CN103183336A - Preparation method of large-area graphene on Si substrate based on Ni film annealing - Google Patents
Preparation method of large-area graphene on Si substrate based on Ni film annealing Download PDFInfo
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Abstract
The invention discloses a preparation method of large-area graphene on an Si substrate based on Ni film annealing and mainly solves the problems of small area, poor continuity and non-uniform layers of graphene prepared in the prior art. The preparation method comprises the following implementation steps: growing a carburization layer on the 4-12-inch Si substrate to be used as a transition and growing a 3C-SiC heteroepitaxial film at the temperature of 1200 DEG C to 1350 DEG C by utilizing growth gas sources C3H8 and SiH4; carrying out hydrogen etching on the grown 3C-SiC film and removing a compound generated by etching; reacting 3C-SiC with gaseous CCl4 at a temperature of 800-1,000 DEG C to generate a carbon film; electron beam-depositing an Ni film on the carbon film, putting a sample sheet plated with the Ni film into Ar gas and annealing for 10-20 minutes at a temperature of 1,000-1,250 DEG C to generate a graphene sample sheet; and finally removing the Ni film from the graphene sample sheet. The graphene prepared by the method has the advantage that the area can reach 12 inches, the continuity is good, the surface is smooth, and the porosity is low. The graphene can be used for manufacturing microelectronic devices and biological sensors or sealing gas and liquid.
Description
Technical field
The invention belongs to microelectronics technology, relate to a kind of semiconductor material and preparation method thereof, specifically be based on big area graphene preparation method on the Si substrate of Ni film annealing.
Technical background
Graphene is a kind of carbonaceous novel material of the cellular crystalline network of the tightly packed Cheng Erwei of carbon atom, is to construct sp such as zero dimension soccerballene, one dimension carbon nanotube, said three-dimensional body phase graphite
2Hydridization carbon, namely carbon links to each other with two keys or connects the basic structural unit of other atoms, has some special physical propertys, comprising: unique current carrier characteristic; Electronics transport resistance in Graphene is very little, does not have scattering in submicron when mobile, has good electric transmission character; Mechanical property is good, good toughness, and the peak pressure that bears on every 100nm distance can reach 2.9N; The distinctive energy band structure of Graphene is separated from each other hole and electronics, causes the generation of new electronic conduction phenomenon, as quantum Interference, and irregular quantum hall effect etc.The history in existing more than 60 year of the theoretical investigation of Graphene, but until 2004, the physicist An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu, utilizing the method for the high oriented graphite of tape stripping to obtain really can self-existent two-dimentional Graphene crystal.And found the relativistic particles characteristic of Graphene current carrier, just cause Graphene research heat.After this, the novel method of preparation Graphene emerges in an endless stream, and it is found that, the field of Graphene band people suitability for industrialized production is come within a measurable distance.
The application of Graphene
(1) replace silicon to be used for electronic product
Silicon allows people march toward digital times, but the researchist still thirsts for finding some novel materials, makes unicircuit littler, faster, more cheap.In numerous alternative materials, Graphene adds noticeable fully.The superstrength of Graphene, light transmission and superpower electroconductibility make it to become the ideal material of making flexible display equipment and ultra-high speed electron device.Nowadays Graphene has appeared in the middle of the prototype hardware of novel transistor, storer and other devices.Fast tens times than silicon of the speed that Graphene transports electronics, thereby get faster, more power saving with the transistor work that Graphene is made.
(2) be used for photon sensor
As if Graphene also can be used for photon sensor, and this sensor is for detection of the information of carrying in the optical fiber, and now, this role is also being taken on by silicon, but the epoch of silicon will finish.In October, 2010, the research group of IBM has disclosed the Graphene photodetector of their development first.The researchist of univ cambridge uk and French CNR has produced ultrafast locked mode Graphene laser apparatus, and this achievement in research has shown that Graphene is well worth doing at photoelectric device.
(3) be used for nanometer electronic device
Graphene is the ideal material of nanometer circuit, and wherein, the high conduction Graphene is a kind of semiconductor material of excellent performance, is to be applied in the future the material that the tool of nano electron device is wished.BASF and Wal Baker Co., Ltd have developed the high conduction Graphene that is used for conductive coating, and this will pave the way for the commercialization that Graphene is used in electronic industry.
(4) be used for solar cell
Transparent graphene film can be made into good solar cell.U.S. Lu Tege university develops a kind of technology of making transparent graphene film, and the graphene film of manufacturing has only several centimetres wide, l～5nm thick, can be used for organic solar batteries; The researchist of American South University of California has been used for Graphene to make organic photovoltaic cell.Graphene organic solar batteries cost is low, and snappiness is good, so good its application prospect of researchist, and for example this Graphene organic solar batteries can be made the family expenses curtain, even can make the clothes that can generate electricity.
(5) other application
Graphene has surmounted carbon nanotube aspect reinforced composite.3 recent studies on achievements that the investigator of U.S. Rensselaer Polytech Inst delivers show that Graphene can be used for making the reinforced composite of wind turbine and aircraft wing.In addition, Graphene can be used as sorbent material, support of the catalyst, heat transfer medium, also can be applied aspect biotechnology.
Preparation method of graphene
Preparation method of graphene mainly contains 2 kinds of mechanical process and chemical methods.
Mechanical process comprises micromechanics partition method, epitaxy method and heating silicon carbide method. chemical method comprises chemical reduction method and chemical cleavage method etc.The micromechanics partition method is directly graphene platelet to be cut down from bigger crystal, can obtain high-quality Graphene, and cost is low.But shortcoming is that the graphene platelet size is wayward.Can't produce the big area graphite flake sample for practical application reliably, be not suitable for volume production.The epitaxy method is to utilize growth matrix atomic structure " kind " to go out Graphene, and the Graphene performance is satisfactory, but often in uneven thickness.Heating silicon carbide method can controllably be prepared the single or multiple lift Graphene, be a kind of very novel, to realizing the very important preparation method of practical application of Graphene, but the Graphene that the preparation big area has single thickness difficulty relatively.
Chemical reduction method can low-cost prepare, but is difficult to the high-quality graphene platelet that preparation does not have crystal boundary.The chemistry cleavage method is to utilize graphite oxide to prepare the method for Graphene by the thermal reduction method, is a kind of important graphene preparation method.Chemical Vapor deposition process provides a kind of effective ways of controlled preparation Graphene, and its great advantage is to prepare the bigger graphene film of area. and shortcoming is at high temperature to finish, and in making processes, graphene film might form defective.And improved microwave plasma CVD method, its treatment temp is lower, has only about 400 ℃, but still is unsuitable for volume production.
In view of Graphene has broad application prospects and has the limitation of Graphene technology of preparing now, the Graphene of preparation big area, high quality, low defective has become a major issue that needs to be resolved hurrily.
Summary of the invention
The objective of the invention is to avoid the deficiency of above-mentioned prior art, propose a kind of based on big area graphene preparation method on the Si substrate of Ni film annealing, to improve surperficial continuity and slickness, reduction porosity, to reduce cost, be 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) cleans: clean with the mixing solutions of mixing solutions, hydrochloric acid and the hydrogen peroxide of ammoniacal liquor and the hydrogen peroxide Si substrate to 4 cun～12 cun successively;
(2) vacuumize: the Si substrate after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank;
(3) growth carburization zone: at H
2Progressively be warming up to 1000 ℃～1200 ℃ of carbonization temperatures under the situation of protection, feeding flow is the C of 30ml/min
3H
8, substrate is carried out carbonization 4min～8min, growth one deck carburization zone;
(4) extension 3C-SiC film: be warming up to 1200 ℃～1350 ℃ of 3C-SiC growth temperatures rapidly, feed C
3H
8And SiH
4, carry out 3C-SiC hetero epitaxy growth for Thin Film, the time is 30min～60min, then at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film;
(5) hydrogen etching:
5.1) the good 3C-SiC print of will growing puts into the Graphene growth apparatus, opens heating power supply, the hydrogen etching is carried out to the 3C-SiC substrate, to remove cut and the defective of 3C-SiC substrate surface in reacting by heating chamber to 1600 ℃;
5.2) remove the compound that the hydrogen etch step generates;
(6) generate carbon film: adjust heating power supply voltage, making reaction chamber temperature is 800 ℃～1000 ℃, and open gas valve this moment, with Ar gas and CCl
4Gas feeds mixing chamber, after fully mixing, mixed gas is entered in the silica tube reaction chamber via gas passage, makes CCl
43C-SiC reaction 30min～120min in steam and the reaction chamber generates carbon film;
(7) deposition Ni film: the print that will generate carbon film takes out from growth apparatus, puts into electron-beam evaporation equipment, the thick Ni film of carbon film deposition one deck 400nm～600nm that is generating;
(8) reconstruct Graphene: the carbon film print that will deposit the Ni film is put into the Graphene growth apparatus again, intensification degree to 1000 ℃～1250 ℃ also feeds Ar gas annealing 10min～20min, make the carbon film under the covering of Ni film reconstitute Graphene, obtain the Graphene print;
(9) remove the Ni film: the Graphene print is placed HCl and CuSO
4To remove the Ni film, obtain grapheme material in the solution.
The present invention compared with prior art has following advantage:
1. the present invention anneals at the Ni film owing to utilizing, thereby the Graphene continuity that generates is better.
2. the present invention is owing to utilize 3C-SiC and CCl
4Gas reaction, thereby the Graphene smooth surface that generates, porosity is low.
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.
Description of drawings
Fig. 1 is the intention of Graphene growth apparatus of the present invention;
Fig. 2 is the schema that the present invention prepares Graphene.
Embodiment
With reference to Fig. 1, Graphene growth apparatus of the present invention is mainly by the silica tube reaction chamber, electromagnetic heating coil, and heating power supply, gas passage, mixing chamber and a plurality of gas valve are formed.Gas flows into mixing chamber by gas valve control, evenly mixes flowing into the silica tube reaction chamber through gas passage in mixing chamber again.To the heating of silica tube reaction chamber, heating power supply is used for regulating heating power with electromagnetic heating coil.In the process of growth, print is placed on the sample table of reaction chamber.
With reference to Fig. 2, making method of the present invention provides following three kinds of embodiment.
Embodiment 1, at the grapheme material of 4 cun Si substrate preparations based on the annealing of Ni film.
The first step: the mixing solutions with mixing solutions, hydrochloric acid and the hydrogen peroxide of ammoniacal liquor and hydrogen peroxide cleans 4 cun Si substrates successively.
(1.1) according to NH
4OH:H
2O
2: H
2The ratio obtain solution of O=1:2:5 places this solution with 4 cun Si substrates, soaks 10 minutes, and washes the back oven dry repeatedly with deionized water, to remove the sample surfaces organic residue;
(1.2) according to HCl:H
2O
2: H
2The ratio obtain solution of O=1:2:8 places this solution with 4 cun Si substrates behind the surperficial organic residue of removal, soaks 10 minutes, washes the back oven dry repeatedly with deionized water, to remove ionic contamination.
Second step: vacuumize.
The Si substrate is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
The 3rd step: growth carburization zone.
At H
2Under the condition of protection reaction chamber temperature is risen to 1000 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30ml/min
3H
8, at Si substrate growth one deck carburization zone, growth time is 8min.
The 4th step: at carburization zone growth 3C-SiC epitaxial film.
Reaction chamber temperature is risen to 1200 ℃ of growth temperatures rapidly, feed the SiH that flow is respectively 25ml/min
4With flow be the C of 50ml/min
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, finishes the growth of 3C-SiC epitaxial film.
The 5th step: the good 3C-SiC film of growing is carried out the hydrogen etching processing, and remove the Si compound that generates.
(5.1) the good 3C-SiC print of will growing is put into the Graphene growth apparatus, opens heating power supply, and gas valve is opened in reacting by heating chamber to 1600 ℃, and feeding flow is the H of 70L/min
2, the 3C-SiC substrate is carried out 30min hydrogen etching, to remove cut and the defective of 3C-SiC substrate surface;
(5.2) finish the hydrogen etching after, regulate heating power supply voltage, be cooled to 1000 ℃, the hydrogen that feeds flow and be 2L/min kept 15 minutes; Then be cooled to 850 ℃, feeding flow is the SiH of 0.4ml/min
4, kept 10 minutes; Stop ventilation then, be warming up to 1000 ℃, kept 10 minutes; Be warming up to 1100 ℃ at last, kept 10 minutes, to remove the compound that is attached to 3C-SiC surface Si that the hydrogen etching generates.
The 6th step: growth carbon film.
Regulate heating power supply voltage, make temperature reduce to 800 ℃, open gas valve this moment, with Ar gas and CCl
4Gas enters in the reaction chamber through gas passage after feeding and mixing in the mixing chamber, and the Ar airshed is 40ml/min, CCl
4Gas flow is 1ml/min, makes CCl
4With 3C-SiC reaction 30min, generate carbon film.
The 7th step: at carbon film plating layer of Ni film.
The print that generates carbon film is taken out from the Graphene growth apparatus, put on the substrate slide glass of electron beam evaporation deposition machine, it is 50cm to the distance of target that substrate is set, and reaction chamber pressure is evacuated to 5 * 10
-4Pa, the adjusting line is 40mA, evaporation 15min is at the thick Ni film of carbon film deposition one deck 400nm.
The 8th step: reconstitute Graphene.
The print that deposits the Ni film is placed in the Graphene growth apparatus, is heated to 1000 ℃, feeding flow velocity is the Ar gas of 30ml/min, carries out 20 minutes anneal, makes the carbon film under the covering of Ni film reconstitute continuous Graphene, obtains the Graphene print.
The 9th step: remove the Ni film and obtain grapheme material.
Place the mixing solutions of hydrochloric acid and copper sulfate to remove the Ni film print that generates Graphene, obtain grapheme material.
Embodiment 2, at the grapheme material of 8 cun Si substrate preparations based on the annealing of Ni film.
The 1st step: the mixing solutions with mixing solutions, hydrochloric acid and the hydrogen peroxide of ammoniacal liquor and hydrogen peroxide cleans 8 cun Si substrates successively.
Cleaning step is identical with the first step among the embodiment 1.
The 2nd step: vacuumize.
The Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
The 3rd step: growth carburization zone.
At H
2Under the situation of protection reaction chamber temperature is risen to 1100 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30ml/min
3H
8, at Si substrate growth one deck carburization zone, growth time is 6min.
The 4th step: at carburization zone growth 3C-SiC epitaxial film.
Reaction chamber temperature is risen to 1300 ℃ of growth temperatures rapidly, feed the SiH that flow is respectively 30ml/min and 60ml/min
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, finishes the growth of 3C-SiC epitaxial film.
The 5th step: the good 3C-SiC film of growing is carried out the hydrogen etching processing, and remove the Si compound that generates.
(5.1) the good 3C-SiC print of will growing is put into the Graphene growth apparatus, opens heating power supply, and gas valve is opened in reacting by heating chamber to 1600 ℃, and feeding flow is the H of 90L/min
2, the 3C-SiC substrate is carried out 40min hydrogen etching, to remove cut and the defective of 3C-SiC substrate surface;
(5.2) finish the hydrogen etching after, regulate heating power supply voltage, be cooled to 1000 ℃, the hydrogen that feeds flow and be 3L/min kept 15 minutes; Then be cooled to 850 ℃, feeding flow is the SiH of 0.8ml/min
4, kept 10 minutes; Stop ventilation then, be warming up to 1000 ℃, kept 10 minutes; Be warming up to 1100 ℃ at last, kept 10 minutes, to remove the compound that is attached to 3C-SiC surface Si that the hydrogen etching generates.
The 6th step: growth carbon film.
Regulate heating power supply voltage, make temperature reduce to 900 ℃, open gas valve this moment, with Ar gas and CCl
4Gas enters in the reaction chamber through gas passage after feeding and mixing in the mixing chamber, and the Ar airshed is 60ml/min, CCl
4Gas flow is 3ml/min, makes CCl
4With 3C-SiC reaction 60min, generate carbon film.
The 7th step: at carbon film plating layer of Ni film.
The print that generates carbon film is taken out from the Graphene growth apparatus, put on the substrate slide glass of electron beam evaporation deposition machine, it is 50cm to the distance of target that substrate is set, and reaction chamber pressure is evacuated to 5 * 10
-4Pa, the adjusting line is 40mA, evaporation 25min is at the thick Ni film of carbon film deposition one deck 500nm.
The 8th step: reconstitute Graphene.
The print that deposits the Ni film is placed in the Graphene growth apparatus, is heated to 1150 ℃, feeding flow velocity is the Ar gas of 60ml/min, carries out 15 minutes anneal, makes the carbon film under the covering of Ni film reconstitute continuous Graphene, obtains the Graphene print.
The 9th step: remove the Ni film and obtain grapheme material.
Place the mixing solutions of hydrochloric acid and copper sulfate to remove the Ni film print that generates Graphene, obtain grapheme material.
Embodiment 3, at the grapheme material of 12 cun Si substrate preparations based on the annealing of Ni film.
Step 1: the mixing solutions with mixing solutions, hydrochloric acid and the hydrogen peroxide of ammoniacal liquor and hydrogen peroxide cleans 12 cun Si substrates successively.
Cleaning step is identical with the first step among the embodiment 1.
Step 2: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
Step 3: 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 30ml/min
3H
8, continue 4min, with one deck carburization zone of growing at the Si substrate.
Step 4: reaction chamber temperature is risen to 1350 ℃ of growth temperatures rapidly, feed the SiH that flow is 35ml/min respectively
4With flow be the C of 70ml/min
3H
8, carry out the 3C-SiC hetero epitaxy film growth of 30min; Then at H
2Protection progressively is cooled to room temperature down.
Step 5:
5a) the good 3C-SiC print of will growing is put into the Graphene growth apparatus, opens heating power supply, and gas valve is opened in reacting by heating chamber to 1600 ℃, and feeding flow is the H of 100L/min
2, the 3C-SiC substrate is carried out 50min hydrogen etching, to remove cut and the defective of 3C-SiC substrate surface;
5b) finish the hydrogen etching after, regulate heating power supply voltage, be cooled to 1000 ℃, the hydrogen that feeds flow and be 4L/min kept 15 minutes; Then be cooled to 850 ℃, feeding flow is the SiH of 1.2ml/min
4, kept 10 minutes; Stop ventilation then, be warming up to 1000 ℃, kept 10 minutes; Be warming up to 1100 ℃ at last, kept 10 minutes, to remove the compound that is attached to 3C-SiC surface Si that the hydrogen etching generates.
Step 6: regulate heating power supply voltage, make temperature reduce to 1000 ℃, open gas valve this moment, with Ar gas and CCl
4Gas enters in the reaction chamber through gas passage after feeding and mixing in the mixing chamber, and the Ar airshed is 80ml/min, CCl
4Gas flow is 5ml/min, makes CCl
4With 3C-SiC reaction 120min, generate carbon film.
Step 7: the print that will generate carbon film takes out from the Graphene growth apparatus, puts on the substrate slide glass of electron beam evaporation deposition machine, and it is 50cm to the distance of target that substrate is set, and reaction chamber pressure is evacuated to 5 * 10
-4Pa, the adjusting line is 40mA, evaporation 35min is at the thick Ni film of carbon film deposition one deck 600nm.
Step 8: the print that will deposit the Ni film is placed in the Graphene growth apparatus, is heated to 1250 ℃, and feeding flow velocity is the Ar gas of 90ml/min, carries out 10 minutes anneal, makes the carbon film under the covering of Ni film reconstitute continuous Graphene, obtains the Graphene print.
Step 9: the print that will generate Graphene places the mixing solutions of hydrochloric acid and copper sulfate to remove the Ni film, obtains grapheme material.
Claims (8)
1. one kind based on big area graphene preparation method on the Si substrate of Ni film annealing, may further comprise the steps:
(1) cleans: clean with the mixing solutions of mixing solutions, hydrochloric acid and the hydrogen peroxide of ammoniacal liquor and the hydrogen peroxide Si substrate to 4 cun～12 cun successively;
(2) vacuumize: the Si substrate after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank;
(3) growth carburization zone: at H
2Progressively be warming up to 1000 ℃～1200 ℃ of carbonization temperatures under the situation of protection, feeding flow is the C of 30ml/min
3H
8, substrate is carried out carbonization 4min～8min, growth one deck carburization zone;
(4) extension 3C-SiC film: be warming up to 1200 ℃～1350 ℃ of 3C-SiC growth temperatures rapidly, feed C
3H
8And SiH
4, carry out 3C-SiC hetero epitaxy growth for Thin Film, the time is 30min～60min, then at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film;
(5) hydrogen etching:
5.1) the good 3C-SiC print of will growing puts into the Graphene growth apparatus, opens heating power supply, the hydrogen etching is carried out to the 3C-SiC substrate, to remove cut and the defective of 3C-SiC substrate surface in reacting by heating chamber to 1600 ℃;
5.2) remove the compound that the hydrogen etch step generates;
(6) generate carbon film: adjust heating power supply voltage, making reaction chamber temperature is 800 ℃～1000 ℃, and open gas valve this moment, with Ar gas and CCl
4Gas feeds mixing chamber, after fully mixing, mixed gas is entered in the silica tube reaction chamber via gas passage, makes CCl
43C-SiC reaction 30min～120min in steam and the reaction chamber generates carbon film;
(7) deposition Ni film: the print that will generate carbon film takes out from growth apparatus, puts into electron-beam evaporation equipment, the thick Ni film of carbon film deposition one deck 400nm～600nm that is generating;
(8) reconstruct Graphene: the carbon film print that will deposit the Ni film is put into the Graphene growth apparatus again, intensification degree to 1000 ℃～1250 ℃ also feeds Ar gas annealing 10min～20min, make the carbon film under the covering of Ni film reconstitute Graphene, obtain the Graphene print;
(9) remove the Ni film: place HCl and CuSO4 solution to remove the Ni film Graphene print, obtain grapheme material.
2. according to claim 1ly it is characterized in that in the described step (1) the Si substrate being cleaned based on big area graphene preparation method on the Si substrate of Ni film annealing, carry out as follows:
(1a) use NH
4OH+H
2O
2Reagent soaked the SiC print 10 minutes, took out the back oven dry, to remove print surface organic residue;
(1b) 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 big area graphene preparation method on the Si substrate of Ni film annealing, it is characterized in that the SiH that feeds in the described step (4)
4And C
3H
8, its flow is respectively: SiH
4Flow is 25ml/min～35ml/min, C
3H
8Flow is 50ml/min～70ml/min.
4. according to claim 1 based on big area graphene preparation method on the Si substrate of Ni film annealing, it is characterized in that the processing parameter of hydrogen etching in the described step (5) is: H
2Flow is 70L/min～100L/min, and etching time is 30min～50min.
5. according to claim 1 based on big area graphene preparation method on the Si substrate of Ni film annealing, it is characterized in that removing the compound that the hydrogen etching generates in the described step (5), its key step is:
(5a) finish the hydrogen etching after, be cooled to 1000 ℃, the hydrogen that feeds flow and be 2L/min～4L/min kept 15 minutes;
(5b) be cooled to 850 ℃, feeding flow is the SiH of 0.4ml/min～1.2ml/min
4, kept 10 minutes;
(2c) stop ventilation, be warming up to 1000 ℃, kept 10 minutes;
(2d) be warming up to 1100 ℃, kept 10 minutes.
6. according to claim 1 based on big area graphene preparation method on the Si substrate of Ni film annealing, it is characterized in that Ar gas and CCl in the described step (6)
4Gas, its flow velocity is respectively: Ar gas velocity 40ml/min～80ml/min, CCl
4Gas flow rate 1ml/min～5ml/min.
7. according to claim 1 based on big area graphene preparation method on the Si substrate of Ni film annealing, it is characterized in that electron beam deposition Ni film in the described step (7), to be substrate be made as 50cm to the distance of target to its processing condition, and reaction chamber pressure is made as 5 * 10
-4Pa, line is made as 40mA, and evaporation time is made as 15min～35min.
8. according to claim 1 based on big area graphene preparation method on the Si substrate of Ni film annealing, the flow velocity of Ar gas is 30ml/min～90ml/min when it is characterized in that described step (8) annealing.
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Cited By (5)
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| CN103482622A (en) * | 2013-09-18 | 2014-01-01 | 武汉理工大学 | Preparing method for single-layer graphene film with strong stability and high conductivity |
| CN104477903A (en) * | 2014-12-22 | 2015-04-01 | 上海集成电路研发中心有限公司 | Preparation method of graphene film |
| CN105140102A (en) * | 2015-07-08 | 2015-12-09 | 中国电子科技集团公司第五十五研究所 | Improved method for epitaxial growth of [Beta]-silicon carbide film on silicon substrate |
| CN114797772A (en) * | 2022-04-02 | 2022-07-29 | 中国科学院理化技术研究所 | Adsorption film, preparation method thereof and electric heating adsorption bed for low-temperature system |
| CN115584478A (en) * | 2022-09-27 | 2023-01-10 | 中国电子科技集团公司第五十五研究所 | Preparation method of low-defect-density epitaxial film |
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