CN102689897A - Method for preparing atomic scale graphene groove - Google Patents
Method for preparing atomic scale graphene groove Download PDFInfo
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- CN102689897A CN102689897A CN2012102131395A CN201210213139A CN102689897A CN 102689897 A CN102689897 A CN 102689897A CN 2012102131395 A CN2012102131395 A CN 2012102131395A CN 201210213139 A CN201210213139 A CN 201210213139A CN 102689897 A CN102689897 A CN 102689897A
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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, have using value in materialogy, physics, microtronics and nano-electron field based on the various microstructures and the device of this method.
Background technology
Graphene is a kind of novel 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 extensive studies and using value in a lot of fields.
Because the unique crystal structures of Graphene makes it have high carrier mobility, reaches as high as 2 * 10
5Cm
2V
-1s
-1, be about 140 times of electronic mobility in the silicon, and mobility does not have obvious degeneration when highfield transports.Carbon atom forms stable sp in the Graphene
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 great application prospect in the novel high speed field of electronic devices.
It graphically is the gordian technique that Graphene is applied to 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 (for example: interconnection line, transmission line etc.) of specific function; Can realize that all its key is the imaging technique of Graphene by Graphene.The Graphene imaging technique of main flow is to combine electron beam exposure and plasma etching to realize at present; The yardstick of groove is at micron and nanoscale; And the Graphene edge defect that etching forms is more, chirality is uncontrollable, still can't on atomic scale, carry out so far Graphene graphical, can't etch the Graphene groove of width at 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 realize through following technical scheme:
1. preparation Graphene, and on placing it at the bottom of the high temperature-resistant liner or unsettled, the size of Graphene and the number of plies all do not have particular requirement.
The method of Graphene preparation has multiple: methods such as mechanically peel, chemical gas phase synthetic (CVD) and graphene oxide reduction.
If Graphene is positioned on the substrate, the substrate that then should select 400 ℃ ~ 800 ℃ following Stability Analysis of Structures for use 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 the metal atomic cluster formed by some atoms.It is multiple that but the metal of catalysis etching Graphene has, like Fe, Co, Ni, Cu, Ag, Zn etc.The yardstick of metal atomic cluster is below 10nm.
Deposit single metal atom: needle tip of scanning tunnel microscope moving metal atom capable of using is realized; Earlier sample is placed in the low pressure metal steam more than the 1min; Make atoms metal be adsorbed on the surface of sample, again sample put into the STM chamber, and be evacuated to ultrahigh vacuum(HHV) (<10
-7Torr), be cooled to below the 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 near atoms metal, until catching this atoms metal, treat in stable condition after more at the uniform velocity, move needle point along the surface lentamente, atoms metal moves to Graphene zone to be etched synchronously with the STM needle point; Atoms metal is separated with needle point, atoms metal is placed preset position.
The method of depositing metal cluster has two kinds:
(1) pass through physical vapour deposition (PVD) method depositing metal on the Graphene surface, thickness is 0.5nm ~ 5nm, can form metal atomic cluster through anneal again;
(2) salts solution that spin coating is made up of metals ion and volatile acid ion on Graphene surface is (like 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), annealed again processing can form metal atomic cluster.
Anneal in above-mentioned two kinds of approach all is naturally cooling behind insulation 5min～30min under 150 ℃～400 ℃, and annealing process is at Ar/H
2Carry out under the 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 the atmosphere: design temperature can be selected in 400 ℃～800 ℃ scopes, and sample needs slowly to rise temperature rise rate when room temperature rises to design temperature<25 ° of Cmin, the TRT 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 the 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 the 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.This method is reliable, efficient; The Graphene groove width may command of preparation can reach monatomic yardstick thus; Or several atomic scales, as depicted in figs. 1 and 2, the Graphene groove that etching forms has the smooth edge of atomic scale; And the edge chirality is consistent, has reduced edge defect to the Graphene Effect on Performance.
Description of drawings
Fig. 1 prepares the synoptic diagram of atomic scale Graphene groove for metal atomic cluster etching Graphene of the present invention;
Fig. 2 prepares the synoptic diagram of atomic scale Graphene groove for the single atom etching of the present invention Graphene.
Embodiment
The following combination illustrates specific embodiment of the present invention, but the scope that does not limit the present invention in any way.
Embodiment 1
(1) utilizes the method for mechanically peel, by natural graphite flake, at 300nm-SiO
2Prepare Graphene on the/p-Si substrate.
(2) utilize electron beam evaporation at the surperficial evenly vapor deposition 2nmCo of entire sample, can form the metal Co cluster through anneal again, anneal is a naturally cooling behind 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
2The etching Graphene forms groove under the atmosphere.Specifically comprise: feed Ar and H before the beginning earlier
2, flow is controlled at 100sccm and 20sccm respectively, begins to heat up behind the ventilation 10min, and 20 ℃/min of heat-up rate, temperature is incubated 1.5h after rising to 750 ℃, cooling then, temperature-fall period continues to feed Ar and H by above-mentioned flow
2, the temperature in tube furnace is cooled to room temperature.
Embodiment 2
(1) on Copper Foil, utilizes CVD technology growth Graphene, then Graphene is transferred to 90nm-SiO
2On/p-Si the 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, can form metal Fe cluster through anneal again, and anneal is a naturally cooling behind 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
2The etching Graphene forms groove under the atmosphere: specifically comprise: feed Ar and H
2, flow is controlled at 200sccm and 30sccm respectively, is incubated 2h after being warming up to 700 ℃, and 20 ℃/min of heat-up rate, temperature-fall period must continue to feed Ar and H by above-mentioned flow
2, temperature is cooled to room temperature in tube furnace.
Embodiment 3
(1) utilizes the method for mechanically peel, by high orientation graphite, at 90nm-SiO
2Prepare Graphene on the/p-Si substrate.
(2) sample is placed on 10
-5Handle 10min in the middle of the Ni steam of Torr.
(3) put into STM to sample, 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.Through improve the tunnel current value make needle point and Ni atom near, reach steady state after, move needle point more at the uniform velocity, lentamente, make the Ni atom near moving to synchronously with needle point Graphene to be etched surperficial.And then reduce the tunnel current value needle point is lifted, the Ni atom is separated with needle point.This moment, single Ni atom was just attached to the Graphene surface.So repeatable operation is placed single Ni atom in the predetermined position on Graphene surface.
(3) sample is put into high temperature process furnances at certain temperature, Ar/H
2The etching Graphene forms groove under the atmosphere: specifically comprise: feed Ar and H before the beginning earlier
2, flow is controlled at 150sccm and 40sccm respectively, begins to heat up behind the ventilation 10min, and 15 ℃/min of heat-up rate makes temperature-stable after 450 ℃, be incubated 45min, continues to feed Ar and H
2, until being cooled to room temperature.
Claims (8)
1. the preparation method of an atomic scale Graphene groove, its step comprises:
1) preparation Graphene, and on placing it at the bottom of the high temperature-resistant liner or unsettled;
2) yardstick of forming at Graphene surface deposition single metal atom or by some atoms is at the following metal atomic cluster of 10nm;
3) single metal atom or metal atomic cluster are at 400 ℃ ~ 800 ℃ of design temperatures and Ar/H
2Etching Graphene under the atmosphere takes out after naturally cooling to room temperature subsequently, and is kept in drying, vacuum or the 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 the high temperature-resistant liner for use
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, Zn.
5. preparation method as claimed in claim 1; It is characterized in that; Step 2) concrete steps at Graphene surface deposition single metal atom in are: earlier the Graphene sample is placed in the low pressure metal steam more than the 1min, makes atoms metal be adsorbed on the surface of sample, again sample is put into the STM chamber; And be evacuated to ultrahigh vacuum(HHV), be cooled to below the 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 near atoms metal, until catching this atoms metal, treat in stable condition after more at the uniform velocity, move needle point along the surface lentamente, atoms metal moves to Graphene zone to be etched synchronously with the STM needle point; Atoms metal is separated with needle point, atoms metal is placed preset position.
6. preparation method as claimed in claim 1; It is characterized in that; Step 2) concrete steps at Graphene surface deposition metal atomic cluster in are: through physical vapour deposition method depositing metal, thickness is 0.5nm ~ 5nm, can form metal atomic cluster through anneal again on the Graphene surface; Or the salts solution that spin coating is made up of metals ion and volatile acid ion on Graphene surface, annealed again processing can form metal atomic cluster.
7. preparation method as claimed in claim 6 is characterized in that anneal comprises: naturally cooling behind insulation 5min ~ 30min under 150 ℃ ~ 400 ℃, annealing process is at Ar/H
2Carry out under the atmosphere, wherein Ar and H
2Flow is respectively in 100sccm ~ 500sccm and 5sccm ~ 50sccm scope.
8. preparation method as claimed in claim 1 is characterized in that, at first when room temperature rises to design temperature, needs slowly to rise temperature rise rate in the step 3)<25oC/>min, the TRT 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 the 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107073448A (en) * | 2015-08-14 | 2017-08-18 | 沙特基础工业全球技术公司 | The method of metal cluster of the manufacture with desired size is reacted using PSTM art tip induced |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| CN111916708A (en) * | 2020-08-12 | 2020-11-10 | 贵州梅岭电源有限公司 | Ag modified interlayer inlaid SnS2Method for preparing composite material |
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| CN101941696A (en) * | 2010-09-15 | 2011-01-12 | 复旦大学 | Nanolithographic method applied to manufacture of graphene-based field effect tube |
| US20110052813A1 (en) * | 2008-01-03 | 2011-03-03 | Peter Ho | Functionalised graphene oxide |
| CN102285631A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for processing nanoscale pattern on graphite or graphene surface |
| 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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2012
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| US20110052813A1 (en) * | 2008-01-03 | 2011-03-03 | Peter Ho | Functionalised graphene oxide |
| CN101941696A (en) * | 2010-09-15 | 2011-01-12 | 复旦大学 | Nanolithographic method applied to manufacture of graphene-based field effect tube |
| 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107073448A (en) * | 2015-08-14 | 2017-08-18 | 沙特基础工业全球技术公司 | The method of metal cluster of the manufacture with desired size is reacted using PSTM art tip induced |
| US10118155B2 (en) | 2015-08-14 | 2018-11-06 | Sabic Global Technologies B.V. | Method of metallic clusters fabrication with desired size using scanning tunneling microscopy tip induced reactions |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| 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 |
| CN111916708A (en) * | 2020-08-12 | 2020-11-10 | 贵州梅岭电源有限公司 | Ag modified interlayer inlaid SnS2Method for preparing composite material |
| 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 |
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| CN102689897B (en) | 2013-11-06 |
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