CN105019030B - Height crystal orientation matching stacked structure of graphene/hexagonal boron nitride and preparation method thereof - Google Patents

Height crystal orientation matching stacked structure of graphene/hexagonal boron nitride and preparation method thereof Download PDF

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CN105019030B
CN105019030B CN201410174485.6A CN201410174485A CN105019030B CN 105019030 B CN105019030 B CN 105019030B CN 201410174485 A CN201410174485 A CN 201410174485A CN 105019030 B CN105019030 B CN 105019030B
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graphene
boron nitride
stacked structure
hexagonal boron
crystal orientation
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CN105019030A (en
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王多明
张广宇
时东霞
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Institute of Physics of CAS
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Abstract

The present invention provides the height crystal orientation of a kind of graphene/hexagonal boron nitride matching stacked structures and preparation method thereof.This method comprises: forming the preliminary stacked structure of graphene/hexagonal boron nitride;Preliminary stacked structure is heat-treated, matches stacked structure to obtain the height crystal orientation of graphene/hexagonal boron nitride.Graphene can rotate on hexagonal boron nitride crystal when based on heat treatment, be conducive to the crystal orientation matching of the two, to obtain having the matched graphene of height perfection crystal orientation/boron nitride stacked structure.This method avoid uncertainties present in mechanical registeration mode in the prior art, and unrelated with the boundary crystal orientation of graphene and hexagonal boron nitride, can be carried out matched the graphene on random boundary and hexagonal boron nitride.In addition, this method processing and manipulation technology are mature, it is applicable not only to graphene/hexagonal boron nitride stacked structure, can also be extended to and prepare in other similar structures, such as graphene/graphite system.

Description

Height crystal orientation matching stacked structure of graphene/hexagonal boron nitride and preparation method thereof
Technical field
The present invention relates to field of nanometer technology, match more particularly to a kind of height crystal orientation of graphene/hexagonal boron nitride Stacked structure and preparation method thereof.
Background technique
Graphene had many excellent properties as two-dimentional carbon material, since the section by Univ Manchester UK in 2004 Since scholar prepares (Science306,666 (2004)), the numerous characteristics of graphene are gradually understood by people.Graphite Alkene can suspend or be adhered on substrate by Van der Waals for, and the characteristic of graphene on various substrates is shown Significant different, this illustrates the importance of the substrate material thin to this atom level.
Hexagonal boron nitride has the surface of atomically flating, and surface is almost without suspension valence link and doping charge density pole Low, showing it can be as the great potential of the substrate of graphene.Graphene material of the people in hexagonal boron nitride as substrate Up to 60,0000cm is observed in material2V-1s-1Mobility and quantum hall effect.Hexagonal boron nitride is as graphene For honeycomb structure, lattice constant has 1.8% difference with graphene, which causes graphene/hexagonal boron nitride to stack knot Structure has Moire fringe to be formed on the surface of graphene.This Moire fringe has large effect, electricity to the energy band of graphene It learns property and shows peculiar superlattices dirac point, in addition, interface is rubbed to the performance such as Raman trait of the other aspects such as graphene Wiping etc. has apparent influence.Meanwhile the size of Moire fringe and the opposite crystal orientation of graphene and hexagonal boron nitride are closely related, Research finds that only close to can just obtain the Morie fringe with larger size when matching, this matched structure of crystal orientation is crystal orientation A kind of good material.Superlattices dirac point in the numerous characteristics such as electrology characteristic of graphene is shown as to be easily observe that, and And such structure shows biggish interface friction and fabulous thermal stability, is conducive to the stable device of processability.Although Structure with matched well has many excellent properties, however preparation method is relatively difficult.People develop at present Method mainly include mechanical transfer method and epitaxial growth method.
The usual crystal orientation of graphene/hexagonal boron nitride stacked structure obtained using mechanical transfer method is random, is difficult control and turns Relative angle when shifting is to reach crystal orientation matching.The method that relative angle is controlled when transfer is only limitted to the graphite with regular borders Alkene and boron nitride, and the graphene and boron nitride for irregularity boundary cannot then be used and use this method, therefore, mechanical transfer method With biggish limitation, turn especially for mechanical transfer to the graphene of nitridation boron surface due to pollution and fold Crystal orientation after shifting is then difficult to change again.
Epitaxial growth method is usually heavy using plasma enhanced chemical vapor i.e. in nitridation boron surface extending and growing graphene Product is being deposited and is being nucleated although the graphene/hexagonal boron nitride stacked structure that this method obtains is matched with perfect crystal orientation During be easy to cause uneven, the graphene grown has more defect, inevitably generates to the performance of material Adverse effect.
Therefore, there is an urgent need to a kind of system of the height crystal orientation matching stacked structure of graphene/hexagonal boron nitride occur at present Preparation Method.
Summary of the invention
The purpose of the present invention is intended to provide the height crystal orientation matching stacked structure and its system of a kind of graphene/hexagonal boron nitride The stacked structure of Preparation Method, this method preparation matches within 1 °, and accuracy is high, and can be by the graphene of arbitrary orientation and six sides The matching of boron nitride crystal orientation,
According to an aspect of the invention, there is provided a kind of height crystal orientation matching of graphene/hexagonal boron nitride stacks knot The preparation method of structure, comprising: form the preliminary stacked structure of graphene/hexagonal boron nitride;Hot place is carried out to preliminary stacked structure Reason matches stacked structure to obtain the height crystal orientation of graphene/hexagonal boron nitride.
Further, before the heat treatment, using the manipulation technology based on scanning probe to the stone in preliminary stacked structure Black alkene is operated, so that preliminary stacked structure pre-matching.
Further, heat treatment includes heating operation, and the heating temperature of heating operation is 600 DEG C~800 DEG C, soaking time It is 10~40 minutes.
Further, the heating rate and drop to carry out high annealing to preliminary stacked structure, when high annealing are heat-treated Warm rate is 5~15 DEG C/min;Preferably 10 DEG C/min.
Further, the step of forming the preliminary stacked structure of graphene/hexagonal boron nitride includes: in hexagonal boron nitride crystalline substance Graphene layer is formed on body, and defect is introduced on graphene layer;Expand defect to obtain mutually discrete graphene block, thus Obtain multiple preliminary stacked structures.
Further, defect is introduced on graphene layer using electron beam lithography and reactive ion oxygen lithographic technique.
Further, the rounded hole of defect, the size of circular hole are 50~800nm.
Further, hydrogen plasma anisotropic etching is used to expand the defect on graphene layer.
Further, the condition of hydrogen plasma anisotropic etching are as follows: temperature is 400 DEG C, and Hydrogen Vapor Pressure is 0.4torr, power 10W, etch rate are 3nm/ minutes.
According to another aspect of the present invention, a kind of matched graphene/hexagonal boron nitride stacking knot of height crystal orientation is provided The structure stacked structure is prepared by any of the above-described kind of preparation method.
It was found by the inventors of the present invention that graphene can rotate on hexagonal boron nitride crystal in heat treatment, the rotation The crystal orientation for turning to be conducive to the two matches, and inventors herein proposes a kind of height for preparing graphene/hexagonal boron nitride based on the phenomenon The method of crystal orientation matching stacked structure.This method is heat-treated preliminary graphene/hexagonal boron nitride stacked structure, passes through The operation so that graphene is matched with hexagonal boron nitride crystal orientation, obtained having the matched graphene of height perfection crystal orientation/ Boron nitride stacked structure.
Using present method avoids the difficulties such as uncertainty present in mechanical registeration mode in the prior art, and And the preparation method is unrelated with the boundary crystal orientation of graphene and hexagonal boron nitride, even if the graphene on random boundary and six side's nitrogen Changing boron also can be carried out perfect matched, it can by the graphene of arbitrary orientation and hexagonal boron nitride crystal orientation matched. In addition, processing of the invention, manipulation technology are more mature, anneal convenient and easy, there is universality, be applicable not only to graphene/six The stacked structure of square boron nitride can also extend in the lamination layer structure for being applied to and preparing other similar matcheds, such as stone Black alkene/graphite system.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter The above and other objects, advantages and features of the present invention.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter. Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is to transfer graphene to the structural representation obtained on hexagonal boron nitride according to an embodiment of the present invention Figure;
Fig. 2 be according to an embodiment of the present invention using after electron beam lithography and reactive ion oxygen etching on graphene Introduce the structural schematic diagram of artifacts;
Fig. 3 be according in an embodiment of the present invention use hydrogen plasma anisotropic etching after obtain have it is discrete Graphene graphene/hexagonal boron nitride preliminary stacked structure schematic diagram;
Fig. 4 is the atomic force microscopy diagram of Fig. 3;
Fig. 5 to Fig. 7 according to the present invention a kind of exemplary embodiments prepare graphene/boron nitride height crystal orientation matching stack The process schematic of structure;Wherein, Fig. 5 to Fig. 6 is the manipulation process schematic diagram for scanning probe, and the arrow in Fig. 5 shows graphite The position and direction that alkene is manipulated;Fig. 6 to Fig. 7, which illustrates rotation caused by high annealing, makes graphene and hexagonal boron nitride The further matched procedure chart of crystal orientation;And
Fig. 8 is the atomic force of the matched stacked structure of the graphene/hexagonal boron nitride obtained after Fig. 7 high temperature is annealed Microscope figure.
Specific embodiment
In order to solve the stacked structure crystal orientation matching for the graphene/hexagonal boron nitride that preparation method in the prior art obtains The problem of spending not high or stacked structure existing defects, the present invention provides a kind of height crystal orientation of graphene/hexagonal boron nitride Match the preparation method of stacked structure.The preparation method includes: the preliminary stacked structure to form graphene/hexagonal boron nitride;It is right Preliminary stacked structure is heat-treated, and matches stacked structure to obtain the height crystal orientation of graphene/hexagonal boron nitride.
In heat treatment, graphene can rotate on hexagonal boron nitride crystal, which is conducive to the crystal orientation of the two Match, a kind of side of height crystal orientation matching stacked structure for preparing graphene/hexagonal boron nitride is inventors herein proposed based on the phenomenon Method is heat-treated preliminary graphene/hexagonal boron nitride stacked structure, by the operation so that graphene and six sides nitrogenize Boron crystal orientation matches, and has obtained having the matched graphene of height perfection crystal orientation/boron nitride stacked structure.
In one embodiment of the invention, the step of forming the preliminary stacked structure of graphene/hexagonal boron nitride include: Graphene layer is formed on hexagonal boron nitride crystal, and defect is introduced on graphene layer;It is mutually discrete to obtain to expand defect Graphene block, to obtain multiple preliminary stacked structures.Generally substrate is first set, such as silica/silicon substrate, by six side's nitrogen Change boron crystal setting on substrate, transfers graphene on hexagonal boron nitride crystal.Specifically it is detailed in Fig. 1 to Fig. 4, Fig. 1 to Fig. 4 In on hexagonal boron nitride discrete graphene formed graphene/hexagonal boron nitride preliminary stacked structure procedure chart.
Specifically, first use instrument and equipment such as adhesive tape by hexagonal boron nitride crystal mechanical stripping to nanoscale dioxy On SiClx/silicon substrate, later by graphene mechanical transfer to hexagonal boron nitride crystal, structure as shown in Figure 1 has been obtained.Turn What is obtained after shifting is the lower graphene/hexagonal boron nitride stacked structure of crystal orientation matching degree.In order to remove some absorption physical property Impurity first anneals the structure 10 hours as 340 DEG C.
It is similar with the situation that graphite layers stack, the thermal stability of stacked structure when stacked structure is matched closer to crystal orientation Better.Therefore, it is necessary to the graphene/hexagonal boron nitride stacked structures to low crystal orientation matching degree to be heat-treated, heat treated Graphene that height crystal orientation occur with hexagonal boron nitride crystal orientation in journey to match.Thus the present invention creatively uses heat treatment Mode make graphene/hexagonal boron nitride stacked structure reach height crystal orientation matching, and then obtained crystal orientation matching 1 ° with Interior perfect graphene/boron nitride stacked structure.This method is unrelated with the boundary crystal orientation of graphene and hexagonal boron nitride, it can By the graphene of arbitrary orientation and hexagonal boron nitride crystal orientation matched, and it is easy to operate, and temperature is easily controllable.
In the preliminary stacked structure for preparing graphene/hexagonal boron nitride, it is contemplated that size and performance issue need pair Entire preliminary stacked structure progress is discrete, i.e., forms multiple discrete graphene blocks on hexagonal boron nitride, form multiple points The preliminary stacked structure of vertical graphene/hexagonal boron nitride.
In a preferred embodiment of the invention, using electron beam lithography and reactive ion oxygen lithographic technique in stone Defect is introduced on black alkene layer.Fig. 2 shows have artifacts on the graphene after electron beam lithography and reactive ion oxygen etching Structure chart.From figure 2 it can be seen that the rounded hole of defect, the size of circular hole is dozens to a few hundred nanometers.
After forming defect on graphene, discrete graphene block, the present invention use expansion defect area in order to obtain Mode reaches the fracture of graphene layer.In a specific embodiment, use hydrogen plasma anisotropic etching to expand Defect on graphene layer.Specifically, the condition of hydrogen plasma anisotropic etching are as follows: temperature is 400 DEG C, and Hydrogen Vapor Pressure is 0.4torr, power 10W, etch rate are 3nm/ minutes.Fig. 3 is using remaining after hydrogen plasma anisotropic etching Discrete graphene block is presented in part, having a size of several hundred nanometers to several microns.Fig. 4 be Fig. 3 in it is discrete after graphene block original Sub- force microscope figure.
From in Fig. 3 and Fig. 4 as can be seen that it is discrete after graphene block be in irregular diamond shaped, these graphene blocks While being usually zigzag (zigzag) structure.As it can be seen that not only available with whole using hydrogen plasma anisotropic etching The graphene block of edging circle, and can be used to process to obtain various other graphenes of atomically flating zigzag borderline structure Nano-pattern, for studying graphene size confinement effect, marginality and the various devices of construction include single electron quantum dot for this Device, field-effect tube device etc. are all a kind of effective methods.
Crystal orientation and mismatch between the discrete graphene block and hexagonal boron nitride obtained after above-mentioned processing, this influence The performances of graphene various aspects, such as thermal stability.The matched graphene/hexagonal boron nitride of height crystal orientation stacks in order to obtain Structure, the present invention use heat treatment mode and then promote graphene to rotate to reach and hexagonal boron nitride crystal orientation matched.Fig. 5 It is the preparation matched graphene of height crystal orientation/boron nitride stacked structure procedure chart to Fig. 7.
There is the graphene/hexagonal boron nitride stacked structure of more perfect matching degree in order to obtain, according to stacked structure crystalline substance It is maximum to interface friction when matching, in a preferred embodiment of the invention, before carrying out heat treatment step to graphene block, The graphene in preliminary stacked structure is operated using the manipulation technology based on scanning probe, so that graphene/six side's nitrogen Change the preliminary stacked structure pre-matching of boron.Wherein, Fig. 5 to Fig. 6 is the manipulation process schematic diagram for scanning probe, the arrow in Fig. 5 It shows the position and direction manipulated to graphene, rotates graphene by manipulation scanning probe, so that its crystal orientation be made to connect Closely matched with hexagonal boron nitride crystal orientation.
Graphene block is operated using the manipulation technology based on scanning probe, approximately as: mainly pass through atom Nanolithographic (nanolithography) function of force microscope is realized, using the silicon needle point (elastic constant: 20 of standard p doping ~80N/m, needle point radius of curvature :~20nm) manipulate sample.Existed by the programmable script setting needle point of control scanning probe The height and horizontal movement route of material surface.Operation based on scanning probe is to contact and push realization with sample by needle point , the rotation of the different directions of manipulation object may be implemented by the active position and direction that change needle point.Graphene block is in needle When being rotated under the promotion of point, when close to matching the case where frictional force noticeably greater than separate matching, therefore, when it is rotated Graphene can eventually stop at closest with the matched crystal orientation of boron nitride.
In a preferred embodiment of the invention, heat treatment includes heating operation, and the heating temperature of heating operation is 600 DEG C~800 DEG C, soaking time is 10~40 minutes.Heating in this temperature range facilitates to the matched graphite of higher crystal orientation Alkene/hexagonal boron nitride stacked structure.Otherwise, if heat treatment temperature is higher than 800 DEG C, it will lead to graphene/boron nitride and stack Structure generation is Texturized, influences the interface friction and thermal stability of the stacked structure, is unfavorable for subsequent prepared device Stability.If heat treatment temperature is lower than 600 DEG C, crystal orientation matching degree can be reduced.
In a preferred embodiment of the invention, in step s3, using high annealing to stone in preliminary stacked structure Black alkene is heat-treated.Fig. 6 to Fig. 7, which shows rotation caused by high annealing, keeps graphene and hexagonal boron nitride crystal orientation further Matched procedure chart;Fig. 8 is that the height crystal orientation of graphene/hexagonal boron nitride in Fig. 7 matches the atomic force microscope of stacked structure Figure.The relative angle that can be seen that graphene/hexagonal boron nitride from the clear Moire fringe in Fig. 8 controls the explanation within 1 ° Stacked structure height crystal orientation matching.Heating rate and rate of temperature fall when high annealing are 5~15 DEG C/min.It is preferred that rising Warm rate and rate of temperature fall are 10 DEG C/min.
High annealing, which refers to, is heated slowly to certain temperature for metal, keeps enough time, then cooling with Reasonable Speed A kind of metal heating processing technology of (usually Slow cooling, sometimes control cooling).Present invention preferably employs high annealings, main If in view of the processing mode can obtain the matched stacked structure of higher crystal orientation.
According to another aspect of the present invention, a kind of matched graphene/hexagonal boron nitride composite layer of height crystal orientation is provided Structure, the lamination layer structure are prepared by any of the above-described kind of preparation method.Graphene/the nitrogen prepared using method of the invention The height crystal orientation for changing boron matches stacked structure, not only can provide controllable building method, Er Qie for research superlattice structure Many special performances are all shown in terms of electricity, optics, tribology, if stacked structure thermal stability is very high, are conducive to prepare The stable all kinds of devices of performance.
Beneficial effects of the present invention are further illustrated below with reference to embodiment:
Embodiment 1
1) the hexagonal boron nitride crystal with a thickness of 20nm is taken, by its mechanical stripping to the silica/silicon with a thickness of 300nm On substrate.Then the single-layer graphene having a size of 5 μm is transferred on hexagonal boron nitride using the method for mechanical transfer, is formed such as Stepped construction shown in Fig. 1.
2) electron beam lithography and reactive ion oxygen lithographic technique is used to prepare diameter on graphene layer as 300nm Circular hole, as shown in Figure 2.Enlarged rounded hole defect is etched using hydrogen plasma, so that obtaining has isolated graphite The preliminary stacked structure of the graphene/hexagonal boron nitride of alkene fritter, as shown in Figure 3.Reaction condition are as follows: temperature is 400 DEG C, hydrogen Pressure is 0.4torr, and power 10W, etch rate is 3nm/ minutes.
3) graphene in preliminary stacked structure is operated using the manipulation technology based on scanning probe, so that graphite The preliminary stacked structure pre-matching of alkene/hexagonal boron nitride, as shown in Figure 5 to Figure 6.Graphene block rotates under the promotion of needle point When, when frictional force significantly becomes larger, graphene can eventually stop at closest with the matched crystal orientation of boron nitride.
4) stacked structure after pre-matching in step 3) is subjected to the high temperature anneal, is warming up to 700 with 10 DEG C/min DEG C, 30 minutes are kept the temperature, is then reduced to room temperature with 10 DEG C/min.Microscope photograph after the high temperature anneal is as shown in Figure 7.
Embodiment 2
1) the hexagonal boron nitride crystal with a thickness of 20nm is taken, by its mechanical stripping to the silica/silicon with a thickness of 300nm On substrate.Then the single-layer graphene having a size of 5 μm is transferred on hexagonal boron nitride using the method for mechanical transfer, is formed such as Stepped construction shown in Fig. 1.
2) electron beam lithography and reactive ion oxygen lithographic technique is used to prepare diameter on graphene layer as 100nm Circular hole, as shown in Figure 2.Enlarged rounded hole defect is etched using hydrogen plasma, so that obtaining has isolated graphite The preliminary stacked structure of the graphene/hexagonal boron nitride of alkene fritter, as shown in Figure 3.Reaction condition are as follows: temperature is 400 DEG C, hydrogen Pressure is 0.4torr, and power 10W, etch rate is 3nm/ minutes.
3) graphene in preliminary stacked structure is operated using the manipulation technology based on scanning probe, so that graphite The preliminary stacked structure pre-matching of alkene/hexagonal boron nitride, as shown in Figure 5 to Figure 6.Graphene block rotates under the promotion of needle point When, when frictional force significantly becomes larger, graphene can eventually stop at closest with the matched crystal orientation of boron nitride.
4) stacked structure after pre-matching in step 3) is subjected to the high temperature anneal, is warming up to 600 DEG C with 5 DEG C/min, 10 minutes, room temperature then was reduced to 5 DEG C/min.
Embodiment 3
1) the hexagonal boron nitride crystal with a thickness of 20nm is taken, by its mechanical stripping to the silica/silicon with a thickness of 300nm On substrate.Then the single-layer graphene having a size of 5 μm is transferred on hexagonal boron nitride using the method for mechanical transfer, is formed such as Stepped construction shown in Fig. 1.
2) electron beam lithography and reactive ion oxygen lithographic technique is used to prepare diameter on graphene layer as 700nm Circular hole, as shown in Figure 2.Enlarged rounded hole defect is etched using hydrogen plasma, so that obtaining has isolated graphite The preliminary stacked structure of the graphene/hexagonal boron nitride of alkene fritter, as shown in Figure 3.Reaction condition are as follows: temperature is 400 DEG C, hydrogen Pressure is 0.4torr, and power 10W, etch rate is 3nm/ minutes.
3) graphene in preliminary stacked structure is operated using the manipulation technology based on scanning probe, so that graphite The preliminary stacked structure pre-matching of alkene/hexagonal boron nitride, as shown in Figure 5 to Figure 6.Graphene block rotates under the promotion of needle point When, when frictional force significantly becomes larger, graphene can eventually stop at closest with the matched crystal orientation of boron nitride.
4) stacked structure after pre-matching in step 3) is subjected to the high temperature anneal, is warming up to 800 with 15 DEG C/min DEG C, 40 minutes are kept the temperature, is then reduced to room temperature with 15 DEG C/min.
Embodiment 4
Its operating procedure is same as Example 1, the difference is that the heating and cooling mechanism when high annealing are not Together, 900 DEG C are warming up to 20 DEG C/min in embodiment 4, keep the temperature 5 minutes, is then reduced to room temperature with 20 DEG C/min.
Embodiment 5
Its operating procedure is same as Example 1, the difference is that not using step 3), that is, is not based on scanning probe Manipulation technology operates the graphene in preliminary stacked structure.
Calculate the matching angle of the stacked structure for the graphene/hexagonal boron nitride prepared in embodiment 1 to 5.It calculates public Formula is as follows:
Wherein, a is the lattice constant 0.246nm of graphene, and it is the wavelength of Morie fringe that δ, which takes 1.8%, λ, can be using original Sub- force microscope measures its numerical value;Φ represents the angle between graphene and boron nitride crystal orientation, and Φ numerical value illustrates closer to 0 ° It is higher with degree.See Table 1 for details for specific value.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
λ 14nm 13nm 12nm 10nm 7nm
Φ 0.5° 1.5°
From table 1 it follows that stacking knot using the graphene/hexagonal boron nitride that heat treatment method of the invention is prepared The Φ value of structure is lower, illustrates the stacked structure crystal orientation matching degree with higher prepared using method of the invention, especially In embodiment 1 to 3.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly Determine or deduce out many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes It is set to and covers all such other variations or modifications.

Claims (8)

1. a kind of preparation method of the height crystal orientation matching stacked structure of graphene/hexagonal boron nitride, comprising:
Form the preliminary stacked structure of graphene/hexagonal boron nitride;
The preliminary stacked structure is heat-treated, matches heap to obtain the height crystal orientation of the graphene/hexagonal boron nitride Stack structure;
Wherein, the step of forming the preliminary stacked structure of the graphene/hexagonal boron nitride include:
Graphene layer is formed on hexagonal boron nitride crystal, and introduces defect on the graphene layer;
Expand the defect to obtain mutually discrete graphene block, to obtain multiple preliminary stacked structures;
Wherein, the heat treatment includes heating operation, and the heating temperature of the heating operation is 600 DEG C~800 DEG C, soaking time It is 10~40 minutes;Before the heat treatment, using the manipulation technology based on scanning probe in the preliminary stacked structure Graphene operated so that the preliminary stacked structure pre-matching.
2. preparation method according to claim 1, which is characterized in that it is described heat treatment for the preliminary stacked structure into Row high annealing, heating rate and rate of temperature fall when the high annealing are 5~15 DEG C/min.
3. preparation method according to claim 2, which is characterized in that heating rate and cooling speed when the high annealing Rate is 10 DEG C/min.
4. preparation method according to claim 1, which is characterized in that carved using electron beam lithography and reactive ion oxygen Erosion technology introduces defect on the graphene layer.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the rounded hole of defect, institute The size for stating circular hole is 50~800nm.
6. preparation method described in any one of -4 according to claim 1, which is characterized in that using hydrogen plasma respectively to different Property etching to expand the defect on the graphene layer.
7. preparation method according to claim 6, which is characterized in that the condition of the hydrogen plasma anisotropic etching Are as follows: temperature is 400 DEG C, Hydrogen Vapor Pressure 0.4torr, power 10W, and etch rate is 3nm/ minutes.
8. a kind of matched graphene/hexagonal boron nitride stacked structure of height crystal orientation, which is characterized in that the stacked structure is by weighing Benefit require any one of 1 to 7 described in preparation method be prepared.
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CN102392225A (en) * 2011-07-22 2012-03-28 中国科学院上海微系统与信息技术研究所 Method for preparing graphene nanoribbon on insulating substrate
CN102910614A (en) * 2011-08-04 2013-02-06 中国科学院物理研究所 Method for heterogeneous epitaxial growth of graphene
CN103502507A (en) * 2011-05-03 2014-01-08 韩国科学技术院 Method for manufacturing high quality graphene using continuous heat treatment chemical vapor deposition method

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CN103502507A (en) * 2011-05-03 2014-01-08 韩国科学技术院 Method for manufacturing high quality graphene using continuous heat treatment chemical vapor deposition method
CN102392225A (en) * 2011-07-22 2012-03-28 中国科学院上海微系统与信息技术研究所 Method for preparing graphene nanoribbon on insulating substrate
CN102910614A (en) * 2011-08-04 2013-02-06 中国科学院物理研究所 Method for heterogeneous epitaxial growth of graphene

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