CN103172059A - Method for preparing graphene - Google Patents
Method for preparing graphene Download PDFInfo
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- CN103172059A CN103172059A CN2013100954477A CN201310095447A CN103172059A CN 103172059 A CN103172059 A CN 103172059A CN 2013100954477 A CN2013100954477 A CN 2013100954477A CN 201310095447 A CN201310095447 A CN 201310095447A CN 103172059 A CN103172059 A CN 103172059A
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Abstract
The invention discloses a method for preparing graphene. The method comprises the steps of: preparing a graphene layer on a first-class metal catalyst layer; mixing second-class metal into the first-class metal catalyst layer to form alloy, wherein the melting point of the alloy is less than the melting point of first-class metal; and mixing the second-class metal into the first-class metal catalyst layer to form the alloy so as to reduce the melting point of the catalyst layer. The catalyst layer can volatilize at the temperature which cannot damage a graphene structure, the metal catalyst layer below the prepared graphene layer is changed into a series of incontinuous metal points, and the graphene layer is contacted with partial metal points on a bottom substrate, is basically in a suspension state and is easy to transfer.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, relate in particular to a kind of method for preparing the Graphene that is easy to shift.
Background technology
Since Geim in 2004 has successfully 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 that forms of monolayer carbon atom, and outstanding optics, electricity, calorifics and mechanical property are arranged, and shows huge application potential at nano electron device, sensor and field of photoelectric devices.The Main Means of preparation Graphene has at present: mechanical phonograph recorder separation, oxidation reduction process and chemical Vapor deposition process (Chemical Vapor Deposition, CVD).The CVD method is to utilize the hydrocarbon gas such as methane, ethene at high temperature to be adsorbed on the metal catalyst substrate surface, and the method for decomposing, recombinating the formation Graphene under the metal catalytic effect.The CVD method can prepare the larger area Graphene than mechanical separation and oxidation reduction process, therefore receives scientist's especially concern.
But itself also has very large defective this method.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 ℃, 1453 ℃, and the temperature commonly used of growing graphene is 900 ~ 1000 ℃, therefore after growth finishes, metal catalyst does not have loss substantially, and the Graphene of growth is attached on metal catalyst fully.The Graphene practical application of this method preparation also to be needed an extra transfer step on device.Shifting usually need to be at FeCl
3In solution, immersion etched away metal substrate in nearly ten hours, and then fished for, dries with target substrate.This process time and effort consuming, and wayward, also can introduce tramp material, even cause the destruction of graphene-structured.These impurity and defective are likely the arch-criminal who causes the Graphene electric property to descend.Therefore scientists is attempted to seek and can be grown easy transfer Graphene or directly Graphene is grown in method on target substrate.
Summary of the invention
For problems of the prior art, the purpose of this invention is to provide a kind of method for preparing the Graphene that is easy to shift.
For achieving the above object, the invention provides following technical scheme:
A kind of preparation method of Graphene, the method comprises: S1, preparation carbon film on first kind metal catalyst layer; 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.
Form alloy by mix the Equations of The Second Kind metal in first kind metal catalyst layer, to reduce the fusing point of catalyst layer; At the temperature of not destroying graphene-structured, catalyst layer can volatilize, and below the graphene layer after preparation is completed, metal catalyst layer becomes a series of discontinuous metal dots, and Graphene only contacts with part underlying metal point, substantially be in vacant state, thereby 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 to be at deionized water for ultrasonic 30s, and Graphene just comes off from substrate; Fish for, dry with target substrate again, Graphene can be transferred to target substrate.Method provided by the invention has been simplified the loaded down with trivial details transfer step that traditional preparation method brings, and compares simultaneously traditional method, and transfer Graphene provided by the invention can keep the complete of shape and structure, alleviates in transfer process the damage and pollution to Graphene.
Description of drawings
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or description of the Prior Art, apparently, the accompanying drawing that the following describes is only some embodiment that put down in writing in the application, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the preparation method's of the present invention's one specific embodiment Graphene schematic flow sheet;
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene for preparing of the present invention's one specific embodiment;
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 transferring on silicon chip for as shown in Figure 2 Graphene;
Fig. 5 is the Raman spectral image of Graphene as shown in Figure 2.
Embodiment
The purpose of this invention is to provide a kind of method for preparing the Graphene that is easy to shift.
For achieving the above object, the invention provides following technical scheme:
A kind of preparation method of Graphene, the method comprises: S1, preparation carbon film on first kind metal catalyst layer; 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.
Form alloy by mix the Equations of The Second Kind metal in first kind metal catalyst layer, to reduce the fusing point of catalyst layer; At the temperature of not destroying graphene-structured, catalyst layer can volatilize, and below the graphene layer after preparation is completed, metal catalyst layer becomes a series of discontinuous metal dots, and Graphene only contacts with part underlying metal point, substantially be in vacant state, thereby very easily in transfer.
Fig. 1 shows the schematic flow sheet of the preparation Graphene of this specific embodiment; Concrete preparation method is:
S101, the preparation of metal catalyst layer: preparation 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 for 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 for preparing is 100 ~ 500nm;
S102, carbon thin film technology: utilize vacuum sputtering coating instrument sputter one deck carbon film on above-mentioned metal catalyst layer; The thickness of described carbon film is 2 ~ 10nm;
S103, the preparation of Equations of The Second Kind source metal: dripping the Equations of The Second Kind molten drop 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 that forms the Ga-Ni alloy, and the Ga steam that at high temperature forms and the catalyst metal Ni on substrate form alloy;
S104, sample is placed: the first substrate and the second substrate are positioned in Reaktionsofen; The order of placing is: along the direction that air-flow is advanced, the second substrate is positioned at the place ahead 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: the temperature in the rising reaction chamber is to specified temp, insulation annealing for some time; Wherein, described specific range of temperatures is 700 ~ 1000 ℃, and described soaking time scope is 5 ~ 30 minutes;
S107, cooling: quick cooling reaction chamber, be down to room temperature;
S108, supersound process: will be placed on deionized water for ultrasonic with the sample of graphene film 0.5 ~ 5 minute, graphene layer is separated with the alloy layer of its below;
S109 fishes for: fish for clean target substrate.
The below is to the explanation that is further explained in above steps.
That restructuring forms the catalyzer of Graphene to Ni as carbon atom during at high temperature in the purpose of metallizing Ni on substrate in described step S101; Carbon atom at first at high temperature dissolves and enters metal Ni, and then carbon atom is separated out again when cooling, and forms Graphene under the katalysis of Ni.
The agraphitic carbon film of sputter in described step S102 provides as the carbon source of growing graphene the carbon atom that forms Graphene; The agraphitic carbon film of sputter herein can not surpass 10nm.Because provide carbon atom too much, the Graphene number of plies of growth is blocked up, will lose the characteristic of Graphene.
Drip metal Ga in described step S103, as the gallium source that forms the Ga-Ni alloy, the Ga steam that at high temperature forms and the catalyst metal Ni on substrate form alloy.
To note the position that sample is placed in described step S104, must first place sample with the Ga source along the direction of gas flow purging, place again the sample with metal Ni, Ga steam could form alloy with the metal Ni that locates on the leeward like this, otherwise Ga steam will be taken away and can not fully contact with the Ni metal by air-flow.
In described step S106, in high-temperature annealing process, agraphitic carbon decomposes under the katalysis of metal, dissolves, recombinates and forms Graphene, and when forming Graphene, alloy catalytic is in constantly evaporation disappearance.Temperature can not be too low herein, and scope is 700 ~ 1000 degree, and the too low metal of temperature can't effectively evaporate.
In described step S108 the purpose of deionized water for ultrasonic be with graphene film with below alloy substrate break away from; Because alloy evaporates substantially, only more remaining metal dots, Graphene only contacts with part metals point, substantially is in suspension status; Thereby supersound process 0.5 ~ 5min can make it to separate with the below alloy.
In described step S109, as long as fish for clean target substrate, Graphene just is attached on target substrate.
Graphene provided by the invention does not need the FeCl of nearly ten hours
3The etching process of solution only need to be at deionized water for ultrasonic 30s, and Graphene just comes off from substrate; Fish for, dry with target substrate again, Graphene can be transferred to target substrate.Method provided by the invention has been simplified the loaded down with trivial details transfer step that traditional preparation method brings, and compares simultaneously traditional method, and transfer Graphene provided by the invention can keep the complete of shape and structure, alleviates in transfer process the damage and pollution to Graphene.
Next provide a concrete embodiment of the present invention, consult Fig. 1, this embodiment concrete operation step is:
1) get a SiO
2/ Si sheet is designated as silicon chip No. 1, utilizes electron beam evaporation at SiO
2Surface evaporation one deck 300nm metalNicatalyst;
2) utilize sputter coating instrument sputter thickness on the metalNicatalyst layer to be 6nm agraphitic carbon film;
3) get another SiO
2/ Si sheet is designated as silicon chip No. 2, drips a dropping liquid attitude gallium metal drop thereon;
4) along the air-flow direct of travel take 2, No. 1 as the order sample is put into reaction chamber;
5) pass into 2slm Ar gas, 0.2 slm H in normal pressure downhill reaction chamber
2, and heat up with the speed of 5 ℃/min;
6) reach 950 ℃ after, be incubated 20min under 950 ℃;
7) be down to room temperature; The final circular graphene sheet layer that obtains diameter 200 ~ 500um.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene for preparing of above specific embodiment; As can be seen from Figure 2 continuous 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 separates substantially with underlying metal as can be seen from Figure 3, only has part position and below metallic contact, thereby is very easy to shift.
Prepared Graphene be transferred to target substrate is, also will carry out following processing:
8) processing 30s in deionized water for ultrasonic comes off Graphene;
9) with clean SiO
2/ Si sheet is fished for, is dried.
Scanning electron microscope image after transfer such as Fig. 4, Graphene can keep perfectly round-shaped; This tranfer system has been simplified the loaded down with trivial details step of traditional method greatly, has reduced destruction and pollution to Graphene.
Fig. 5 is the Raman spectral image of the Graphene for preparing of above specific embodiment, can judge by force that from peak position, peak shape, peak prepared Graphene is approximately 5 layers.
Need to prove, in this article, relational terms such as the first and second grades only is used for an entity or operation are separated with another entity or operational zone, and not necessarily requires or hint and have the relation of any this reality or sequentially between these entities or operation.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thereby make the process, method, article or the equipment that comprise a series of key elements not only comprise those key elements, but also comprise other key elements of clearly not listing, or also be included as the intrinsic key element of this process, method, article or equipment.In the situation that not more restrictions, the key element that is limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment that comprises described key element and also have other identical element.
The above is only the embodiment that the application enumerates; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the application's protection domain.
Claims (9)
1. the preparation method of a Graphene, the method comprises:
S1, on the first kind metal catalyst layer preparation carbon 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.
2. the preparation method of Graphene according to claim 1, it is characterized in that, chemical vapor deposition method is adopted in the described evaporation of step S1, S2, and its processing condition are: in the mixed atmosphere of rare gas element and hydrogen, and carried out insulation annealing 5 ~ 30 minutes under the high temperature of 700 ~ 1000 ° of C.
3. the preparation method of Graphene according to claim 2, is characterized in that, the flow range of rare gas element is 1000 ~ 2000 slm; The flow range of hydrogen is 100 ~ 500 slm.
4. the preparation method of Graphene according to claim 1, is characterized in that, described first kind metal catalyst layer is Ni.
5. the preparation method of according to claim 1 or 4 described Graphenes, is characterized in that, described Equations of The Second Kind metal is Ga.
6. 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.
7. the preparation method of according to claim 1 or 6 described Graphenes, is characterized in that, the method for preparing first kind metal catalyst layer comprises one of them of electron beam evaporation, magnetron sputtering and pulsed laser deposition.
8. the preparation method of Graphene according to claim 5, is characterized in that, the thickness of described carbon film is 2 ~ 10nm.
9. the preparation method of Graphene according to claim 1, is characterized in that, the method also comprises step: deionized water for ultrasonic 0.5 ~ 5 minute, graphene layer is separated with the alloy layer of its below graphene layer.
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| CN106276863A (en) * | 2015-05-12 | 2017-01-04 | 武汉大学 | A kind of method shifting Graphene |
| CN106573780A (en) * | 2014-09-09 | 2017-04-19 | 东北泰克诺亚奇股份有限公司 | Method for producing porous graphite, and porous graphite |
| CN112730558A (en) * | 2020-12-24 | 2021-04-30 | 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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| 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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