CN106283179A - A kind of preparation method of grade monolayer single crystal graphene - Google Patents

A kind of preparation method of grade monolayer single crystal graphene Download PDF

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Publication number
CN106283179A
CN106283179A CN201610588332.5A CN201610588332A CN106283179A CN 106283179 A CN106283179 A CN 106283179A CN 201610588332 A CN201610588332 A CN 201610588332A CN 106283179 A CN106283179 A CN 106283179A
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China
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grade
single crystal
sccm
copper foil
crystal graphene
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CN201610588332.5A
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Chinese (zh)
Inventor
刘金养
徐杨阳
左传东
林丽梅
黄志高
赖***
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Fujian Normal University
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Fujian Normal University
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Priority to CN201610588332.5A priority Critical patent/CN106283179A/en
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements

Abstract

The invention belongs to low-dimension nano material field, be specifically related to the preparation method of a kind of grade monolayer single crystal graphene.Particularly as follows: applied chemistry vapour deposition process (CVD), by optimizing the annealing conditions of Copper Foil, after i.e. Copper Foil carries out long term annealing under an argon atmosphere, form low-density copper oxide nanometer particle on surface；Then pass to CH4And H2, using copper oxide nanometer particle as nucleating point, grade monolayer single crystal graphene can be grown.The method preparation process is simple, is suitable to mass production, has broad application prospects.

Description

A kind of preparation method of grade monolayer single crystal graphene
Technical field
The invention belongs to low-dimension nano material field, be specifically related to the preparation side of a kind of grade monolayer single crystal graphene Method.
Background technology
Graphene is that one is made up of carbon atom, with sp2Hybrid orbital composition hexangle type is the two dimensional crystal of honeycomb lattice, It has attracted the interest of more and more researcher at the excellent properties that power, heat, the aspect such as optical, electrical are had.At present, graphite The preparation method of alkene has a lot, such as mechanical stripping method, oxidation-reduction method, silicon carbide epitaxial growth method, chemical vapour deposition technique Deng.In these methods, chemical vapour deposition technique because of its can preparation of industrialization high-quality, big size graphene and be subject to more to come The most concerns.But the Graphene that conventional chemical vapor sedimentation is prepared on Copper Foil is a kind of polycrystalline structure, there is many Crystal boundary, these defects can be greatly reduced its character such as electron mobility, thermal conductivity, is substantially reduced the correlated performance of Graphene and answers By value.In order to overcome this problem, it is necessary to the crystal boundary of Graphene is decreased or even eliminated, i.e. grow large-sized monocrystalline stone Ink alkene.The present invention uses chemical vapour deposition technique, with CH4For carbon source, H2It is carrier gas with Ar, by optimizing Copper Foil annealing conditions, adjusts Control reacting gas ratio, grows grade monolayer single crystal graphene.This experiment preparation process is simple, can industrialized production, tool Have broad application prospects.
Summary of the invention
Present invention aims to a large amount of crystal boundaries of existence that current chemical vapour deposition technique prepared on Copper Foil etc. lack The deficiencies such as sunken or monocrystalline size is less, it is provided that the preparation method of a kind of grade monolayer single crystal graphene.
First the present invention carries out a surface preparation to Copper Foil, is then further made annealing treatment by hot conditions, Form low-density copper oxide nanometer particle on its surface and as nucleating point, grow grade monolayer list under suitable conditions Brilliant Graphene.This experimentation is simple, it is adaptable to produce high-quality grade monolayer single crystal graphene in enormous quantities.
For achieving the above object, the present invention adopts the following technical scheme that
The preparation method of a kind of grade monolayer single crystal graphene, concretely comprises the following steps:
1) substrate annealing: Copper Foil is put into tube furnace quartz ampoule, is passed through 300 sccm Ar, is warming up under an argon atmosphere 1070 DEG C, and carry out at such a temperature making annealing treatment 2 ~ 6 h；
2) growth: after copper foil annealing, be passed through 0.5 sccm CH4With 50 sccm H2Carrying out growing 2 h, this process keeps tubular type The temperature of stove is 1070 DEG C；
3) cooling: open tube furnace, fast cooling, and be passed through 300 sccm Ar and 4 sccm H2, room temperature to be down to i.e. grows Go out grade monolayer single crystal graphene.
Before tube furnace quartz ampoule put into by Copper Foil in step 1), need to first carry out pretreatment；Described pretreatment is: use shears Copper foil shearing is become suitable size, puts it into and dilute hydrochloric acid carries out ultrasonic cleaning, be then transferred in acetone soln ultrasonic clearly Wash, clean and dry up with nitrogen after terminating, stand-by.
The beneficial effects of the present invention is:
The present invention uses chemical vapour deposition technique, with CH4For carbon source, H2It is carrier gas with Ar, by optimizing Copper Foil annealing conditions, adjusts Control reacting gas ratio, grows mobility and is up to 2600cm-2V-1s-1Grade monolayer single crystal graphene.Prepared by this experiment Journey is simple, can industrialized production, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is Graphene nucleation density and annealing time graph of relation；
The photo of Fig. 2 grade monolayer single crystal graphene and microphotograph；
The Raman spectrum of Fig. 3 grade monolayer single crystal graphene；
The I-V characteristic of Fig. 4 field-effect transistor based on grade monolayer single crystal graphene (long 4.80um, wide 0.16um) and Transfer characteristic curve (VDS=0.1V).
Detailed description of the invention
For the openest rather than restriction present invention, below in conjunction with example, the present invention is described in further detail.
Embodiment 1
The preparation method of grade monolayer single crystal graphene, concretely comprises the following steps:
1) rectangular shape that a size of 2.5cm*2.5cm size will be cut into as the Copper Foil of growing substrate；
2) Copper Foil of well cutting is put into ultrasonic cleaning in dilute hydrochloric acid, be then transferred in acetone soln carry out ultrasonic cleaning, clearly Dry up with nitrogen after washing end；
3) Copper Foil is put into the quartz ampoule of tube furnace, is passed through the Ar of 300sccm and is heated to 1070 DEG C；
4) at 1070 DEG C, it is passed through 300sccmAr and 50sccmH2And high annealing 4 hours；
5), after high annealing, at 1070 DEG C, the CH of 0.5sccm it is passed through4And 50sccmH2Growth Graphene 2 hours；
6), after growth terminates, open tube furnace and make sample lower the temperature rapidly and be passed through 300sccmAr and 4sccmH2, it is cooled to room temperature Rear taking-up sample.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modify, all should belong to the covering scope of the present invention.

Claims (2)

1. the preparation method of a grade monolayer single crystal graphene, it is characterised in that: concretely comprise the following steps:
1) substrate annealing: Copper Foil is put into tube furnace quartz ampoule, is passed through 300 sccm Ar, is warming up under an argon atmosphere 1070 DEG C, and carry out at such a temperature making annealing treatment 2 ~ 6 h；
2) growth: after copper foil annealing, be passed through 0.5 sccm CH4With 50 sccm H2Carrying out growing 2 h, this process keeps tubular type The temperature of stove is 1070 DEG C；
3) cooling: open tube furnace, fast cooling, and be passed through 300 sccm Ar and 4 sccm H2, room temperature to be down to i.e. grows Grade monolayer single crystal graphene.
The preparation method of grade monolayer single crystal graphene the most according to claim 1, it is characterised in that: copper in step 1) Before tube furnace quartz ampoule put into by paper tinsel, need to first carry out pretreatment；Described pretreatment is: with shears, copper foil shearing is become suitable big Little, put it into and dilute hydrochloric acid carries out ultrasonic cleaning, be then transferred to ultrasonic cleaning in acetone soln, clean and use nitrogen after terminating Dry up, stand-by.
CN201610588332.5A 2016-07-25 2016-07-25 A kind of preparation method of grade monolayer single crystal graphene Pending CN106283179A (en)

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Cited By (8)

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CN107640763A (en) * 2017-11-17 2018-01-30 信阳师范学院 A kind of preparation method of individual layer single crystal graphene
CN108163846A (en) * 2018-01-19 2018-06-15 复旦大学 A kind of method of the chemical vapor deposition synthesizing graphite alkene of carbon oxide auxiliary
CN108423659A (en) * 2018-05-30 2018-08-21 绍兴文理学院 A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil
CN109023291A (en) * 2018-08-14 2018-12-18 北京镭硼科技有限责任公司 A kind of graphene film and the preparation method and application thereof
CN109107500A (en) * 2018-10-15 2019-01-01 盐城师范学院 A kind of preparation method of copper/graphene core-shell structure
CN109957836A (en) * 2019-04-10 2019-07-02 福建师范大学 A kind of preparation method of single layer monocrystalline square graphite alkene
CN110408990A (en) * 2019-07-31 2019-11-05 中国电子科技集团公司第十三研究所 The preparation method of single crystal graphene
CN110699749A (en) * 2018-07-09 2020-01-17 中国科学院化学研究所 Method for preparing large-area continuous single-layer single-crystal graphene film

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107640763A (en) * 2017-11-17 2018-01-30 信阳师范学院 A kind of preparation method of individual layer single crystal graphene
CN107640763B (en) * 2017-11-17 2020-02-04 信阳师范学院 Preparation method of single-layer single crystal graphene
CN108163846A (en) * 2018-01-19 2018-06-15 复旦大学 A kind of method of the chemical vapor deposition synthesizing graphite alkene of carbon oxide auxiliary
CN108423659A (en) * 2018-05-30 2018-08-21 绍兴文理学院 A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil
CN110699749A (en) * 2018-07-09 2020-01-17 中国科学院化学研究所 Method for preparing large-area continuous single-layer single-crystal graphene film
CN109023291A (en) * 2018-08-14 2018-12-18 北京镭硼科技有限责任公司 A kind of graphene film and the preparation method and application thereof
CN109107500A (en) * 2018-10-15 2019-01-01 盐城师范学院 A kind of preparation method of copper/graphene core-shell structure
CN109107500B (en) * 2018-10-15 2021-06-04 盐城师范学院 Preparation method of copper/graphene core-shell structure
CN109957836A (en) * 2019-04-10 2019-07-02 福建师范大学 A kind of preparation method of single layer monocrystalline square graphite alkene
CN110408990A (en) * 2019-07-31 2019-11-05 中国电子科技集团公司第十三研究所 The preparation method of single crystal graphene

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