CN103523770B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN103523770B CN103523770B CN201310492787.3A CN201310492787A CN103523770B CN 103523770 B CN103523770 B CN 103523770B CN 201310492787 A CN201310492787 A CN 201310492787A CN 103523770 B CN103523770 B CN 103523770B
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Abstract
The invention provides a kind of preparation method of Graphene, the preparation method of this Graphene at least comprises step: first, provides a SiC substrate; Then, ion implantation technique is adopted to inject Ge in described SiC substrate; Finally, carry out anneal to the structure of above-mentioned formation, the Ge of injection can force Si and the C very easily scission of link of described SiC in annealing process, and the Ge of the Si after scission of link and injection forms SiGe, the C after scission of link and forms Graphene in described SiGe surface restructuring.The present invention only needs normal pressure or low pressure and low temperature just can prepare Graphene, lower to the requirement of apparatus for preparation, and save energy, minimizing cost, be applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to semiconductor applications, particularly relate to a kind of preparation method of Graphene.
Background technology
2004, the method that two scientists of Univ Manchester UK use micromechanics to peel off found Graphene, and obtains Nobel Prize in physics in 2010.Graphene, the i.e. monoatomic layer of graphite are the two-dirnentional structure of carbon atom by honeycomb arrangement.After Graphene is found, because the performance of its excellence and huge application prospect have caused the research boom in the field such as physics and Materials science.The application of Graphene in optical, electrical field also widely, comprises based on the lithium ion battery of Graphene, solar cell, gas detector and some devices etc.The application of Graphene in optical, electrical field is all based on the basis of the controlled graphene film of big area, the number of plies.But the grapheme material problem that controlledly synthesis has specific morphology is not still resolved.Based on this, the research of Graphene still rests on fundamental research field, and the large-scale application of distance still has a segment distance.
The method preparing Graphene at present mainly contains micromechanics stripping, chemical vapor deposition and graphite oxide reduction method, SiC subliming method.Micromechanics stripping method can prepare high-quality Graphene, but the Graphene area that at present prepared by this method is less than 1mm × 1mm, can only be used for Basic Experiment Study.Although CVD (Chemical Vapor Deposition) method can prepare large-area graphene film, but the controllability of the graphene film thickness that this method obtains is poor, as on Cu, CVD prepares Graphene (Xuesong Li, Weiwei Cai, Jinho An, Ruoff et al, Large-Area Synthesis of High-Quality and Uniform GrapheneFilms on Copper Foils, Science, 2009, 324, 1312) be a kind of self-limit growth mechanism of surface catalysis, when the first layer Graphene covers Cu surface 95% time, the catalytic effect on Cu surface will weaken and even lost efficacy, so the Graphene prepared on Cu is that be individual layer with a small amount of bilayer, on Ni, CVD prepares Graphene (Qingkai Yu, Jie Lian, SujitraSiriponglert, et al, Graphene segregated on Ni surfaces and transferred to insulators, APPLIEDPHYSICS LETTERS, 2008,93,113103) be that a kind of solution modeling mechanism prepares Graphene, the stage of graphene growth occurs in temperature-fall period, and the number of plies is subject to the impact of rate of temperature fall, so the Graphene of preparation is multilayer film in uneven thickness.And graphite oxide reduction method can a large amount of Graphene sample of chemical preparation, meets industrial application requirement to a certain extent, but due to the introducing of oxygenant, destroy the conjugated structure of Graphene.Although chemical reduction and high-temperature heat treatment can recover the conjugated structure of Graphene to a certain extent, but the intrinsic electric property of Graphene reduces greatly.
It is one of preparation method of comparatively main flow at present that SiC subliming method prepares Graphene, large-area high-quality can be obtained and the controlled graphene film of thickness, but the SiC subliming method of routine needs at high temperature, (T=1550 DEG C is prepared under ultrahigh vacuum(HHV), P=1bar), very high requirement is had to instrument, cost increases, prevent its suitability for industrialized production (Konstantin V.Emtsev et al.Towardswafer-size graphene layers by atmospheric pressure graphitization of silicon carbide.NatureMaterials, 8, 203-207 (2009)).
In view of the shortcoming of above-mentioned graphene preparation method, the present invention proposes a kind of method preparing Graphene under normal pressure, lesser temps, can large-area high-quality be obtained and the controlled graphene film of thickness, save energy, reduce cost, be applicable to suitability for industrialized production.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparation method of Graphene, prepares for solving SiC subliming method in prior art the problem that Graphene needs carry out causing not easily suitability for industrialized production under high temperature, ultrahigh vacuum(HHV).
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of Graphene, described graphene preparation method at least comprises:
1) a SiC substrate is provided;
2) ion implantation technique is adopted to inject Ge in described SiC substrate;
3) to step 2) structure that formed carries out anneal, and the Ge of injection can force Si and the C very easily scission of link of described SiC in annealing process, the Ge of the Si after scission of link and injection forms SiGe, the C after scission of link and forms Graphene in described SiGe surface restructuring.
Preferably, described step 2) in the Implantation Energy scope of Ge be 5 ~ 30keV, the dosage range of injection is 1E15 ~ 1E20atoms/cm
2.
Preferably, in described step 3), the temperature range of anneal is 800 ~ 1000 DEG C, and the time range of anneal is 10 ~ 100min, and annealing adopts Ar gas as shielding gas.
Preferably, the flow range of described Ar gas is 1 ~ 1000sccm.
Preferably, under normal pressure or low pressure, anneal is carried out; The scope of described low pressure is 1E-1 ~ 1E-5mbar.
Preferably, the thickness range forming SiGe is 1-3nm.
Preferably, the Graphene formed in described step 3) is individual layer, bilayer or multilayer.
Preferably, the thickness range forming Graphene is 0.34 ~ 1nm.
Preferably, the step of described SiC substrate being carried out surface cleaning is also comprised in described step 1).
Preferably, the crystal formation of described SiC substrate adopts 4H-SiC, 6H-SiC or 3C-SiC.
As mentioned above, the preparation method of Graphene of the present invention, comprises step: first, provides a SiC substrate; Then, ion implantation technique is adopted to inject Ge in described SiC substrate; Finally, the structure of above-mentioned formation carries out anneal, and the Ge of injection can force Si and the C very easily scission of link of described SiC in annealing process, and the Ge of the Si after scission of link and injection forms SiGe, the C after scission of link and forms Graphene in described SiGe surface restructuring.The present invention only needs normal pressure and low temperature just can prepare Graphene, lower to the requirement of apparatus for preparation, and save energy, minimizing cost, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the preparation method of Graphene of the present invention.
The structural representation of the SiC substrate provided in the preparation method of Fig. 2 for Graphene of the present invention.
Fig. 3 is the structural representation adopting ion implantation technique to inject Ge in the preparation method of Graphene of the present invention in SiC substrate.
Fig. 4 is the structural representation of SiGe and the Graphene formed after annealing in the preparation method of Graphene of the present invention.
The original SiC provided and inject Ge and the Raman comparison diagram of SiC after annealing in the preparation method of Fig. 5 for Graphene of the present invention.
Element numbers explanation
S1 ~ S3 step
1 Si atom
2 C atoms
3 Ge atoms
4 SiGe
5 Graphenes
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to accompanying drawing 1 to Fig. 5.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
The invention provides a kind of preparation method of Graphene, as shown in Figure 1, the preparation method of described Graphene at least comprises the following steps:
First perform step S1, as shown in Figure 2, provide a SiC substrate, described SiC substrate is made up of some Si atoms 1 and C atom 2.
Preferably, before carrying out subsequent technique, surface cleaning is carried out to described SiC substrate.Be specially: SiC substrate is carried out sonic oscillation 10 minutes to remove the organism such as the grease on its surface with acetone, ethanol and deionized water respectively according to sequencing, afterwards SiC substrate is dried up.Wherein, the crystal formation of described SiC substrate can adopt 4H-SiC, 6H-SiC or 3C-SiC etc.In the present embodiment, described SiC substrate adopts 6H-SiC.
Then perform step S2, as shown in Figure 3, adopt ion implantation technique to inject Ge atom 3 in described SiC substrate.
Wherein, adopt ion implantation Implantation Energy can within the scope of 5 ~ 30keV, preferably, ion implantation Implantation Energy is 5 ~ 20keV.Particularly, in the present embodiment, the energy adopting ion implantation technique to inject Ge is 10keV.The energy injected due to Ge is low, and therefore, Ge is only infused in the top layer of described SiC substrate, injects the degree of depth and is about 1 ~ 10nm.The implantation dosage scope of described Ge can at 1E15 ~ 1E20atoms/cm
2interior selection, preferably, the implantation dosage of described Ge is 1E15 ~ 1E16atoms/cm
2.Particularly, in the present embodiment, the implantation dosage of described Ge is 1E15atoms/cm
2.As can be seen from Figure 3, the Ge atom 3 of injection is embedded between Si atom 1 and C atom 2.
Finally perform step S3, as shown in Figure 4, anneal is carried out to the structure that step S2 is formed, the Ge atom 3 injected can force Si atom 1 and the C atom 2 very easily scission of link of described SiC in annealing process, the Ge of the Si after scission of link and injection forms SiGe4, the C after scission of link and forms Graphene 5 in described SiGe4 surface restructuring.
The temperature of carrying out anneal can complete within the scope of 800 ~ 1000 DEG C, and annealing time is 10 ~ 100 minutes.In the present embodiment, the temperature of carrying out anneal is 800 DEG C, and the set of time of process is 10 minutes.
Preferably; when carrying out anneal; Ar gas can be passed into as protective gas in annealing device; be used for preventing the Graphene of follow-up generation oxidized; but be not limited to Ar gas as shielding gas in the present invention, also can adopt the one in other rare gas element or inactive gas and combination thereof.In the present embodiment, adopt Ar gas as shielding gas.The flow range of the Ar gas passed into is 1 ~ 1000sccm(per minute standard milliliters), preferably, Ar airshed is 200 ~ 800sccm.In the present embodiment, pass into the Ar gas of 500sccm as shielding gas during annealing.
Anneal can be carried out at atmospheric or low pressure, and preferably under low pressure carry out anneal prepares Graphene to the present embodiment.Concrete, the air pressure range under low pressure is 1E-1 ~ 1E-5mbar.In the present embodiment, be carry out anneal in the low pressure environment of 1E-2mbar at air pressure.
In annealing process, the Ge atom 3 of injection can force Si atom 1 and C atom 2 very easily scission of link under annealing process, and the thickness range of the SiGe4 of formation is 1 ~ 3nm.In the present embodiment, the thickness of the SiGe4 of formation is 2nm.After Si atom 1 and C atom 2 bond rupture, 2, remaining C atom is separated out on SiGe4 surface and is reassembled into core and to grow up formation Graphene 5.The thickness range of the Graphene 5 formed is 0.34 ~ 1nm.In the present embodiment, the thickness of the Graphene of formation is 0.34nm.According to the dosage that Ge injects, the Graphene 5 of formation can be individual layer, bilayer or multilayer.In the present embodiment, the implantation dosage of Ge is 1E15atoms/cm
2, the Graphene 5 of formation is individual layer.
Compare the method that Graphene is prepared in traditional SiC distillation, preparation temperature in graphene preparation method provided by the invention is adopted obviously to reduce (800 ~ 1000 DEG C), its reason is: on the one hand may be relevant with ion implantation technology, implantation membership causes SiC lattice damage, and the atomic bond contributing to Si atom 1 in SiC substrate and C atom 2 disconnects; On the other hand, after ion implantation Ge, Ge with Si atom very easily becomes key to form SiGe4 in this temperature range, and this has also impelled the disconnection of Si and C atomic bond indirectly.
Raman spectroscopy is adopted to characterize process results, to confirm to have prepared Graphene in SiC substrate.Exemplarily, refer to Fig. 5, the Raman figure (curve below) of the original SiC substrate provided in the preparation method of Graphene of the present invention and Ge is provided and injects SiC and Raman figure (curve above) after annealing.Concrete technology parameter is: ion implantation energy is 10keV, Ge implantation dosage is 1E15atoms/cm
2, annealing temperature is 900 DEG C, annealing time is 30min, and air pressure is the flow of 1E-3mbar, Ar gas is 200sccm.As can be seen from Figure 5, in the Raman spectrum of SiC substrate, do not have the characteristic peak of Graphene, and SiC injects Ge through top layer and after carrying out anneal, has occurred the characteristic feature peak of Graphene in Raman spectrum: G peak and 2D peak.Wherein, G peak is in 1570cm
-1near, 2D peak is in 2700cm
-1near, this shows, adopts graphene preparation method of the present invention successfully to prepare Graphene, and the technological temperature preparing Graphene is low compared with the technological temperature of traditional technology.It should be noted that, Graphene prepared by one group of processing parameter is show only in the present embodiment, in fact, change the position that the processing parameter preparing Graphene can't change G and 2D characteristic peak in Raman spectrum, and be only the change of relative intensity, show the Raman spectrum of the Graphene utilizing other processing parameters to prepare in the present invention no longer one by one.
In sum, the invention provides a kind of preparation method of Graphene, the preparation method of this Graphene at least comprises: first, provides a SiC substrate; Then, ion implantation technique is adopted to inject Ge in described SiC substrate; Finally, the structure of above-mentioned formation carries out anneal, and the Ge of injection can force Si and the C very easily scission of link of described SiC in annealing process, and the Ge of the Si after scission of link and injection forms SiGe, the C after scission of link and forms Graphene in described SiGe surface restructuring.The present invention only needs low pressure and low temperature just can prepare Graphene, lower to the requirement of apparatus for preparation, and save energy, minimizing cost, be applicable to suitability for industrialized production.
So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (9)
1. a graphene preparation method, is characterized in that, described graphene preparation method at least comprises:
1) a SiC substrate is provided;
2) ion implantation technique is adopted to inject Ge in described SiC substrate;
3) to step 2) structure that formed carries out anneal, the Ge injected can force Si and the C very easily scission of link of described SiC in annealing process, the Ge of the Si after scission of link and injection forms SiGe, C after scission of link forms Graphene in described SiGe surface restructuring, wherein, the temperature range of anneal is 800 ~ 1000 DEG C, and anneal is carried out under the low pressure of normal pressure or 1E-1 ~ 1E-5mbar.
2. graphene preparation method according to claim 1, is characterized in that: described step 2) in the Implantation Energy scope of Ge be 5 ~ 30keV, the dosage range of injection is 1E15 ~ 1E20atoms/cm
2.
3. graphene preparation method according to claim 1, is characterized in that: described step 3) in the temperature range of anneal be 800 ~ 1000 DEG C, the time range of anneal is 10 ~ 100min, adopts Ar gas as shielding gas during anneal.
4. graphene preparation method according to claim 3, is characterized in that: the flow range of described Ar gas is 1 ~ 1000sccm.
5. graphene preparation method according to claim 1, is characterized in that: described step 3) in form the thickness range of SiGe be 1 ~ 3nm.
6. graphene preparation method according to claim 1, is characterized in that: described step 3) in formed Graphene be individual layer, bilayer or multilayer.
7. graphene preparation method according to claim 6, is characterized in that: the thickness range forming Graphene is 0.34 ~ 1nm.
8. graphene preparation method according to claim 1, is characterized in that: described step 1) in also comprise the step of described SiC substrate being carried out surface cleaning.
9. graphene preparation method according to claim 8, is characterized in that: the crystal formation of described SiC substrate adopts 4H-SiC, 6H-SiC or 3C-SiC.
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| CN105990091B (en) * | 2015-01-29 | 2019-01-01 | 中国科学院微电子研究所 | The growing method of graphene |
| CN105174268A (en) * | 2015-09-21 | 2015-12-23 | 中国科学院上海微***与信息技术研究所 | Nanowire and graphene composite material and preparation method thereof |
| CN107437505B (en) * | 2016-05-26 | 2020-04-10 | 上海新昇半导体科技有限公司 | Method of fabricating graphene field effect transistor |
| CN107653446A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院上海微***与信息技术研究所 | A kind of graphene growth method for improving graphene nucleation density |
| CN109055895B (en) * | 2018-07-20 | 2020-09-15 | 中国科学院上海微***与信息技术研究所 | Method for directly preparing graphene quantum dot array on insulating substrate |
| CN109879275A (en) * | 2019-01-30 | 2019-06-14 | 宁波大学 | A kind of method that the concentration of combination germanium prepares graphene with ion implantation technique |
| CN110697696B (en) * | 2019-10-23 | 2021-07-13 | 西安交通大学 | Method for preparing single-layer graphene in large area by utilizing metal intercalation |
| CN111717911B (en) * | 2019-10-28 | 2022-09-02 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene film |
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| CN103247520A (en) * | 2012-02-07 | 2013-08-14 | 中国科学院上海微***与信息技术研究所 | Method for preparing grapheme on basis of controlling ion implantation energy |
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| CN102683183A (en) * | 2012-05-16 | 2012-09-19 | 西安电子科技大学 | Preparation method of graphene nanobelt injecting Si to SiC based on Ni film annealing |
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