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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003989 dielectric material Substances 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 150000003384 small molecules Chemical class 0.000 claims abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical group C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000137 annealing Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 2
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 claims 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 238000001237 Raman spectrum Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDOKHBNNNHBVNJ-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12.N1C=CC=CC=C1 Chemical class C1=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12.N1C=CC=CC=C1 KDOKHBNNNHBVNJ-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开一种在介电材料上直接生长石墨烯的方法，包括以下步骤：通过热阻蒸发将芳香烃的小分子蒸镀到二氧化硅的硅片上形成前驱物层，所述香烃的小分子为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲、N,N'-二苯基-N,N'-（1-萘基）-1,1'-联苯-4,4'-二胺中的一种；再通过电子束蒸发将铜蒸镀到前驱物层与硅片相背的表面上从而形成铜层；将样品放入到管式炉中，通入200sccm的氩气，保持压力为10mtorr，升温退火15分钟，在铜层的催化作用下且在600～1000℃高温退火，将形成前驱物层转变为石墨烯层。本发明将石墨烯直接生长到基底上，避免转移等操作，降低了石墨烯的生长温度，也打开了石墨烯的禁带，使得石墨烯变为半导体材料。
The invention discloses a method for directly growing graphene on a dielectric material, comprising the following steps: vapor-depositing small molecules of aromatic hydrocarbons on a silicon wafer of silicon dioxide by thermal resistance evaporation to form a precursor layer, the aromatic hydrocarbons The small molecules are 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, N,N'-diphenyl-N, One of N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine; then copper is evaporated onto the surface of the precursor layer opposite the silicon wafer by electron beam evaporation to form a copper layer; put the sample into a tube furnace, pass in 200 sccm of argon gas, keep the pressure at 10mtorr, heat up and anneal for 15 minutes, under the catalytic action of the copper layer and anneal at a high temperature of 600-1000°C, the Formation of the precursor layer transforms into a graphene layer. The invention directly grows the graphene on the substrate, avoids operations such as transfer, reduces the growth temperature of the graphene, and opens the forbidden band of the graphene, so that the graphene becomes 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.
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Cited By (2)
| 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 |
| 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 |
Citations (2)
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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 |
-
2014
- 2014-09-10 CN CN201410458676.5A patent/CN104195512A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 卓其奇: "石墨烯及其金属复合物的合成与应用", 《万方数据 企业知识服务平台》 * |
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 | 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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