CN103172059B - The preparation method of Graphene - Google Patents
The preparation method of Graphene Download PDFInfo
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- CN103172059B CN103172059B CN201310095447.7A CN201310095447A CN103172059B CN 103172059 B CN103172059 B CN 103172059B CN 201310095447 A CN201310095447 A CN 201310095447A CN 103172059 B CN103172059 B CN 103172059B
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Abstract
The invention discloses a kind of preparation method of Graphene, the method comprises: in first kind metal catalyst layer, prepare graphene layer; And, in first kind metal catalyst layer, mix Equations of The Second Kind metal form alloy, make the fusing point of described alloy lower than the fusing point of first kind metal; Alloy is formed, to reduce the fusing point of catalyst layer by mixing Equations of The Second Kind metal in first kind metal catalyst layer; At the temperature not destroying graphene-structured, catalyst layer can volatilize, and the graphene layer lower-lying metal catalyst layer after having prepared becomes a series of discontinuous metal dots, graphene layer only with the Metal Point Contact at the bottom of part back lining, substantially vacant state is in, thus very easily in transfer.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, particularly relate to a kind of method preparing the Graphene being easy to transfer.
Background technology
Since Geim in 2004 have successfully been obtained single-layer graphene by mechanical phonograph recorder separation, Graphene has just started research boom widely.Graphene is by the tightly packed two-dimentional honeycomb structure of monolayer carbon atom, has outstanding optics, electricity, calorifics and mechanical property, shows huge application potential at nano electron device, sensor and field of photoelectric devices.The Main Means preparing Graphene at present has: mechanical phonograph recorder separation, oxidation reduction process and chemical Vapor deposition process (Chemical Vapor Deposition, CVD).CVD utilizes the hydrocarbon gas such as methane, ethene to be at high temperature adsorbed on metal catalyst substrate surface, and the method for decomposition under metal catalytic effect, restructuring formation Graphene.CVD can prepare the Graphene of larger area compared to mechanical separation and oxidation reduction process, therefore receives the especially concern of scientist.
But this method itself also has very large defect.General CVD method adopts the magnesium-yttrium-transition metals such as Cu, Ni as catalyzer, because the fusing point of Cu, Ni metal is very high, be respectively 1083 DEG C, 1453 DEG C, and the conventional temperature of growing graphene is 900 ~ 1000 DEG C, therefore after growth terminates, metal catalyst does not lose substantially, and the Graphene of growth is attached on metal catalyst completely.The Graphene practical application this method will prepared also needs an extra transfer step on device.Transfer needs usually at FeCl
3soak in solution and etch away metal substrate in nearly ten hours, and then fish for by target substrate, dry.This process time and effort consuming, and wayward, also can introduce tramp material, even cause the destruction of graphene-structured.These defect struchures are likely the arch-criminal causing Graphene electric property to decline.Therefore scientists is attempted to find and can be grown easily transfer Graphene or directly by the method for graphene growth in target substrate.
Summary of the invention
For problems of the prior art, the object of this invention is to provide a kind of method preparing the Graphene being easy to transfer.
For achieving the above object, the invention provides following technical scheme:
A preparation method for Graphene, the method comprises: S1, in first kind metal catalyst layer, prepare C film; S2, evaporation Equations of The Second Kind metal make it be doped into described first kind metal catalyst layer to form alloy, and the fusing point of described alloy is less than the fusing point of described first kind metal catalyst; S3, evaporated alloying obtain graphene layer.
Wherein, the material of described first kind metal catalyst layer is selected from one of them of Ni, Cu, Co, Pt, Ir, Ru and Fe, and described Equations of The Second Kind metal is selected from one of them of Ga, Bi, Sn, Pb and In.
Alloy is formed, to reduce the fusing point of catalyst layer by mixing Equations of The Second Kind metal in first kind metal catalyst layer; At the temperature not destroying graphene-structured, catalyst layer can volatilize, and the graphene layer lower-lying metal catalyst layer after having prepared becomes a series of discontinuous metal dots, Graphene only with part underlying metal point cantact, substantially vacant state is in, thus very easily in transfer.
The Graphene that the present invention prepares does not need the FeCl of nearly ten hours
3the etching process of solution, only need ultrasonic 30s in deionized water, Graphene just comes off from substrate; Fish for by target substrate, dry again, Graphene can be transferred to target substrate.Method provided by the invention, simplifies the loaded down with trivial details transfer step that traditional preparation methods brings, compares traditional method simultaneously, and transfer Graphene provided by the invention can keep the complete of shape and structure, alleviates the damage and pollution to Graphene in transfer process.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the application, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schematic flow sheet of the preparation method of the present invention one specific embodiment Graphene;
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene that the present invention one specific embodiment prepares;
Fig. 3 is the scanning electron microscope vertical view of Graphene rotation 80 degree as shown in Figure 2;
Fig. 4 is the scanning electron microscope image after Graphene is as shown in Figure 2 transferred on silicon chip;
Fig. 5 is the Raman spectral image of Graphene as shown in Figure 2.
Embodiment
The object of this invention is to provide a kind of method preparing the Graphene being easy to transfer.
For achieving the above object, the invention provides following technical scheme:
A preparation method for Graphene, the method comprises: S1, in first kind metal catalyst layer, prepare C film; S2, evaporation Equations of The Second Kind metal make it be doped into described first kind metal catalyst layer to form alloy, and the fusing point of described alloy is less than the fusing point of described first kind metal catalyst; S3, evaporated alloying obtain graphene layer.
Wherein, the material of described first kind metal catalyst layer is selected from one of them of Ni, Cu, Co, Pt, Ir, Ru and Fe, and described Equations of The Second Kind metal is selected from one of them of Ga, Bi, Sn, Pb and In.
Alloy is formed, to reduce the fusing point of catalyst layer by mixing Equations of The Second Kind metal in first kind metal catalyst layer; At the temperature not destroying graphene-structured, catalyst layer can volatilize, and the graphene layer lower-lying metal catalyst layer after having prepared becomes a series of discontinuous metal dots, Graphene only with part underlying metal point cantact, substantially vacant state is in, thus very easily in transfer.
Fig. 1 shows the schematic flow sheet preparing Graphene of this specific embodiment; Concrete preparation method is:
S101, the preparation of metal catalyst layer: prepare first kind metal catalyst layer on the first substrate; Wherein said substrate is SiO
2/ Si substrate; The material of the first kind metal catalyst layer in the present embodiment is Ni; The method preparing first kind metal catalyst layer comprises one of them of electron beam evaporation, magnetron sputtering and pulsed laser deposition; The thickness of the first kind metal catalyst layer prepared is 100 ~ 500nm;
S102, the preparation of C film: utilize vacuum sputtering coating instrument to sputter one deck C film in above-mentioned metal catalyst layer; The thickness of described C film is 2 ~ 10nm;
S103, the preparation of Equations of The Second Kind source metal: Equations of The Second Kind molten drop on dripping on the second substrate; Wherein said substrate is SiO
2/ Si substrate; The material of the Equations of The Second Kind metal in the present embodiment is Ga; Molten drop Ga is as the gallium source forming Ga-Ni alloy, and the catalyst metal Ni on the Ga steam at high temperature formed and substrate forms alloy;
S104, sample is placed: be positioned in Reaktionsofen by the first substrate and the second substrate; The order of placing is: the direction of advancing along air-flow, and the second substrate is positioned at the front of the first substrate;
S105, gas purging: pass into rare gas element and hydrogen purge reaction chamber and keep air-flow; Wherein, the flow range of rare gas element is 1000 ~ 2000 mark condition milliliter per minutes; The flow range of hydrogen is 100 ~ 500 mark condition milliliter per minutes;
S106, annealing: raise temperature in reaction chamber to specified temp, insulation annealing for some time; Wherein, described specific range of temperatures is 700 ~ 1000 DEG C, and described soaking time scope is 5 ~ 30 minutes;
S107, cooling: cool reaction chamber fast, be down to room temperature;
S108, supersound process: the sample with graphene film is placed on deionized water for ultrasonic 0.5 ~ 5 minute, makes graphene layer be separated with the alloy layer below it;
S109, fishes for: fish for by clean target substrate.
Below to being further explained in above steps.
In described step S101, on substrate, the object of metallizing Ni is Ni forms Graphene as carbon atom restructuring catalyzer when high temperature; Carbon atom first at high temperature dissolves and enters W metal, and then when lowering the temperature, carbon atom is separated out again, and forms Graphene under the katalysis of Ni.
The agraphitic carbon film sputtered in described step S102, as the carbon source of growing graphene, provides the carbon atom of composition Graphene; The agraphitic carbon film herein sputtered can not more than 10nm.Because provide carbon atom too much, the Graphene number of plies of growth is blocked up, will lose the characteristic of Graphene.
In described step S103 drip metal Ga, as the gallium source forming Ga-Ni alloy, the catalyst metal Ni on the Ga steam at high temperature formed and substrate forms alloy.
The position that sample is placed will be noted in described step S104, the sample with Ga source first must be placed along the direction of gas flow purging, place the sample with W metal again, such Ga steam could form alloy with place's W metal on the leeward, otherwise Ga steam will be taken away by air-flow and fully can not contact with Ni metal.
In described step S106 in high-temperature annealing process, agraphitic carbon decomposes under the katalysis of metal, dissolve, recombinating forms Graphene, and while formation Graphene, alloy catalytic is constantly evaporating disappearance.Temperature can not be too low herein, and scope is 700 ~ 1000 degree, and the too low metal of temperature cannot effectively evaporate.
Object ultrasonic in deionized water in described step S108 is departed from the alloy substrate of graphene film and below; Because alloy evaporates substantially, only more remaining metal dots, Graphene only and part metals point cantact, is in suspension status substantially; Thus supersound process 0.5 ~ 5min can make it to be separated with below alloy.
As long as fish for by clean target substrate in described step S109, Graphene is just attached in target substrate.
Graphene provided by the invention does not need the FeCl of nearly ten hours
3the etching process of solution, only need ultrasonic 30s in deionized water, Graphene just comes off from substrate; Fish for by target substrate, dry again, Graphene can be transferred to target substrate.Method provided by the invention, simplifies the loaded down with trivial details transfer step that traditional preparation methods brings, compares traditional method simultaneously, and transfer Graphene provided by the invention can keep the complete of shape and structure, alleviates the damage and pollution to Graphene in transfer process.
Next provide a concrete embodiment of the present invention, consult Fig. 1, this embodiment concrete operation step is:
1) SiO is got
2/ Si sheet, is designated as No. 1 silicon chip, utilizes electron beam evaporation at SiO
2surface evaporation one deck 300nm metalNicatalyst;
2) sputter coating instrument is utilized on metalNicatalyst layer, to sputter thickness for 6nm agraphitic carbon film;
3) another SiO is got
2/ Si sheet, is designated as No. 2 silicon chips, drips a dropping liquid state gallium metal drop thereon;
4) along air-flow direct of travel with 2, No. 1 for order sample is put into reaction chamber;
5) 2slm Ar gas, 0.2 slm H is passed into reaction chamber at ambient pressure
2, and heat up with the speed of 5 DEG C/min;
6), after reaching 950 DEG C, at 950 DEG C, 20min is incubated;
7) room temperature is down to; The circular graphitic alkene lamella of final acquisition diameter 200 ~ 500um.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene that above specific embodiment prepares; As can be seen from Figure 2 continuous print metal catalyst layer has become a series of discontinuous metal dots.
Fig. 3 is the scanning electron microscope vertical view of Graphene rotation 80 degree as shown in Figure 2; Graphene is separated substantially with underlying metal as can be seen from Figure 3, only has portion to contact with lower-lying metal, is thus very easy to transfer.
Prepared Graphene be transferred to target substrate is also will carry out following process:
8) supersound process 30s makes Graphene come off in deionized water;
9) with clean SiO
2/ Si sheet is fished for, is dried.
Scanning electron microscope image after transfer is as Fig. 4, and Graphene can keep perfectly round-shaped; This tranfer system enormously simplify the tedious steps of traditional method, reduces the destruction to Graphene and pollution.
Fig. 5 is the Raman spectral image of the Graphene that above specific embodiment prepares, and can judge by force that prepared Graphene is approximately 5 layers from peak position, peak shape, peak.
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operational zone, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the embodiment that the application enumerates; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the protection domain of the application.
Claims (8)
1. a preparation method for Graphene, the method comprises:
S1, in first kind metal catalyst layer, prepare C film by sputtering method, the material of described first kind metal catalyst layer is selected from one of them of Ni, Cu, Co, Pt, Ir, Ru and Fe;
S2, evaporation Equations of The Second Kind metal make it be doped into described first kind metal catalyst layer to form alloy, and the fusing point of described alloy is less than the fusing point of described first kind metal catalyst, and described Equations of The Second Kind metal is selected from one of them of Ga, Bi, Sn, Pb and In;
S3, at 700 ~ 1000 temperature evaporated alloying obtain graphene layer, described evaporation adopts chemical vapor deposition method, its processing condition are: in the mixed atmosphere of rare gas element and hydrogen, and carry out insulation annealing 5 ~ 30 minutes under the high temperature of 700 ~ 1000 ° of C.
2. the preparation method of Graphene according to claim 1, is characterized in that, the flow range of rare gas element is 1000 ~ 2000 slm; The flow range of hydrogen is 100 ~ 500 slm.
3. the preparation method of Graphene according to claim 1, is characterized in that, described first kind metal catalyst layer is Ni.
4. the preparation method of the Graphene according to claim 1 or 3, is characterized in that, described Equations of The Second Kind metal is Ga.
5. the preparation method of Graphene according to claim 1, is characterized in that, the thickness of described first kind metal catalyst layer is 100 ~ 500nm.
6. the preparation method of Graphene according to claim 1 or 5, it is characterized in that, the method preparing first kind metal catalyst layer comprises one of them of electron beam evaporation, magnetron sputtering and pulsed laser deposition.
7. the preparation method of Graphene according to claim 4, is characterized in that, the thickness of described C film is 2 ~ 10nm.
8. the preparation method of Graphene according to claim 1, is characterized in that, the method also comprises step: by graphene layer ultrasonic 0.5 ~ 5 minute in deionized water, graphene layer is separated with the alloy layer below it.
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| KR102003112B1 (en) * | 2014-09-09 | 2019-07-23 | 가부시키가이샤 토호쿠 테크노 아치 | Method for producing porous graphite, and porous graphite |
| CN106276863B (en) * | 2015-05-12 | 2018-05-11 | 武汉大学 | A kind of method for shifting graphene |
| CN112730558B (en) * | 2020-12-24 | 2023-10-31 | 宁波材料所杭州湾研究院 | Ultrasonic-resistant electrode based on diamond/graphene heterojunction and preparation method thereof |
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| KR20110102132A (en) * | 2010-03-09 | 2011-09-16 | 국립대학법인 울산과학기술대학교 산학협력단 | Method for manufacturing graphene, transparent electrode, active layer comprising thereof, display, electronic device, optoelectronic device, solar cell and dye-sensitized solar cell including the electrode or active layer |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102583359A (en) * | 2012-04-01 | 2012-07-18 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene by adopting liquid catalyst aided chemical vapor deposition |
| KR20130000964A (en) * | 2011-06-24 | 2013-01-03 | 삼성전자주식회사 | Method for manufacturing graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110102132A (en) * | 2010-03-09 | 2011-09-16 | 국립대학법인 울산과학기술대학교 산학협력단 | Method for manufacturing graphene, transparent electrode, active layer comprising thereof, display, electronic device, optoelectronic device, solar cell and dye-sensitized solar cell including the electrode or active layer |
| KR20130000964A (en) * | 2011-06-24 | 2013-01-03 | 삼성전자주식회사 | Method for manufacturing graphene |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102583359A (en) * | 2012-04-01 | 2012-07-18 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene by adopting liquid catalyst aided chemical vapor deposition |
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