CN102583331A - Preparation method for large-area graphene based on Ni film auxiliary annealing and Cl2 reaction - Google Patents

Preparation method for large-area graphene based on Ni film auxiliary annealing and Cl2 reaction Download PDF

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CN102583331A
CN102583331A CN2012100099592A CN201210009959A CN102583331A CN 102583331 A CN102583331 A CN 102583331A CN 2012100099592 A CN2012100099592 A CN 2012100099592A CN 201210009959 A CN201210009959 A CN 201210009959A CN 102583331 A CN102583331 A CN 102583331A
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graphene
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CN102583331B (en
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郭辉
邓鹏飞
张玉明
张克基
雷天民
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Xidian University
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Abstract

The invention discloses a preparation method for large-area graphene based on Ni film auxiliary annealing and Cl2 reaction and mainly solves the problems that the graphene prepared in the prior art is small in area and non-uniform in layer number. The large-area graphene preparation method comprises the following steps: firstly, growing a carbonization layer as transition on a Si-based substrate with 4-12 inches; secondly, growing a 3C-SiC heteroepitaxial film at the temperature of 1200-1300 DEG C by using C3H8 and SiH4 as gas sources; thirdly, reacting 3C-SiC with Cl2 at the temperature of 700-1100 DEG C to generate a carbon film; fourthly, depositing a Ni film with the thickness of 300-500nm on a Si matrix by using an electron beam; and fifthly, feeding a carbon surface of the generated carbon film sample wafer on a Ni film, feeding the generated carbon film sample wafer and the Cu film in Ar gas and annealing at the temperature of 900-1100DEG C for 15-30 minutes to generate graphene. The graphene generated by the method disclosed by the invention has the advantages of large area, smooth surface, favorable continuousness and low porosity and can be used for sealing gas and liquid.

Description

Based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction
Technical field
The invention belongs to microelectronics technology, relate to a kind of semiconductor film material and preparation method thereof, specifically be based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method 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. chemical Vapor deposition process provides a kind of effective ways of controlled preparation Graphene; It is with planar substrates; Place the decomposable presoma of high temperature like mf, metal single crystal etc.; In atmosphere such as methane, ethene, make carbon atom be deposited on substrate surface through high temperature annealing and form Graphene, at last with obtaining independently graphene film after the chemical corrosion method removal metal base.The growth of the adjustable Graphenes of parameter such as flow of the type through selecting substrate, the temperature of growth, presoma; Like growth velocity, thickness, area etc.; The maximum shortcoming of this method is that the Graphene lamella and the substrate that obtain interact strong; Lost the character of many single-layer graphenes, and the continuity of Graphene not fine.
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 the number of plies is inhomogeneous, and size is less, is difficult to big area and makes Graphene.
Summary of the invention
The objective of the invention is to deficiency, propose a kind of based on Ni film auxiliary annealing and Cl to above-mentioned prior art 2The big area graphene preparation method of reaction to improve surface flatness and continuity, reduce porosity, to reduce cost, is implemented in large-area manufacturing Graphene on the 3C-SiC substrate.
For realizing above-mentioned purpose, preparation method of the present invention may further comprise the steps:
(1) the Si substrate base to the 4-12 inch carries out standard cleaning;
(2) the Si substrate base after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10 -7The mbar rank;
(3) at H 2Progressively be warming up to 900 ℃-1200 ℃ of carbonization temperatures under the situation of protection, feeding flow is the C of 30sccm 3H 8, substrate is carried out carbonization 5-10min, growth one deck carburization zone;
(4) be warming up to 1200 ℃-1300 ℃ of growth temperatures rapidly, feed C 3H 8And SiH 4, carry out 3C-SiC hetero epitaxy growth for Thin Film, the time is 30-60min, then at H 2Protection progressively is cooled to room temperature down, accomplishes the growth of 3C-SiC epitaxial film;
(5) the good 3C-SiC print of will growing places silica tube, is heated to 700-1100 ℃;
(6) in silica tube, feed Ar gas and Cl 2The mixed gas of gas, time length 3-5min makes Cl 2Generate carbon film with the 3C-SiC reaction;
(7) the Ni film that electron beam deposition 300-500nm is thick on the Si matrix;
(8) the carbon face with the carbon film print that generates places on the Ni film, together places Ar gas to be 900-1100 ℃ in temperature them again and anneals 15-30 minute down, and carbon film reconstitutes Graphene, the Ni film is taken away from the Graphene print again.
The present invention compared with prior art has following advantage:
The present invention since growth during 3C-SiC earlier on the Si substrate growth one deck carburization zone as transition, and then growth 3C-SiC, thereby the 3C-SiC quality of growth is high.
But the present invention since the 3C-SiC heteroepitaxial growth on the Si disk, and Si disk size can reach 12 inches, thus with this method can growing large-area Graphene, and low price.
3. 3C-SiC and Cl among the present invention 2Can under lower temperature and normal pressure, react, and speed of reaction is fast.
4. the present invention is owing to utilize 3C-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.
5. the present invention anneals owing to being utilized on the Ni film, thereby the easier reconstruct of the carbon film that generates forms continuity Graphene preferably.
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: remove the sample surfaces pollutent.
4 inches Si substrate bases are 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: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10 -7The mbar rank.
Step 3: growth carburization zone.
At H 2Under the situation of protection reaction chamber temperature is risen to 900 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30sccm 3H 8, growth one deck carburization zone on the Si substrate, growth time is 10min.
Step 4: growth 3C-SiC epitaxial film on carburization zone.
Reaction chamber temperature is risen to 1200 ℃ of growth temperatures rapidly, feed the SiH that flow is respectively 20sccm and 40sccm 4And C 3H 8, carrying out 3C-SiC hetero epitaxy growth for Thin Film, growth time is 60min; Then at H 2Protection progressively is cooled to room temperature down, accomplishes the growth of 3C-SiC epitaxial film.
Step 5: with the 3C-SiC print silica tube of packing into, and the exhaust heating.
(5.1) the good 3C-SiC epitaxial film print of will growing takes out from CVD system response chamber and is placed on the silica tube 5, places resistance furnace 2 to silica tube;
(5.2) to silica tube, feed the Ar gas that flow velocity is 80sccm from inlet mouth 3, silica tube was carried out emptying 10 minutes, gas is 4 discharges from the air outlet;
(5.3) open the resistance furnace power switch, be warming up to 700 ℃, make silica tube therein also be heated to 700 ℃.
Step 6: 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 3C-SiC reaction.
Step 7: get another Si substrate print and put on the substrate slide glass of electron beam evaporation deposition machine, substrate is 50cm to the distance of target, and reaction chamber pressure is evacuated to 5 * 10 -4Pa, the adjusting line is 40mA, evaporation 10min, the thick Ni film of deposition one deck 300nm on Si substrate print.
Step 8: reconstitute Graphene.
(7.1) the carbon film print that generates is taken out from silica tube, its carbon face is placed on the Ni film;
(7.2) carbon film print and Ni film integral body being placed flow velocity is the Ar gas of 90sccm, is 1100 ℃ of annealing 15 minutes down in temperature, and the katalysis through metal Ni makes carbon film reconstitute the successive Graphene;
(7.3) the Ni film is taken away from the Graphene print.
Embodiment 2
Step 1: remove the sample surfaces pollutent.
8 inches Si substrate bases are 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: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10 -7The mbar rank.
Step 3: growth carburization zone.
At H 2Under the situation of protection reaction chamber temperature is risen to 1050 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30sccm 3H 8, growth one deck carburization zone on the Si substrate, growth time is 7min.
Step 4: growth 3C-SiC epitaxial film on carburization zone.
Reaction chamber temperature is risen to 1200 ℃ of growth temperatures rapidly, feed the SiH that flow is respectively 25sccm and 50sccm 4And C 3H 8, carrying out 3C-SiC hetero epitaxy growth for Thin Film, growth time is 45min; Then at H 2Protection progressively is cooled to room temperature down, accomplishes the growth of 3C-SiC epitaxial film.
Step 5: with the 3C-SiC print silica tube of packing into, and the exhaust heating.
The 3C-SiC epitaxial film print that growth is good takes out from CVD system response chamber and is placed on the silica tube 5, 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, gas is 4 discharges from the air outlet; Open the resistance furnace power switch again, be warming up to 1000 ℃, make silica tube therein also be heated to 1000 ℃.
Step 6: generate carbon film
Feed Ar gas and the Cl that flow velocity is respectively 97sccm and 3sccm to silica tube 2Gas, the time is 4 minutes, makes Cl 2Generate carbon film with the 3C-SiC reaction.
Step 7: get another Si substrate print and put on the substrate slide glass of electron beam evaporation deposition machine, substrate is 50cm to the distance of target, and reaction chamber pressure is evacuated to 5 * 10 -4Pa, the adjusting line is 40mA, evaporation 15min, the thick Ni film of deposition one deck 400nm on Si substrate print.
Step 8: reconstitute Graphene.
The carbon film print that generates is taken out from silica tube, its carbon face is placed on the Ni film; It is the Ar gas of 55sccm that carbon film print and Ni film integral body are placed flow velocity, is 1000 ℃ of annealing 20 minutes down in temperature, and the katalysis through metal Ni makes carbon film reconstitute the successive Graphene; The Ni film is taken away from the Graphene print.
Embodiment 3
Steps A: 12 inches Si substrate bases are 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 Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10 -7The mbar rank.
Step C: at H 2Under the situation of protection reaction chamber temperature is risen to 1200 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30sccm 3H 8, continue 5min, with growth one deck carburization zone on the Si substrate.
Step D: reaction chamber temperature is risen to 1300 ℃ of growth temperatures rapidly, feed the SiH that flow is respectively 30sccm and 60sccm 4And C 3H 8, carry out 3C-SiC hetero epitaxy growth for Thin Film 30min; Then at H 2Protection progressively is cooled to room temperature down.
Step e: the good 3C-SiC epitaxial film print of will growing takes out from CVD system response chamber and is placed on the silica tube 5, 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, gas is 4 discharges from the air outlet; Open the resistance furnace power switch again, be warming up to 1100 ℃, make silica tube therein also be heated to 1100 ℃.
Step F: in silica tube, feed Ar gas and the Cl that flow velocity is respectively 95sccm and 5sccm 2Gas, the time is 3 minutes, makes Cl 2Generate carbon film with the 3C-SiC reaction.
Step G: get another Si substrate print and put on the substrate slide glass of electron beam evaporation deposition machine, substrate is 50cm to the distance of target, and reaction chamber pressure is evacuated to 5 * 10 -4Pa, the adjusting line is 40mA, evaporation 20min, the thick Ni film of deposition one deck 500nm on Si substrate print.
Step H: the carbon film print that generates is taken out from silica tube, its carbon face is placed on the Ni film; It is the Ar gas of 30sccm that carbon film print and Ni film integral body are placed flow velocity, is 900 ℃ of annealing 30 minutes down in temperature, and the katalysis through metal Ni makes carbon film reconstitute the successive Graphene; The Ni film is taken away from the Graphene print.

Claims (5)

1. one kind based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction is characterized in that the preparation method may further comprise the steps:
(1) the Si substrate base to the 4-12 inch carries out standard cleaning;
(2) the Si substrate base after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10 -7The mbar rank;
(3) at H 2Progressively be warming up to 900 ℃-1200 ℃ of carbonization temperatures under the situation of protection, feeding flow is the C of 30sccm 3H 8, substrate is carried out carbonization 5-10min, growth one deck carburization zone;
(4) be warming up to 1200 ℃-1300 ℃ of growth temperatures rapidly, feed C 3H 8And SiH 4, carry out 3C-SiC hetero epitaxy growth for Thin Film, the time is 30-60min, then at H 2Protection progressively is cooled to room temperature down, accomplishes the growth of 3C-SiC epitaxial film;
(5) the good 3C-SiC print of will growing places silica tube, is heated to 700-1100 ℃;
(6) in silica tube, feed Ar gas and Cl 2The mixed gas of gas, time length 3-5min makes Cl 2Generate carbon film with the 3C-SiC reaction;
(7) the Ni film that electron beam deposition 300-500nm is thick on the Si matrix;
(8) the carbon face with the carbon film print that generates places on the Ni film, together places Ar gas to be 900-1100 ℃ in temperature them again and anneals 15-30 minute down, and carbon film reconstitutes Graphene, the Ni film is taken away from the Graphene print again.
2. according to claim 1 based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction is characterized in that the SiH of the said feeding of step (4) 4And C 3H 8, its flow is respectively 20-30sccm and 40-60sccm.
3. according to claim 1 based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction is characterized in that the Ar gas and the Cl of the said feeding of step (6) 2Gas, its flow velocity is respectively 95-98sccm and 5-2sccm.
4. according to claim 1 based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction, the condition of electron beam deposition in the said step (7) of it is characterized in that are substrate to the distance of target is 50cm, and reaction chamber pressure is 5 * 10 -4Pa, line are 40mA, and evaporation time is 10-20min.
5. according to claim 1 based on Ni film auxiliary annealing and Cl 2The big area graphene preparation method of reaction, the flow velocity of Ar gas is 30-90sccm when it is characterized in that said step (8) annealing.
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CN102938368A (en) * 2012-11-23 2013-02-20 西安电子科技大学 Si-substrate patterned graphene preparation method based on Ni film annealing
CN103183338A (en) * 2013-03-12 2013-07-03 西安电子科技大学 Preparation method of large-area graphene based on Ni film annealing and chlorine reaction
CN103183336A (en) * 2013-03-12 2013-07-03 西安电子科技大学 Preparation method of large-area graphene on Si substrate based on Ni film annealing
WO2013102359A1 (en) * 2012-01-03 2013-07-11 西安电子科技大学 Method for preparing graphene on sic substrate based on annealing with assistant metal film
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CN106637393A (en) * 2016-11-07 2017-05-10 山东大学 Method for utilizing metal to assist epitaxial growth of graphene on 6H/4H-SiC carbon surface
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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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US9048092B2 (en) 2012-01-03 2015-06-02 Xidian University Process for preparing graphene based on metal film-assisted annealing and the reaction with Cl2
WO2013102359A1 (en) * 2012-01-03 2013-07-11 西安电子科技大学 Method for preparing graphene on sic substrate based on annealing with assistant metal film
WO2013102360A1 (en) * 2012-01-03 2013-07-11 西安电子科技大学 Method for preparing graphene by reaction with cl2 based on annealing with assistant metal film
US9691612B2 (en) 2012-01-03 2017-06-27 Xidian University Process for preparing graphene on a SiC substrate based on metal film-assisted annealing
US9951418B2 (en) 2012-05-23 2018-04-24 Xidian University Method for preparing structured graphene on SiC substrate based on Cl2 reaction
CN102938368A (en) * 2012-11-23 2013-02-20 西安电子科技大学 Si-substrate patterned graphene preparation method based on Ni film annealing
CN103183338A (en) * 2013-03-12 2013-07-03 西安电子科技大学 Preparation method of large-area graphene based on Ni film annealing and chlorine reaction
CN103183336A (en) * 2013-03-12 2013-07-03 西安电子科技大学 Preparation method of large-area graphene on Si substrate based on Ni film annealing
CN103590099A (en) * 2013-12-03 2014-02-19 西安电子科技大学 Wafer level graphene controllable epitaxy method based on MOCVD devices
CN103590099B (en) * 2013-12-03 2016-05-25 西安电子科技大学 The controlled epitaxy method of wafer level Graphene based on MOCVD equipment
CN106637393A (en) * 2016-11-07 2017-05-10 山东大学 Method for utilizing metal to assist epitaxial growth of graphene on 6H/4H-SiC carbon surface
CN106637393B (en) * 2016-11-07 2019-01-29 山东大学 A method of utilizing metal auxiliary extending and growing graphene on 6H/4H-SiC carbon face
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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