CN104195512A - Method for directly growing graphene on dielectric material - Google Patents
Method for directly growing graphene on dielectric material Download PDFInfo
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- CN104195512A CN104195512A CN201410458676.5A CN201410458676A CN104195512A CN 104195512 A CN104195512 A CN 104195512A CN 201410458676 A CN201410458676 A CN 201410458676A CN 104195512 A CN104195512 A CN 104195512A
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Abstract
The invention discloses a method for directly growing graphene on a dielectric material. The method comprises the following steps: evaporating small molecules of aromatic hydrocarbon to a silicon dioxide silicon wafer by virtue of a thermal-resistance evaporation method to form a precursor layer; evaporating copper to the surface, back on to the silicon wafer, of the precursor layer to form a copper layer through electron beam evaporation; placing the sample into a tubular furnace, introducing 200sccm of argon, maintaining the pressure at 10mtorr, raising the temperature and annealing for 15 minutes, under the catalytic action of the copper layer, annealing at a high temperature of 600-1000 DEG C and converting the formed precursor layer into the graphene layer, wherein the small molecules of aromatic hydrocarbon are one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene and N, N'-diphenyl -N, N'-(1-naphthyl) -1,1'-biphenyl-4,4'-diamine. Since the graphene directly grows on the substrate, the operations such as transfer are avoided, the growth temperature of the graphene is reduced, and the forbidden bands of the graphene are opened so that the graphene is changed into a semiconductor material.
Description
Technical field
The present invention relates to a kind of method of growing graphene, belong to Graphene technical field.
Background technology
Graphene has high breaking tenacity and Young's modulus, great specific surface area, and outstanding electroconductibility and optical property, can be widely used in photovoltaic cell, semiconducter device, sensor numerous areas.
At present, the method for synthesizing graphite alkene mainly comprises: micromechanics stripping method, chemistry redox, organic synthesis, epitaxy and chemical vapour deposition etc. are several.The method is to make (Cu, Ni, Fe etc.) catalyzer with metal, does carbon source at high temperature descend growing graphene with methane or acetylene, and the Graphene quality growing can compare favourably with natural flake graphite, has therefore been subject to extensive concern.But the Graphene that the method is synthesized conventionally need to be transferred in dielectric substrate and just can be applied to the fields such as photovoltaic cell, semiconducter device.
Before the present invention, work is in the past mainly to shift Graphene with organic polymer, but comparatively complicated difficult is to obtain the continuous Graphene of big area for the process shifting, and the organic polymer of transfer is difficult to be removed completely, reduced the quality of Graphene.Therefore, there are some researchs to attempt directly growing graphene in substrate, save transfer step.For example, the people such as Zhang gradually vapor away Cu as carbon source by continuous heating with methane, thus by Graphene direct growth to quartz plate.The people such as Lee are spun to SiO by organic polymer
2upper, then plate layer of metal Ni, after heat growth, Ni layer is above etched away, thereby Graphene direct growth is arrived to SiO
2on.But these methods cannot grow the continuous Graphene of big area, and growth temperature too high (approximately 1000 ℃), limited its use.
Summary of the invention
The object of the invention be to provide a kind of on dielectric materials the method for direct growth Graphene, the method to substrate, is avoided the operations such as transfer by Graphene direct growth, has reduced the growth temperature of Graphene, also open the forbidden band of Graphene simultaneously, made Graphene become semiconductor material.
For achieving the above object, the technical solution used in the present invention is: a kind of on dielectric materials the method for direct growth Graphene, comprise the following steps:
Step 1, surface there is is the silicon chip of the silicon-dioxide of 300 nanometer thickness use respectively ethanol, acetone and deionized water ultrasonic cleaning;
Step 2, the small molecules of Powdered aromatic hydrocarbon is positioned in crucible and is evaporated its evaporation is formed to precursor layer to the silicon chip of silicon-dioxide by thermal resistance, the small molecules of described fragrant hydrocarbon is 2,3,6,7,10,11-six cyano group-Isosorbide-5-Nitrae, 5,8,9,12-, six azepine benzophenanthrenes, N, N'-phenylbenzene-N, N'-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines;
Step 3, by electron beam evaporation, thereby copper evaporation is formed to copper layer to precursor layer surface again;
Step 4, sample is put in tube furnace, passed into the argon gas of 200sccm, maintenance pressure is 10mtorr, and the annealing 15 minutes that heats up, under the katalysis of copper layer and at 600～1000 ℃ of high temperature annealings, changes formation precursor layer into graphene layer;
Step 5: will in the silicon chip after the annealing through step 4, the copper layer as catalyzer be etched away, thereby expose graphene layer at the silicon chip surface of silicon-dioxide.
In technique scheme, further improved plan is as follows:
1. in such scheme, the thickness of described precursor layer is 5 ~ 10 nanometers.
2. in such scheme, the thickness of described copper layer is 100 ~ 300 nanometers.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect:
The present invention is directed to that Graphene that current chemical Vapor deposition process grows need to shift and the shortcoming such as growth temperature comparatively high temps high energy consumption is large, by small molecules evaporation in the middle of substrate and catalyzer, by high temperature annealing and etching, thereby by Graphene direct growth to substrate, avoid the operations such as transfer, directly in dielectric base, grow the continuous Graphene of big area; Secondly, select aromatic hydrocarbon small molecules as carbon source, to reduce the growth temperature of Graphene, reduced energy consumption, also for Graphene direct growth provides possibility to the substrate of low melting point; Secondly, in growing graphene, also carried out nitrogen doping, thereby the forbidden band of having opened Graphene makes Graphene become semiconductor material simultaneously.
Accompanying drawing explanation
Accompanying drawing 1 is the method flow diagram of the present invention's direct growth Graphene on dielectric materials.
Accompanying drawing 2 is the graphite Raman spectrum that different thickness presoma grows;
Accompanying drawing 3 is the graphite Raman spectrum that different thickness copper layer growth goes out.
In above accompanying drawing: 1, silicon dioxide layer; 2, silicon chip; 3, precursor layer; 4, copper layer; 5, graphene layer.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: a kind of on dielectric materials the method for direct growth Graphene, comprise the following steps:
Step 1, surface there is is the silicon chip of the silicon-dioxide of 300 nanometer thickness use respectively ethanol, acetone and deionized water ultrasonic cleaning;
Step 2, by the small molecules of Powdered aromatic hydrocarbon 2,3,6,7,10,11-six cyano group-Isosorbide-5-Nitrae, 5,8,9,12-, six azepine benzophenanthrenes are positioned in crucible and are evaporated its evaporation is formed to precursor layer to the silicon chip of silicon-dioxide by thermal resistance;
Step 3, by electron beam evaporation, thereby copper evaporation is formed to copper layer to precursor layer surface again;
Step 4, sample is put in tube furnace, passed into the argon gas of 200sccm, maintenance pressure is 10mtorr, and the annealing 15 minutes that heats up, under the katalysis of copper layer and 800 ℃ of high temperature annealings 30 minutes, changes the precursor layer of formation into graphene layer;
Step 5: will in the silicon chip after the annealing through step 4, the copper layer as catalyzer be etched away, thereby expose graphene layer at the silicon chip surface of silicon-dioxide.
The thickness of above-mentioned precursor layer is 5 nanometers, and accompanying drawing 2 is Raman spectrums of the Graphene that obtains of different thickness precursor, and when precursor thickness is 5 nanometer as we know from the figure, the Graphene defect obtaining is less, and is single-layer graphene; The thickness of above-mentioned copper layer is 200 nanometers, accompanying drawing 3 is Raman spectrums of the Graphene that obtains of different Cu layer thickness, as we know from the figure when the thickness of copper layer is less than or equal to 100 nanometer, the Graphene defect obtaining is more, when copper layer thickness is 200 nanometer, the defect of Graphene is obviously less, and the quality of Graphene is better.
Embodiment 2: a kind of on dielectric materials the method for direct growth Graphene, comprise the following steps:
Step 1, surface there is is the silicon chip of the silicon-dioxide of 300 nanometer thickness use respectively ethanol, acetone and deionized water ultrasonic cleaning;
Step 2, by the small molecules N of Powdered aromatic hydrocarbon, N'-phenylbenzene-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines is positioned in crucible and is evaporated its evaporation is formed to precursor layer to the silicon chip of silicon-dioxide by thermal resistance;
Step 3, by electron beam evaporation, thereby copper evaporation is formed to copper layer to precursor layer surface again;
Step 4, sample is put in tube furnace, passed into the argon gas of 200sccm, maintenance pressure is 10mtorr, and the annealing 15 minutes that heats up, under the katalysis of copper layer and 1000 ℃ of high temperature annealings 30 minutes, changes the precursor layer of formation into graphene layer;
Step 5: will in the silicon chip after the annealing through step 4, the copper layer as catalyzer be etched away, thereby expose graphene layer at the silicon chip surface of silicon-dioxide.
The thickness of above-mentioned precursor layer is 5 nanometers; The thickness of above-mentioned copper layer is 200 nanometers.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (3)
1. a method for direct growth Graphene on dielectric materials, is characterized in that: comprise the following steps:
Step 1, surface there is is the silicon chip of the silicon-dioxide of 300 nanometer thickness use respectively ethanol, acetone and deionized water ultrasonic cleaning;
Step 2, the small molecules of Powdered aromatic hydrocarbon is positioned in crucible and is evaporated its evaporation is formed to precursor layer to the silicon chip of silicon-dioxide by thermal resistance, the small molecules of described fragrant hydrocarbon is 2,3,6,7,10,11-six cyano group-Isosorbide-5-Nitrae, 5,8,9,12-, six azepine benzophenanthrenes, N, N'-phenylbenzene-N, N'-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines;
Step 3, by electron beam evaporation, thereby copper evaporation is formed to copper layer to precursor layer surface again;
Step 4, sample is put in tube furnace, passed into the argon gas of 200sccm, maintenance pressure is 10mtorr, and the annealing 15 minutes that heats up, under the katalysis of copper layer and at 600～1000 ℃ of high temperature annealings, changes formation precursor layer into graphene layer;
Step 5: will in the silicon chip after the annealing through step 4, the copper layer as catalyzer be etched away, thereby expose graphene layer at the silicon chip surface of silicon-dioxide.
2. the method for direct growth Graphene according to claim 1, is characterized in that: the thickness of described copper layer is 100 ~ 300 nanometers.
3. the method for direct growth Graphene according to claim 1, is characterized in that: the thickness of described precursor layer is 5 ~ 10 nanometers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109052377A (en) * | 2018-10-25 | 2018-12-21 | 济南大学 | A kind of preparation method of large-area graphene |
| CN111326310A (en) * | 2020-02-24 | 2020-06-23 | 上海景瑞阳实业有限公司 | High-temperature-resistant samarium-cobalt permanent magnet and preparation method thereof |
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| CN102102215A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Method for preparing graphene and diamond-like carbon composite film |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
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| CN102102215A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Method for preparing graphene and diamond-like carbon composite film |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052377A (en) * | 2018-10-25 | 2018-12-21 | 济南大学 | A kind of preparation method of large-area graphene |
| CN109052377B (en) * | 2018-10-25 | 2020-05-22 | 济南大学 | Preparation method of large-area graphene |
| CN111326310A (en) * | 2020-02-24 | 2020-06-23 | 上海景瑞阳实业有限公司 | High-temperature-resistant samarium-cobalt permanent magnet and preparation method thereof |
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Application publication date: 20141210 |