CN102689897B - Method for preparing atomic scale graphene groove - Google Patents
Method for preparing atomic scale graphene groove Download PDFInfo
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- CN102689897B CN102689897B CN2012102131395A CN201210213139A CN102689897B CN 102689897 B CN102689897 B CN 102689897B CN 2012102131395 A CN2012102131395 A CN 2012102131395A CN 201210213139 A CN201210213139 A CN 201210213139A CN 102689897 B CN102689897 B CN 102689897B
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- graphene
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Abstract
The invention discloses a method for preparing an atomic scale graphene groove, comprising the following steps of: firstly, preparing graphene and placing the graphene on a high-temperature resistant substrate or suspending; then, deposting a single metal atom or a metal atom cluster which is formed by a plurality of atoms on the surface of graphene; etching graphene by the single metal ion or the atom cluster metal at the set temperature of between 400 and 800 DEG C under the Ar/H2 atmosphere to form the atomic scale graphene groove; subsequently, naturally cooling the atomic scale graphene groove to reach to the room temperature and then taking out the atomic scale graphene groove; and preserving the atomic scale graphene groove in a dry, vacuum or ultraclean environment. The atomic scale graphene groove formed by etching has a flat edge with the atomic scale, and the edge chirality is consistent, so that the influence of edge defects on the graphene performance is reduced.
Description
Technical field
The present invention proposes a kind of method for preparing atomic scale Graphene groove, can be used for making the Graphene groove of atomic scale and based on various microstructures and the device of this method, have using value in materialogy, physics, microtronics and nano-electron field.
Background technology
Graphene is a kind of New Two Dimensional material, being found by A.K.Geim and K.S.Novoselov in 2004, is the film of monoatomic layer, can stable existence under atmospheric environment, have perfect crystalline structure and excellent performance, have in a lot of fields research and using value widely.
Due to the unique crystal structures of Graphene, make it have high carrier mobility, reach as high as 2 * 10
5cm
2V
-1s
-1, be about 140 times of electronic mobility in silicon, and mobility does not have obvious degeneration when highfield transports.In Graphene, carbon atom forms stable sp
2Hybridized orbital makes it have higher current load density and stronger deelectric transferred ability.In conjunction with the advantage of physical size aspect, Graphene has huge application prospect in the novel high speed field of electronic devices.
Graphically Graphene to be applied to the gordian technique of electron device and integrated circuit fields, in theory, all active and passive devices (comprising: transistor, resistance, inductance, electric capacity etc.) and other have the microstructure (such as interconnection line, transmission line etc.) of specific function, all can be realized by Graphene, its key is the imaging technique of Graphene.The Graphene imaging technique of main flow is to realize in conjunction with electron beam exposure and plasma etching at present, the yardstick of groove is at micron and nanoscale, and the Graphene edge defect that etching forms is more, chirality is uncontrollable, the method that there is no so far carry out on atomic scale Graphene graphical, can't etch width at the Graphene groove of atomic scale.
Summary of the invention
The object of the invention is to provide a kind of method for preparing atomic scale Graphene groove.
The present invention proposes a kind of preparation method of atomic scale Graphene groove, can be achieved through the following technical solutions:
1. preparation Graphene, and on placing it at the bottom of high temperature-resistant liner or unsettled, the size of Graphene and the number of plies are all without particular requirement.
The method of Graphene preparation has multiple: the methods such as mechanically peel, chemical gas phase synthetic (CVD) and graphene oxide reduction.
If Graphene is positioned on substrate, the substrate that should select 400 ℃ ~ 800 ℃ lower Stability Analysis of Structures and not react with Graphene, as: SiO
2/ Si, BN, quartz, mica, sapphire, graphite oxide etc.
2. at Graphene surface deposition single metal atom or or by some former molecular metal atomic clusters.It is multiple that but the metal of catalysis etching Graphene has, as Fe, Co, Ni, Cu, Ag, Zn etc.The yardstick of metal atomic cluster is below 10nm.
Deposit single metal atom: can utilize needle tip of scanning tunnel microscope moving metal atom to realize, first sample is placed in the low pressure metal steam more than 1min, make atoms metal be adsorbed on the surface of sample, then sample is put into the STM chamber, and be evacuated to ultrahigh vacuum(HHV) (＜10
-7Torr), be cooled to below 10K; Image scanning is carried out in the zone that the STM needle point is moved to depositing metal, then needle point is moved to a certain atoms metal place to be moved, and close atoms metal is until catch this atoms metal, after in stable condition more at the uniform velocity, lentamente along surperficial mobile needle point, atoms metal synchronously moves to Graphene zone to be etched with the STM needle point, atoms metal is separated with needle point, atoms metal is placed in default position.
The method of depositing metal cluster has two kinds:
(1) surperficial by physical vapour deposition (PVD) method depositing metal at Graphene, thickness is 0.5nm ~ 5nm, then can form metal atomic cluster through anneal;
(2) salts solution that is comprised of metal ion and volatile acid ion in the spin coating of Graphene surface is (as NiCl
2, FeCl
2, FeCl
3, ZnCl
2, CuCl
2, Zn (NO
3)
2, Cu (NO
3)
2, Fe (NO
3)
2, Fe (NO
3)
3Deng), more annealed processing can form metal atomic cluster.
Anneal in above-mentioned two kinds of approach is all naturally cooling after being incubated 5min～30min under 150 ℃～400 ℃, and annealing process is at Ar/H
2Carry out under atmosphere, wherein Ar and H
2Flow is respectively in 100sccm～500sccm and 5sccm～50sccm scope.
3. monatomic or cluster metal catalyst is at a certain design temperature, Ar/H
2Etching Graphene under atmosphere: design temperature can be selected in 400 ℃～800 ℃ scopes, when rising to design temperature from room temperature, sample needs rising, temperature rise rate＜25 ° C/min, the heating-up time is no more than 40min, is controlled between 15min～2h in the soaking time of design temperature; All need keep Ar/H in intensification, insulation and temperature-fall period
2Atmosphere is constant, Ar and H
2Flow respectively in 100sccm～500sccm and 5sccm～50sccm scope; Take out after at last sample being naturally cooled to room temperature, and be kept in drying, vacuum or super-clean environment.
The present invention has following technique effect:
The present invention proposes a kind of method of utilizing metal catalytic etching Graphene to prepare atomic scale Graphene groove.The method is reliable, efficient, the Graphene groove width of preparation can be controlled and can reach monatomic yardstick thus, or several atomic scales, as depicted in figs. 1 and 2, the Graphene groove that etching forms has atomic scale smooth edge, and the edge chirality is consistent, has reduced the impact of edge defect on the Graphene performance.
Description of drawings
Fig. 1 is the schematic diagram that metal atomic cluster etching Graphene of the present invention prepares atomic scale Graphene groove;
Fig. 2 is the schematic diagram that the single atom-lithography Graphene of the present invention prepares atomic scale Graphene groove.
Embodiment
Combination illustrates specific embodiments of the invention below, but the scope that does not limit the present invention in any way.
Embodiment 1
(1) utilize the method for mechanically peel, by natural graphite flake, at 300nm-SiO
2Prepare Graphene on/p-Si substrate.
(2) utilize electron beam evaporation at the even evaporation 2nmCo of whole sample surfaces, then can form the metal Co cluster through anneal, anneal is naturally cooling after insulation 20min under 300 ℃, and annealing process is at Ar/H
2(100sccm/15sccm) carry out under the atmosphere.
(3) sample is put into high temperature process furnances at certain temperature, Ar/H
2Under atmosphere, the etching Graphene forms groove.Specifically comprise: first pass into Ar and H before beginning
2, flow is controlled at respectively 100sccm and 20sccm, begins to heat up after ventilation 10min, and 20 ℃/min of heat-up rate, temperature is incubated 1.5h after rising to 750 ℃, then cooling, temperature-fall period continues to pass into Ar and H by above-mentioned flow
2, until the temperature in tube furnace is cooled to room temperature.
Embodiment 2
(1) utilize CVD technology growth Graphene on Copper Foil, then Graphene is transferred to 90nm-SiO
2On/p-Si substrate.
(2) be the Fe (NO of 20mg/L in sample surfaces spin coating 10mL concentration
3)
3Solution, spin speed are 2000rpm, and the spin coating time is 1min, then can form metal Fe cluster through anneal, and anneal is naturally cooling after insulation 30min under 250 ℃, and annealing process is at Ar/H
2(150sccm/15sccm) carry out under the atmosphere.
(3) sample is put into high temperature process furnances at certain temperature, Ar/H
2Under atmosphere, the etching Graphene forms groove: specifically comprise: pass into Ar and H
2, flow is controlled at respectively 200sccm and 30sccm, is incubated 2h after being warming up to 700 ℃, and 20 ℃/min of heat-up rate, temperature-fall period must continue pass into Ar and H by above-mentioned flow
2, until in tube furnace, temperature is cooled to room temperature.
Embodiment 3
(1) utilize the method for mechanically peel, by high orientation graphite, at 90nm-SiO
2Prepare Graphene on/p-Si substrate.
(2) sample is placed on 10
-5Process 10min in the middle of the Ni steam of Torr.
(3) sample is put into STM, with being evacuated to ultrahigh vacuum(HHV) in the chamber, cool to 4K, scanning of a surface selects suitable Ni atom as catalyzer near needing the position of etching.Needle point is moved to Ni atom place to be moved.By improve the tunnel current value make needle point and the Ni atom close, after reaching steady state, more at the uniform velocity, mobile needle point lentamente, make the Ni atom with the needle point synchronizing moving near Graphene to be etched surface.And then reduce the tunnel current value needle point is lifted, the Ni atom is separated with needle point.This moment, single Ni atom just was attached to the Graphene surface.Repeatable operation like this, the single Ni atom of predetermined position placement on the Graphene surface.
(3) sample is put into high temperature process furnances at certain temperature, Ar/H
2Under atmosphere, the etching Graphene forms groove: specifically comprise: first pass into Ar and H before beginning
2, flow is controlled at respectively 150sccm and 40sccm, begins to heat up after ventilation 10min, and 15 ℃/min of heat-up rate makes temperature-stable be incubated 45min after 450 ℃, continues to pass into Ar and H
2, until be cooled to room temperature.
Claims (6)
1. the preparation method of an atomic scale Graphene groove, its step comprises:
1) preparation Graphene, and on placing it at the bottom of high temperature-resistant liner or unsettled;
2) Graphene surface deposition single metal atom or by some former molecular yardsticks at the following metal atomic cluster of 10nm;
Wherein, concrete steps at Graphene surface deposition single metal atom are: more than 1min, make atoms metal be adsorbed on the surface of sample, then sample is put into the STM chamber in first the Graphene sample being placed on the low pressure metal steam, and be evacuated to ultrahigh vacuum(HHV), be cooled to below 10K; Image scanning is carried out in the zone that the STM needle point is moved to depositing metal, then needle point is moved to a certain atoms metal place to be moved, and close atoms metal is until catch this atoms metal, after in stable condition more at the uniform velocity, lentamente along surperficial mobile needle point, atoms metal synchronously moves to Graphene zone to be etched with the STM needle point, atoms metal is separated with needle point, atoms metal is placed in default position;
Concrete steps at Graphene surface deposition metal atomic cluster are: surperficial by physical vapour deposition method depositing metal at Graphene, thickness is 0.5nm～5nm, then can form metal atomic cluster through anneal; Or the salts solution that is comprised of metal ion and volatile acid ion in the spin coating of Graphene surface, more annealed processing can form metal atomic cluster.
3) single metal atom or metal atomic cluster are at 400 ℃～800 ℃ of design temperatures and Ar/H
2Etching Graphene under atmosphere takes out after naturally cooling to subsequently room temperature, and is kept in drying, vacuum or super-clean environment.
2. preparation method as claimed in claim 1, is characterized in that, employing mechanically peel, chemical gas phase are synthesized and the graphene oxide method of reducing prepares Graphene.
3. preparation method as claimed in claim 1, is characterized in that, selects SiO at the bottom of high temperature-resistant liner
2/ Si, BN, quartz, mica, sapphire or graphite oxide.
4. preparation method as claimed in claim 1, is characterized in that, the atoms metal of etching Graphene is Fe, Co, Ni, Cu, Ag or Zn.
5. preparation method as claimed in claim 1, is characterized in that, anneal comprises: naturally cooling after being incubated 5min～30min under 150 ℃～400 ℃, annealing process is at Ar/H
2Carry out under atmosphere, wherein Ar and H
2Flow is respectively in 100sccm～500sccm and 5sccm～50sccm scope.
6. preparation method as claimed in claim 1, it is characterized in that step 3) in need rising when at first rising to design temperature from room temperature, temperature rise rate＜25 ℃/min, heating-up time is no more than 40min, is controlled between 15min～2h in the soaking time of design temperature; All need keep Ar/H in intensification, insulation and temperature-fall period
2Atmosphere is constant, Ar and H
2Flow respectively in 100sccm～500sccm and 5sccm～50sccm scope.
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| CN2012102131395A CN102689897B (en) | 2012-06-25 | 2012-06-25 | Method for preparing atomic scale graphene groove |
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| EP3183210B1 (en) | 2015-08-14 | 2018-01-17 | SABIC Global Technologies B.V. | Method of metallic clusters fabrication with desired size using scanning tunneling microscopy tip induced reactions |
| CN107244666B (en) * | 2017-05-31 | 2020-04-21 | 山东大学 | Method for growing large-domain graphene by taking hexagonal boron nitride as point seed crystal |
| CN111916708B (en) * | 2020-08-12 | 2021-11-30 | 贵州梅岭电源有限公司 | Preparation method of Ag modified interlayer inlaid SnS2 composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941696A (en) * | 2010-09-15 | 2011-01-12 | 复旦大学 | Nanolithographic method applied to manufacture of graphene-based field effect tube |
| CN102285631A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for processing nanoscale pattern on graphite or graphene surface |
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| KR20100117570A (en) * | 2008-01-03 | 2010-11-03 | 내셔널 유니버시티 오브 싱가포르 | Functionalised graphene oxide |
| WO2012051597A2 (en) * | 2010-10-15 | 2012-04-19 | The Regents Of The University Of California | Organometallic chemistry of extended periodic ii-electron systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941696A (en) * | 2010-09-15 | 2011-01-12 | 复旦大学 | Nanolithographic method applied to manufacture of graphene-based field effect tube |
| CN102285631A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for processing nanoscale pattern on graphite or graphene surface |
Non-Patent Citations (2)
| Title |
|---|
| Atomic Force and Scanning Tunneling Microscopy Imaging of Graphene Nanosheets Derived from Graphite Oxide;J.I.Paredes, et al.;《Langmuir》;20090402;第5958-5960页 * |
| J.I.Paredes, et al..Atomic Force and Scanning Tunneling Microscopy Imaging of Graphene Nanosheets Derived from Graphite Oxide.《Langmuir》.2009,第5958-5960页. |
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