CN102505113B - Preparation method of large-area graphene based on Cl2 reaction - Google Patents
Preparation method of large-area graphene based on Cl2 reaction Download PDFInfo
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- CN102505113B CN102505113B CN 201210000361 CN201210000361A CN102505113B CN 102505113 B CN102505113 B CN 102505113B CN 201210000361 CN201210000361 CN 201210000361 CN 201210000361 A CN201210000361 A CN 201210000361A CN 102505113 B CN102505113 B CN 102505113B
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Abstract
The invention discloses a preparation method of large-area graphene based on Cl2 reaction, and is mainly used for solving the problems of small area and non-uniform layers of graphene prepared by the prior art. The method comprises the following steps of: (1) growing a carbonization layer on an Si substrate of 4-12 inches; (2) growing a 3C-SiC epitaxy film by use of an air source C3H8 and SiH4 at a temperature of 1150-1300 DEG C; (3) reacting 3C-SiC with Cl2 at 700-1050 DEG C to generate a carbon film; and (4) placing the generated carbon film in Ar, and annealing at a temperature of 1000-1100 DEG C for 10-25 minutes to generate graphene. Through the method disclosed by the invention, generated graphene has large area, smooth surface and low porosity, and can be used for sealing gas and liquid.
Description
Technical field
The invention belongs to microelectronics technology, relate to a kind of semiconductor film material and preparation method thereof, specifically be based on 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, then the two sides with thin slice is bonded on a kind of special adhesive tape, tears adhesive tape, just can be divided into two graphite flake.Constantly like this operation, last so thin slice is more and more thinner, they have obtained the thin slice that only is made 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. micromechanics stripping method: directly graphene platelet is cut down from larger crystal.Novoselovt in 2004 etc. have prepared single-layer graphene in this way, and can be at stable existence under the external environment, see document " K.S.Novoselovt, science, (2004) " Electric field effect in atomically thin carbon films " ".The typical case preparation method is expanded with another material or the pyrolytic graphite of introducing defective rubs, and the surface of body phase graphite can produce the crystal of flocculus shape, contains the Graphene of individual layer in the crystal of these flocculus shapes.Be the graphene platelet that the thin slice that utilizes the friction graphite surface to obtain filters out individual layer but shortcoming is this method, its size is wayward, and factory length is enough for the graphene platelet of using reliably.
2. thermolysis SiC method: to remove Si by lip-deep SiC is decomposed, residual carbon forms Graphene subsequently 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 object of the invention is to the deficiency for above-mentioned prior art, propose a kind of based on Cl
2The big area graphene preparation method of reaction to improve surface flatness, to reduce porosity, Cost reduction, is implemented in large-area manufacturing Graphene on the 3C-SiC substrate.
For achieving the above object, preparation method of the present invention may further comprise the steps:
(1) the Si substrate base of 4-12 inch carried 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 950 ℃-1150 ℃ of carbonization temperatures in the situation of protection, pass into the C that flow is 30sccm
3H
8, substrate is carried out carbonization 3-7min, growth one deck carburization zone;
(4) be warming up to rapidly 1150 ℃-1300 ℃ of growth temperatures, pass into C
3H
8And SiH
4, carry out the growth of 3C-SiC hetero epitaxy film, the time is 36-60min, then at H
2Protection is lower progressively to be cooled to room temperature, finishes the growth of 3C-SiC epitaxial film;
(5) the good 3C-SiC print of will growing places silica tube, is heated to 700-1050 ℃;
(6) in silica tube, pass into Ar gas and Cl
2The mixed gas of gas, time length 3-5min, Cl
2Generate carbon film with the 3C-SiC reaction;
(7) the carbon film print that generates being placed Ar gas is 1000-1100 ℃ of lower annealing 10-25 minute in temperature, makes carbon film reconstitute Graphene.
The present invention compared with prior art has following advantage:
The present invention since growth during 3C-SiC first 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.
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 comprised 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 for the annular 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 process, namely use first NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, 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
2In the situation of protection reaction chamber temperature is risen to 950 ℃ of carbonization temperatures, then pass into the C that flow is 30sccm to reaction chamber
3H
8, at Si Grown one deck carburization zone, growth time is 7min.
Step 4: at carburization zone growth 3C-SiC epitaxial film.
Reaction chamber temperature is risen to rapidly 1150 ℃ of growth temperatures, pass into the SiH that flow is respectively 15sccm and 30sccm
4And C
3H
8, carrying out the growth of 3C-SiC hetero epitaxy film, growth time is 60min; Then at H
2Protection is lower progressively to be cooled to room temperature, finishes 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 1, and silica tube is placed resistance furnace 2;
(5.2) passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, silica tube is carried out emptying 10 minutes, with air 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
Pass into 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: the carbon film that generates is reconstituted Graphene
Resistance furnace temperature is risen to 1000 ℃, in silica tube, pass into the Ar gas that flow velocity is 100sccm, the carbon film that generates is carried out 10 minutes annealing, to reconstitute Graphene.
Embodiment 2
Step 1: remove the sample surfaces pollutent.
8 inches Si substrate bases are carried out cleaning surfaces process, namely use first NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, 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
2In the situation of protection reaction chamber temperature is risen to 1050 ℃ of carbonization temperatures, then pass into the C that flow is 30sccm to reaction chamber
3H
8, at Si Grown one deck carburization zone, growth time is 5min.
Step 4: at carburization zone growth 3C-SiC epitaxial film.
Reaction chamber temperature is risen to rapidly 1200 ℃ of growth temperatures, pass into the SiH that flow is respectively 20sccm and 40sccm
4And C
3H
8, carrying out the growth of 3C-SiC hetero epitaxy film, growth time is 45min; Then at H
2Protection is lower progressively to be cooled to room temperature, finishes 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 1, and silica tube is placed resistance furnace 2; Passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, silica tube is carried out emptying 10 minutes, with air 4 discharges from the air outlet; Open again the resistance furnace power switch, be warming up to 1000 ℃, make silica tube therein also be heated to 1000 ℃.
Step 6: generate carbon film
Pass into 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: the carbon film that generates is reconstituted Graphene
Resistance furnace temperature is risen to 1050 ℃, in silica tube, pass into the Ar gas that flow velocity is 75sccm, the carbon film that generates is carried out 15 minutes annealing, to reconstitute Graphene.
Steps A: 12 inches Si substrate bases are carried out cleaning surfaces process, namely use first NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, 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
2In the situation of protection reaction chamber temperature is risen to 1150 ℃ of carbonization temperatures, then pass into the C that flow is 30sccm to reaction chamber
3H
8, continue 3min, with at Si Grown one deck carburization zone.
Step D: reaction chamber temperature is risen to rapidly 1300 ℃ of growth temperatures, pass into the SiH that flow is respectively 25sccm and 50sccm
4And C
3H
8, carry out the growth 36min of 3C-SiC hetero epitaxy film; Then at H
2The lower room temperature that progressively is cooled to of protection.
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 1, and silica tube is placed resistance furnace 2; Passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, silica tube is carried out emptying 10 minutes, with air 4 discharges from the air outlet; Open again the resistance furnace power switch, be warming up to 1050 ℃, make silica tube therein also be heated to 1050 ℃.
Step F: in silica tube, pass into 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: resistance furnace temperature is risen to 1100 ℃, in silica tube, pass into the Ar gas that flow velocity is 25sccm, the carbon film that generates is carried out 25 minutes annealing, to reconstitute Graphene.
Claims (4)
1. one kind based on 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 of 4-12 inch carried 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 950 ℃-1150 ℃ of carbonization temperatures in the situation of protection, pass into the C that flow is 30sccm
3H
8, substrate is carried out carbonization 3-7min, growth one deck carburization zone;
(4) be warming up to rapidly 1150 ℃-1300 ℃ of growth temperatures, pass into C
3H
8And SiH
4, carry out the growth of 3C-SiC hetero epitaxy film, the time is 36-60min, then at H
2Protection is lower progressively to be cooled to room temperature, finishes the growth of 3C-SiC epitaxial film;
(5) the good 3C-SiC print of will growing places silica tube, is heated to 700-1050 ℃;
(6) in silica tube, pass into 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 carbon film print that generates being placed Ar gas is 1000-1100 ℃ of lower annealing 10-25 minute in temperature, makes carbon film reconstitute Graphene.
2. according to claim 1 based on Cl
2The big area graphene preparation method of reaction is characterized in that the described SiH that passes into of step (4)
4And C
3H
8, its flow is respectively 15-25sccm and 30-50sccm.
3. according to claim 1 based on Cl
2The big area graphene preparation method of reaction is characterized in that described Ar gas and the Cl that passes into of step (6)
2Gas, its flow velocity is respectively 95-98sccm and 5-2sccm.
4. according to claim 1 based on Cl
2The big area graphene preparation method of reaction, the flow velocity of Ar gas is 25-100sccm when it is characterized in that described step (7) annealing.
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| CN102583329B (en) * | 2012-01-03 | 2013-08-14 | 西安电子科技大学 | Preparation method for large-area graphene based on Cu film auxiliary annealing and Cl2 reaction |
| CN102701789B (en) * | 2012-05-23 | 2013-10-16 | 西安电子科技大学 | Method for forming 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 |
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Non-Patent Citations (6)
| Title |
|---|
| Nanostructured Carbon Coatings on Silicon Carbide:Experimental and Theoretical Study;Yury Gogotsi,et al.;《Functional Gradient Materials and Surface Prepared by Fine Particles Technology》;20011231;第16卷;第239-255页。 * |
| Yury Gogotsi,et al..Nanostructured Carbon Coatings on Silicon Carbide:Experimental and Theoretical Study.《Functional Gradient Materials and Surface Prepared by Fine Particles Technology》.2001,第16卷第239-255页。. |
| 刘忠良.碳化硅薄膜的外延生长、结构表征及石墨烯的制备.《中国博士学位论文全文数据库》.2009,摘要，第40-48、92-99页。. |
| 碳化硅外延石墨烯以及分子动力学模拟研究;詹晓伟;《中国优秀硕士学位论文全文数据库》;20110629;摘要，第29-40页。 * |
| 碳化硅薄膜的外延生长、结构表征及石墨烯的制备;刘忠良;《中国博士学位论文全文数据库》;20090810;摘要，第40-48、92-99页。 * |
| 詹晓伟.碳化硅外延石墨烯以及分子动力学模拟研究.《中国优秀硕士学位论文全文数据库》.2011,摘要，第29-40页。. |
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Effective date of registration: 20180926 Address after: 710065 16, 5 20 zhang84 Road, hi tech Zone, Xi'an, Shaanxi. Patentee after: Shaanxi Semiconductor Pioneer Technology Center Co.,Ltd. Address before: No. 2 Taibai Road, Xi'an, Shaanxi Province, Shaanxi Patentee before: Shaanxi Xi'an electronic large Assets Management Co.,Ltd. Effective date of registration: 20180926 Address after: No. 2 Taibai Road, Xi'an, Shaanxi Province, Shaanxi Patentee after: Shaanxi Xi'an electronic large Assets Management Co.,Ltd. Address before: No. 2 Taibai Road, Xi'an, Shaanxi Province, Shaanxi Patentee before: Xidian University |