CN104787754A - Preparation method of suspended graphene - Google Patents
Preparation method of suspended graphene Download PDFInfo
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- CN104787754A CN104787754A CN201510122914.XA CN201510122914A CN104787754A CN 104787754 A CN104787754 A CN 104787754A CN 201510122914 A CN201510122914 A CN 201510122914A CN 104787754 A CN104787754 A CN 104787754A
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Abstract
The invention provides a preparation method of suspended graphene. The preparation method comprises the following steps: step A, adopting a semiconductor technology to prepare an expected structure on a silicon carbide substrate; step B, in a carbon-rich environment, adopting a high-temperature thermal decomposition method to prepare the suspended graphene. The preparation method is simple in preparation process, free of chemical pollution, and suitable for mechanical and automatic manufacture; the obtained suspended graphene is easier to use.
Description
Technical field
The invention belongs to technical field of semiconductors, particularly relate to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of two-dimensional film having polynuclear plane be made up of carbon atom.Be considered to have broad application prospects in various fields such as information technology, semi-conductor, bio-sensing, the energy and environment protection due to the physical strength of the electronic mobility of its excellence, the thickness of monoatomic layer and superelevation.
In technical field of semiconductors, Graphene is considered to because of the electric property of its excellence to replace the base mateiral that silicon becomes generation semiconductor technology.Traditional Graphene generally grows on insulating substrate or transfers on insulating substrate, then for the preparation of functional device.But the interaction of Graphene and substrate can reduce the electronic mobility of Graphene, and then reduce the performance of Graphene functional device.In addition, Graphene has broad application prospects in molecular detection field, prepares the step that high-quality unsettled Graphene is its key.Such as, the nanoporous based on Graphene is considered to potential and is applied to bio-sensing field, particularly DNA sequencing technology of future generation.Therefore, prepare unsettled Graphene is one of direction of association area internal medicine technician effort always.
At present, unsettled Graphene mainly transfer method or etching method is prepared.The Graphene of preparation is transferred on the substrate of structure by the former, forms unsettled functional zone; Substrate etching below Graphene is fallen by latter, obtains unsettled Graphene.The preparation process of these two kinds of methods is loaded down with trivial details, and wherein inevitable chemical pollution can have influence on the Potential performance of unsettled Graphene.
Summary of the invention
Therefore, the object of the invention is to the defect overcoming above-mentioned prior art, a kind of simple, safety be provided, controllably prepare the method for the unsettled Graphene of high-quality, comprise the following steps:
Steps A: adopt semiconductor technology to prepare expected structure on silicon carbide substrates;
Step B: under rich carbocyclic ring border, adopts high temperature thermal decomposition legal system for unsettled Graphene.
According to the preparation method of unsettled Graphene of the present invention, preferably, described silicon carbide substrates is 6H-single-crystal silicon carbide or 4H-single-crystal silicon carbide.
According to the preparation method of unsettled Graphene of the present invention, preferably, the shape of described expected structure is circle, the hexa-atomic annular of similar Graphene or letter shapes.
According to the preparation method of unsettled Graphene of the present invention, preferably, described steps A etches expected structure for adopting focused-ion-beam lithography method in described silicon carbide substrates, or described steps A comprises employing litho pattern transfer method or electron beam exposure method will expect that Graphic transitions is to described silicon carbide substrates, then adopts reactive ion etching method to etch corresponding expected structure in described silicon carbide substrates.
According to the preparation method of unsettled Graphene of the present invention, preferably, described steps A also comprises: annealed under hydrogen argon atmosphere by obtained sample.
According to the preparation method of unsettled Graphene of the present invention, preferably, in stepb, adopt plumbago crucible to provide extra carbon source or pass into carbonaceous gas and obtain described rich carbocyclic ring border.
According to the preparation method of unsettled Graphene of the present invention, preferably, described carbonaceous gas is methane.
According to the preparation method of unsettled Graphene of the present invention, preferably, growth temperature and the growth time of described high temperature thermal decomposition method is determined according to the live width of described expected structure.
According to the preparation method of unsettled Graphene of the present invention, preferably, the scope of described growth temperature is 1300 DEG C-1800 DEG C, and the scope of described growth time is 15min-30min.
Present invention also offers a kind of preparation method of nanopore sensor, comprise the steps:
Step 1: adopt semiconductor technology to prepare round tube hole on silicon carbide substrates;
Step 2: under rich carbocyclic ring border, adopts high temperature thermal decomposition legal system for circular unsettled Graphene;
Step 3: adopt transmission electron microscope to prepare nanoporous on the unsettled graphene film of described circle.
Compared with prior art, the invention has the advantages that:
1. the unsettled Graphene prepared by preparation method provided by the invention is at later stages without the need to through process such as chemical reagent, totally pollution-free, decreases the impact of organic impurity on Graphene performance to greatest extent.
2. preparation method provided by the invention is simple, without the need to tedious steps such as transfer or etchings, is more suitable for robotic and automated manufacturing.
3. preparation method provided by the invention is the unsettled Graphene grown in silicon carbide substrates structure, and the effect of non-unsettled region and substrate is stronger, more firmly, is easier to use.
Accompanying drawing explanation
Referring to accompanying drawing, embodiments of the present invention is further illustrated, wherein:
Fig. 1 is the photo of the unsettled Graphene of circle grown on 6H-silicon carbide pore space structure with scanning electronic microscope shooting according to embodiments of the invention 1, and the illustration in the lower right corner is the stereoscan photograph of this hole before growth;
Fig. 2 is the Raman spectrogram of the unsettled Graphene shown in Fig. 1;
Fig. 3 is the photo of the unsettled Graphene of circle with atomic force microscope shooting according to embodiments of the invention 1;
Fig. 4 is the stereoscan photograph of the graphic structure of similar Graphene six-membered ring structure on the 4H-single-crystal silicon carbide substrate according to embodiments of the invention 2;
Fig. 5 is the stereoscan photograph of the graphic structure of English " IOP " printed words on the 6H-single-crystal silicon carbide substrate according to embodiments of the invention 3;
Fig. 6 is the diagrammatic cross-section of the nanopore sensor according to embodiments of the invention 4 preparation.
Embodiment
In order to make object of the present invention, technical scheme and advantage are clearly understood, below in conjunction with accompanying drawing, by specific embodiment, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
The present embodiment provides the preparation method of the unsettled Graphene of a kind of circle, comprising:
Steps A: diameter is that the circle of 1 μm is transferred to 6H-single-crystal silicon carbide substrate by employing litho pattern transfer method, then uses reactive ion etching (RIE) to run through the corresponding borehole structure of substrate (>10 μm) in (0001) face of silicon carbide etching;
Step B: anneal the defect removing silicon carbide substrate surface in the argon gas of 9 pascal's dividing potential drops and the atmosphere of hydrogen of 1 pascal's dividing potential drop;
Step C: adopt plumbago crucible to provide extra carbon source, under rich carbocyclic ring border, keeps 30 minutes, high temperature thermal decomposition 6H-single-crystal silicon carbide extending and growing graphene at 1300 DEG C.In this process, first, silicon carbide substrates grows a layer graphene, then form the carbon atom border identical with borehole structure at borehole structure edge.Secondly, carbon vapor unnecessary in environment can combine with the carbon atom of boundary the film being formed and extend.Final film healing forms complete unsettled graphene film.
Fig. 1 is the stereoscan photograph of the unsettled Graphene of grown circle, and the illustration in the lower right corner is the stereoscan photograph of the pore space structure before growth.
Fig. 2 is the Raman spectrogram of the unsettled Graphene of the circle shown in Fig. 1.Therefrom can clearly be seen that 1600cm
-1and 2700cm
-1the feature G peak of neighbouring peak position Graphene and 2D peak.
Fig. 3 is the atomic force microscope photo of circular unsettled Graphene.Dotted line is the altitude curve of the drawn part of horizontal solid line on substrate.Under the pressure of probe, the deformation amplitude of Graphene is about 35nm.
Embodiment 2
The present embodiment provides a kind of preparation method of unsettled Graphene of similar Graphene six-membered ring structure, comprising:
Steps A: adopt focused-ion-beam lithography method to etch the graphic structure of similar Graphene six-membered ring structure on 4H-single-crystal silicon carbide substrate, wherein circular port diameter is about 2 μm, and line thickness is about 800nm, and constructional depth is about 3 μm;
Step B: adopt plumbago crucible to provide extra carbon source, under rich carbocyclic ring border, keeps 20 minutes, high temperature thermal decomposition 4H-single-crystal silicon carbide extending and growing graphene at 1600 DEG C.In this process, first, silicon carbide substrates grows a layer graphene, then form the carbon atom border identical with this structure at the graphic structure edge that steps A obtains.Secondly, carbon vapor unnecessary in environment can combine with the carbon atom of boundary the film being formed and extend.Final film healing forms complete unsettled graphene film.
Figure 4 shows that the scanning electron microscopic picture of the graphic structure of similar Graphene six-membered ring structure on 4H-single-crystal silicon carbide substrate.
Embodiment 3
The present embodiment provides the preparation method of the unsettled Graphene of a kind of English alphabet " IOP " printed words, comprising:
Steps A: English alphabet " IOP " printed words adopting litho pattern transfer method line thickness to be about 800nm are transferred to 6H-single-crystal silicon carbide substrate, then use reactive ion etching (RIE) to etch the corresponding construction of the degree of depth about 3 μm on 6H-single-crystal silicon carbide substrate.
Step B: anneal in the argon gas of 9 pascal's dividing potential drops and the atmosphere of hydrogen of 1 pascal's dividing potential drop;
Step C: pass into methane gas and prepare rich carbocyclic ring border, keeps 20 minutes, high temperature thermal decomposition 6H-single-crystal silicon carbide extending and growing graphene at 1300 DEG C.In this process, first, silicon carbide substrates grows a layer graphene, then form the carbon atom border identical with this structure at the corresponding construction edge that steps A obtains.Secondly, carbon vapor unnecessary in environment can combine with the carbon atom of boundary the film being formed and extend.Final film healing forms complete unsettled graphene film.
Figure 5 shows that the scanning electron microscopic picture of the graphic structure of English " IOP " printed words on 6H-single-crystal silicon carbide substrate.
Embodiment 4
The present embodiment provides a kind of preparation method of nanopore sensor, comprises the steps:
Step 1: adopt reaction ion deep etching micro-processing method 4H-silicon carbide substrates is thinned to about 10 μm thick;
Step 2: adopt focused-ion-beam lithography method to prepare the round tube hole in about 1 μm, aperture in these 10 μm thick 4H-silicon carbide substrates;
Step 3: adopt plumbago crucible to provide extra carbon source, under rich carbocyclic ring border, keeps 30 minutes at 1300 DEG C, the circular unsettled graphene film of high temperature thermal decomposition single-crystal silicon carbide epitaxy;
Step 4: adopt transmission electron microscope to prepare the nanoporous of aperture≤5nm on unsettled graphene film.
It will be understood by those skilled in the art that in the preparation method of this nanopore sensor, if the thickness of silicon carbide substrates is suitable, so the reduction steps of step 1 can omit; Alternately, if the thickness G reatT.GreaT.GT10 μm of silicon carbide substrates, suitably extend the etching time of step 2, also can prepare round tube hole in silicon carbide substrates.Other semiconductor technologies such as litho pattern transfer method or electron beam exposure method can be adopted to prepare round tube hole, and the aperture of round tube hole is also not limited to 1 μm.
Fig. 6 shows the diagrammatic cross-section of obtained nanopore sensor, comprises the nanoporous 4 on the round tube hole 2 in silicon carbide substrates 1, silicon carbide substrates, the unsettled graphene layer 3 covering round tube hole 2 and unsettled graphene layer 3.The substrate of this nanopore sensor is silicon carbide, and Graphene is growth in situ, and chemical pollution is little, so performance is more excellent.
According to other embodiments of the invention, in the preparation method of unsettled Graphene, the figure be transferred on substrate is other the expection figure arbitrarily such as square, bar shaped, matrix-like;
According to other embodiments of the invention, can adopt semiconductor technology well known in the art on substrate, prepare the structure of expection;
According to other embodiments of the invention, in the preparation method of unsettled Graphene, the degree of depth of the corresponding expected structure of etching is greater than 1 μm and is less than or equal to substrate thickness;
According to other embodiments of the invention, the growth temperature of high temperature thermal decomposition method and growth time are determined according to the live width of expected structure.Preferably, expected structure live width≤5 μm, the scope of growth temperature is 1300 DEG C-1800 DEG C, and the scope of growth time is 15min-30min;
According to other embodiments of the invention, pass into other carbonaceous gass arbitrarily well known in the art and prepare rich carbocyclic ring border.
Although the present invention is described by preferred embodiment, but the present invention is not limited to embodiment as described herein, also comprises done various change and change without departing from the present invention.
Claims (10)
1. a preparation method for unsettled Graphene, comprises the following steps:
Steps A: adopt semiconductor technology to prepare expected structure on silicon carbide substrates;
Step B: under rich carbocyclic ring border, adopts high temperature thermal decomposition legal system for unsettled Graphene.
2. preparation method according to claim 1, is characterized in that: described silicon carbide substrates is 6H-single-crystal silicon carbide or 4H-single-crystal silicon carbide.
3. preparation method according to claim 1, is characterized in that: the shape of described expected structure is circle, the hexa-atomic annular of similar Graphene or letter shapes.
4. preparation method according to claim 1, it is characterized in that: described steps A etches expected structure for adopting focused-ion-beam lithography method in described silicon carbide substrates, or described steps A comprises employing litho pattern transfer method or electron beam exposure method will expect that Graphic transitions is to described silicon carbide substrates, then adopts reactive ion etching method to etch corresponding expected structure in described silicon carbide substrates.
5. according to the preparation method one of claim 1-4 Suo Shu, described steps A also comprises: annealed under hydrogen argon atmosphere by obtained sample.
6. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that: in stepb, adopt plumbago crucible to provide extra carbon source or pass into carbonaceous gas and obtain described rich carbocyclic ring border.
7. preparation method according to claim 6, is characterized in that: described carbonaceous gas is methane.
8. preparation method according to claim 1, is characterized in that: growth temperature and the growth time of determining described high temperature thermal decomposition method according to the live width of described expected structure.
9. preparation method according to claim 8, is characterized in that: the scope of described growth temperature is 1300 DEG C-1800 DEG C, and the scope of described growth time is 15min-30min.
10. a preparation method for nanopore sensor, comprises the steps:
Step 1: adopt semiconductor technology to prepare round tube hole on silicon carbide substrates;
Step 2: under rich carbocyclic ring border, adopts high temperature thermal decomposition legal system for circular unsettled Graphene;
Step 3: adopt transmission electron microscope to prepare nanoporous on the unsettled graphene film of described circle.
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Cited By (3)
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| CN106198435A (en) * | 2016-07-28 | 2016-12-07 | 国家纳米科学中心 | A kind of preparation method for infrared spectrum substrate |
| CN106206776A (en) * | 2016-07-28 | 2016-12-07 | 国家纳米科学中心 | A kind of substrate for infrared spectrum |
| CN109437176A (en) * | 2018-11-20 | 2019-03-08 | 北京大学 | A kind of method that selective etch growth substrate prepares hanging graphene support membrane |
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| CN109437176A (en) * | 2018-11-20 | 2019-03-08 | 北京大学 | A kind of method that selective etch growth substrate prepares hanging graphene support membrane |
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Effective date of registration: 20180608 Address after: 518000 Shenzhen, Guangdong Pingshan New District, Pingshan street, Jinlong Avenue, Baoshan Road, 16, B 8 strategic building. Patentee after: Shenzhen City Meryl nanopore Technology Co. Ltd. Address before: 100190 South Third Street, Zhongguancun, Haidian District, Haidian District, Beijing Patentee before: Research Institute of Physics, Chinese Academy of Sciences |
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