resistance furnace power supply and water-bath power supply then, make double-layer graphite alkene under the Ar gas shiled, be cooled to room temperature, and the bath water port 9 of fetching boiling water, behind the hot water of draining, introduce cold water from water-in 8, make CCl
4The liquid fast cooling.
Embodiment 3
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 5, and places resistance furnace 6 to silica tube; Check the resistance to air loss of whole preparation equipment, feeding flow velocity from inlet mouth 4 is the Ar gas of 80ml/min, and utilizes three-way valve 3 control Ar gas to get into from first channel 1 silica tube was carried out emptying 30 minutes, makes air 7 discharges from the air outlet in the silica tube; Open the resistance furnace power switch, silica tube is warming up to 1100 ℃.
Step C: bath 11 power supplys of fetching boiling water, to CCl is housed
4The there-necked flask 10 of liquid is heated to 80 ℃; Reach 1100 ℃ of setting when resistance furnace after, the swivel tee valve, making flow velocity is that the Ar gas of 80ml/min flows into there-necked flasks from second passage 2, and carries CCl
4Steam gets into silica tube, makes gaseous state CCl
4In silica tube, reacted 120 minutes with 6H-SiC, generate double-deck carbon film.
Step D: after reaction finished, the swivel tee valve made Ar gas turn to first channel to get into silica tube rapidly, and the flow velocity of Ar gas is adjusted into 100ml/min from 80ml/min; Resistance furnace temperature is risen to 1200 ℃ rapidly, the double-deck carbon film of generation was annealed 10 minutes, reconstitute double-layer graphite alkene; Close resistance furnace power supply and water-bath power supply then, make double-layer graphite alkene under the Ar gas shiled, be cooled to room temperature, and the bath water port 9 of fetching boiling water, behind the hot water of draining, introduce cold water from water-in 8, make CCl
4The liquid fast cooling.
Claims (4)
1. one kind is the graphene preparation method of substrate with SiC, may further comprise the steps:
(1) the SiC print is carried out standard cleaning, promptly use NH earlier
4OH+H
2O
2Reagent soaked print 10 minutes, took out the back oven dry, re-used HCl+H
2O
2Reagent soaked print 10 minutes;
(2) the SiC print after will cleaning places silica tube, is heated to 800-1100 ℃;
(3) to CCl is housed
4The there-necked flask of liquid is heated to 65-80 ℃, utilizes Ar gas to carry CCl
4Steam gets in the silica tube and reacts with SiC, generates double-deck carbon film, and the reaction times is 20-120min;
The double-deck carbon film print that (4) will generate places Ar gas to be 1000-1200 ℃ in temperature and annealed 10-30 minute down, reconstitutes double-layer graphite alkene.
2. according to claim 1 is the graphene preparation method of substrate with SiC, it is characterized in that the Ar gas velocity is 50-80ml/min in the said step (3).
3. according to claim 1 is the graphene preparation method of substrate with SiC, and the flow velocity of Ar gas is 25-100ml/min when it is characterized in that said step (4) annealing.
4. according to claim 1 is the graphene preparation method of substrate with SiC, it is characterized in that the crystal formation of said SiC print adopts 4H-SiC or 6H-SiC.
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|---|---|---|---|
| CN2012101031845A CN102602923A (en) | 2012-04-11 | 2012-04-11 | Method for preparing graphene based on SiC as substrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437914A (en) * | 2018-12-29 | 2019-03-08 | 杭州坚膜科技有限公司 | Silicon carbide film and preparation method thereof |
| CN110137076A (en) * | 2019-05-30 | 2019-08-16 | 深圳爱仕特科技有限公司 | Novel SiC power device high annealing protective film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10188951A (en) * | 1996-12-24 | 1998-07-21 | Komatsu Ltd | Electrode plate and manufacture thereof |
| 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 |
| US20110101302A1 (en) * | 2009-11-05 | 2011-05-05 | University Of Southern California | Wafer-scale fabrication of separated carbon nanotube thin-film transistors |
-
2012
- 2012-04-11 CN CN2012101031845A patent/CN102602923A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10188951A (en) * | 1996-12-24 | 1998-07-21 | Komatsu Ltd | Electrode plate and manufacture thereof |
| 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 |
| US20110101302A1 (en) * | 2009-11-05 | 2011-05-05 | University Of Southern California | Wafer-scale fabrication of separated carbon nanotube thin-film transistors |
Non-Patent Citations (1)
| Title |
|---|
| JIAN SUI, JINJUN LU: "The formation of a dual-layer carbon film on silicon carbide using a combination of carbide-derived carbon process and chemical vapor deposition in a CCl4-containing atmosphere", 《CA R B O N》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437914A (en) * | 2018-12-29 | 2019-03-08 | 杭州坚膜科技有限公司 | Silicon carbide film and preparation method thereof |
| CN109437914B (en) * | 2018-12-29 | 2021-06-22 | 浙江坚膜科技有限公司 | Silicon carbide film and preparation method thereof |
| CN110137076A (en) * | 2019-05-30 | 2019-08-16 | 深圳爱仕特科技有限公司 | Novel SiC power device high annealing protective film and preparation method thereof |
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Application publication date: 20120725 |