CN101964292B - Graphene sheet-carbon nanotube film composite structure and preparation method thereof - Google Patents
Graphene sheet-carbon nanotube film composite structure and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种石墨烯片-碳纳米管膜复合结构，其包括至少一碳纳米管膜结构及多个石墨烯片，该碳纳米管膜结构包括多个微孔，其中，至少一微孔被一石墨烯片覆盖。本发明还涉及一种石墨烯片-碳纳米管膜复合结构的制备方法。
The invention relates to a graphene sheet-carbon nanotube film composite structure, which includes at least one carbon nanotube film structure and a plurality of graphene sheets, and the carbon nanotube film structure includes a plurality of micropores, wherein at least one micropore covered by a graphene sheet. The invention also relates to a preparation method of a graphene sheet-carbon nanotube film composite structure.
Description
This case is that the applicant is 200910109128.0 at the application number of application on July 24th, 2009, and name is called dividing an application of " TEM micro grid and preparation method thereof ".
Technical field
The present invention relates to a kind of graphene film-carbon nano-tube film composite construction and preparation method thereof.
Background technology
In transmission electron microscope, amorphous carbon supporting film (little grid) is to be used to carry powder sample, carries out the important tool that transmission electron microscope high resolution picture (HRTEM) is observed.Along with the continuous development of nano materials research, little grid are increasingly extensive in the application of the electron micrology representational field of nano material.In the prior art, these little grid that are applied to transmission electron microscope normally cover one deck porous organic membrane on metal grills such as copper mesh or nickel screen, and vapor deposition one deck amorphous carbon-film is processed again.Yet in practical application, especially when observation was of a size of the transmission electron microscope high resolution picture of nano level particle, the amorphous carbon-film in little grid was thicker, and the contrast noise is bigger, and is very big to the raising influence of the transmission electron microscope imaging resolution of nano particle.
Summary of the invention
In view of this; The necessary a kind of graphene film-carbon nano-tube film composite construction and preparation method thereof that provides; The TEM micro grid of wherein using this graphene film-carbon nano-tube film composite construction obtains better effects if ground transmission electron microscope high resolution picture more easily for nano-scale particle.
Compared to prior art; Described graphene film-carbon nano-tube film composite construction and preparation method thereof; Obtain the CNT membrane structure through pulling from carbon nano pipe array; And with this CNT membrane structure as a kind of support frame with micropore, through graphene film being covered on the micropore of this support frame, realize the unsettled setting of graphene film.Because graphene film has thickness as thin as a wafer, the contrast noise that in transmission electron microscope observing, produces is less, thereby can obtain the higher transmission electron microscope photo of resolution.
Description of drawings
Fig. 1 is the preparation method's of embodiment of the invention TEM micro grid a schematic flow sheet.
Fig. 2 is the stereoscan photograph of the carbon nano-tube film in the embodiment of the invention TEM micro grid.
Fig. 3 is the stereoscan photograph of the film formed CNT membrane structure of CNT of being intersected by multilayer in the embodiment of the invention TEM micro grid.
Fig. 4 is the structural representation of embodiment of the invention TEM micro grid.
Fig. 5 is the structural representation of a kind of graphene film-CNT membrane structure in the embodiment of the invention TEM micro grid.
Fig. 6 is the structural representation of another kind of graphene film-CNT membrane structure in the embodiment of the invention TEM micro grid.
Fig. 7 is the transmission electron microscope photo of a kind of graphene film-CNT membrane structure in the embodiment of the invention TEM micro grid.
Fig. 8 has the structural representation of the TEM micro grid of sample for embodiment of the invention surface.
Fig. 9 observes the transmission electron microscope photo of nanogold particle for using embodiment of the invention TEM micro grid.
Figure 10 uses the high-resolution transmission electron microscope photo that embodiment of the invention TEM micro grid is observed nanogold particle among Fig. 9.
Embodiment
To combine accompanying drawing and specific embodiment that TEM micro grid provided by the invention and preparation method thereof is done further to specify below.
See also Fig. 1, the preparation method of first embodiment of the invention TEM micro grid mainly comprises following step:
Step 1 provides a CNT membrane structure, and a graphene film dispersion liquid.
This CNT membrane structure comprises the carbon nano-tube film that multilayer is cross layered.This carbon nano-tube film is for directly to pull acquisition from a carbon nano pipe array, its preparation method specifically may further comprise the steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array of ultra in-line arrangement.
This carbon nano pipe array adopts chemical vapour deposition technique preparation, and this carbon nano-pipe array is classified a plurality of pure nano-carbon tube arrays parallel and that form perpendicular to the growth substrate carbon nanotubes grown as.Through above-mentioned control growing condition, do not contain impurity in this carbon nano pipe array that aligns basically, like agraphitic carbon or residual catalyst metal particles etc., be suitable for therefrom pulling carbon nano-tube film.The carbon nano-pipe array that the embodiment of the invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and the array of multi-walled carbon nanotubes as.The diameter of said CNT is 0.5～50 nanometer, and length is 50 nanometers～5 millimeter.In the present embodiment, the length of CNT is preferably 100 microns～900 microns.
Secondly; Adopt a stretching tool from said carbon nano pipe array, to pull CNT and obtain a carbon nano-tube film; It specifically may further comprise the steps: (a) from said ultra in-line arrangement carbon nano pipe array selected one or have a plurality of CNTs of certain width, present embodiment is preferably and adopts adhesive tape, tweezers or clip contact carbon nano pipe array with certain width with selected one or have a plurality of CNTs of certain width; (b) with this selected CNT of certain speed stretching, thereby form end to end a plurality of CNT fragment, and then form a continuous carbon nano tube film.This pulls direction along the direction of growth that is basically perpendicular to carbon nano pipe array.
In above-mentioned drawing process; These a plurality of CNT fragments are when tension lower edge draw direction breaks away from growth substrate gradually; Because Van der Waals force effect; Should selected a plurality of CNT fragments be drawn out continuously end to end with other CNT fragment respectively, thereby form one continuously, evenly and carbon nano-tube film with self-supporting of certain width.So-called " self supporting structure " i.e. this carbon nano-tube film need not through a support body supports, also can keep the shape of a film.See also Fig. 2, this carbon nano-tube film comprises that the same direction in a plurality of basic edges is arranged of preferred orient and through the end to end CNT of Van der Waals force, and this CNT is arranged and is parallel to this carbon nano-tube film surface along draw direction basically.Directly the method for stretching acquisition carbon nano-tube film is simply quick, the suitable industrial applications of carrying out.
The width of this carbon nano-tube film is relevant with the size of carbon nano pipe array, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.When the area of this carbon nano pipe array was 4 inches, the width of this carbon nano-tube film was 3 millimeters～10 centimetres, and the thickness of this carbon nano-tube film is 0.5 nanometer～100 micron.
The preparation method who is appreciated that this CNT membrane structure can further comprise: range upon range of and intersection is laid a plurality of said carbon nano-tube films.Particularly, can earlier a carbon nano-tube film be covered to a framework along a direction, another carbon nano-tube film covered to previous carbon nano-tube film surface along other direction again, so repeated multiple times is laid a plurality of carbon nano-tube films on this framework.These a plurality of carbon nano-tube films can be laid along different separately directions, also can only lay along the direction of two intersections.Be appreciated that this CNT membrane structure also is a self supporting structure.The edge of this CNT membrane structure is through this frame fixation, the unsettled setting in middle part.
Because this carbon nano-tube film has bigger specific area, so this carbon nano-tube film has big viscosity, thus the multilayer carbon nanotube film can be each other through the Van der Waals force stable CNT membrane structure of formation one of combining closely.In this CNT membrane structure, the number of plies of carbon nano-tube film is not limit, and has an intersecting angle α between the adjacent two layers carbon nano-tube film, 0 °＜α≤90 °.Present embodiment is preferably α=90 °, and promptly these a plurality of carbon nano-tube films are only range upon range of each other along two orthogonal directions, and the number of plies of carbon nano-tube film is 2～4 layers in the CNT membrane structure.
After forming above-mentioned CNT membrane structure, can further with an organic solvent handle said CNT membrane structure, thereby in the CNT membrane structure, form a plurality of micropores.
This organic solvent is a volatile organic solvent under the normal temperature, can select in ethanol, methyl alcohol, acetone, dichloroethanes and the chloroform one or several mixing for use, and the organic solvent in the present embodiment adopts ethanol.This organic solvent should have wetability preferably with this CNT.This with an organic solvent processed steps be specially: through test tube organic solvent is dropped in the carbon nano-tube film body structure surface that is formed on the said framework and soaks into whole CNT membrane structure; Perhaps, also can above-mentioned CNT membrane structure be immersed in the container that fills organic solvent and soak into.See also Fig. 3 and Fig. 7; Described CNT membrane structure is after organic solvent soaks into processing; Side by side and adjacent CNT can gather, thereby be shrunk to carbon nano tube line spaced apart, this carbon nano tube line comprises a plurality of through the end to end CNTs of Van der Waals force.Basically between equidirectional carbon nanotubes arranged line, has a gap.Because the CNT in the adjacent two layers carbon nano-tube film has an intersecting angle α, and 0＜α≤90 °, the carbon nano tube line that organic solvent is handled in the adjacent two layers carbon nano-tube film of back intersects each other, thereby forms a plurality of micropores.After organic solvent was handled, the viscosity of carbon nano-tube film reduced.The micropore of this CNT membrane structure is of a size of 1 nanometer～10 micron, is preferably 1 nanometer～900 nanometers.In the present embodiment, this intersecting angle α=90 ° is so the basic square crossing each other of the carbon nano tube line in this CNT membrane structure forms a large amount of micropores.Preferably, when this carbon nano tube structure comprises four folded layer by layer carbon nano-tube films, the micropore that is of a size of nanometer scale in this CNT membrane structure can reach more than 60%.Be appreciated that this range upon range of carbon mitron film quantity is many more, the size of the micropore of this CNT membrane structure is more little.Therefore, can obtain the pore size of needs through the quantity of adjusting this carbon nano-tube film.The size of this micropore should be less than the size of this graphene film, so that a graphene film can cover this micropore fully.Be appreciated that this step for can select step, when the solvent in this graphene film dispersion liquid is volatile organic solvent, can directly the CNT membrane structure be soaked into through this dispersion liquid, reach the effect identical with this step through subsequent step two.
This graphene film dispersion liquid obtains for graphene film is scattered in the solvent.In the present embodiment, the preparation method of this graphene film dispersion liquid specifically comprises: a certain amount of graphene film is provided; This graphene film is inserted formation one mixture in the solvent; This mixture of sonic oscillation obtains a graphene film dispersion liquid thereby graphene film is evenly disperseed and be suspended in this solvent.In the present embodiment, this mixture vibrated in the sonic oscillation appearance about 15 minutes.Be appreciated that and also can adopt other method to disperse this graphene film, as adopt churned mechanically method to stir the mixture of this graphene film and this solvent.
This solvent should be chosen as and be beneficial to graphene film and disperse, and the low molecular weight solvent that can volatilize fully, like one or several mixing in water, ethanol, methyl alcohol, acetone, dichloroethanes and the chloroform.In the present embodiment, this solvent is a water.Be appreciated that this solvent only plays the effect of even dispersion graphene film, thus this solvent should not react with this graphene film, as chemical reaction takes place or graphene film is dissolved in the solvent.
This graphene film is made up of single or multiple lift Graphene (graphene).Preferably, the number of plies of the graphene film in this graphene film dispersion liquid is 1～3 layer, thereby makes TEM micro grid have better contrast.Said Graphene is the two-dimensional sheet structure that is formed through the sp2 bond hybridization by carbon atom.This graphene film is of a size of below 10 microns, can be less than 1 micron.The concentration of this graphene film in this testing sample dispersion liquid is below 5% (volumn concentration).
Step 2 is soaked into said carbon nano-tube film body structure surface with said graphene film dispersion liquid.
This graphene film dispersion liquid can dropwise drop to above-mentioned carbon nano-tube film body structure surface through dropper, and the surface of this CNT membrane structure is soaked into by this graphene film dispersion liquid.Be appreciated that when this carbon nano-tube film structural area is big, can pass through alternate manner,, again this CNT membrane structure is taken out from the graphene film dispersion liquid as with in the said graphene film dispersion liquid of the whole immersion of whole CNT membrane structure.
In the present embodiment, adopt, on framework, form one by the CNT membrane structure of this graphene film dispersion liquid infiltration to the mode that is layed in the carbon nano-tube film body structure surface dropping graphene film dispersion liquid on the framework.
After this CNT membrane structure of graphene film dispersion liquid infiltration, can further another CNT membrane structure be covered in above-mentioned CNT membrane structure through the surface that the graphene film dispersion liquid soaks into, form a sandwich structure.
Be appreciated that this another CNT membrane structure can comprise the single or multiple lift carbon nano-tube film, can have and the identical or different structure of former CNT membrane structure.This step can repeat with step 2, promptly form this sandwich structure after, further this graphene film dispersant liquid drop is added to this sandwich structure surface, and further covers another CNT membrane structure, thereby form a multilayer sandwich structure.This multilayer sandwich structure comprises that multilayer carbon nanotube membrane structure and multi-layer graphene sheet dispersion liquid are alternate range upon range of.In the present embodiment, this sandwich structure is the three-layer sandwich structure that two-layer CNT membrane structure and one deck graphene film dispersion liquid form.Graphene film in the graphene film dispersion liquid in the middle of this two-layer CNT membrane structure clamping, thus make more firm the fixing of graphene film.This step is for can select step.
Step 3 makes this dry by CNT membrane structure that graphene film soaks into, thereby makes this graphene film and this CNT membrane structure compound, forms one graphene film-carbon nano-tube film composite construction.
After this graphene film dispersion liquid drying, this carbon nano-tube film body structure surface forms a Graphene lamella.Graphene film in this Graphene lamella can be in the continuous or discrete distribution of carbon nano-tube film body structure surface, looks dropping number of times and the concentration of graphene film dispersion liquid and decides.See also Fig. 7, in this graphene film-carbon nano-tube film composite construction, at least one graphene film covers at least one micropore in this CNT membrane structure.
When forming the three-layer sandwich structure, the graphene film in this Graphene lamella of the CNT clamping in the two-layer CNT membrane structure, thus make more stable being fixed in this three-layer sandwich structure of this graphene film.
After forming said graphene film-carbon nano-tube film composite construction, can further handle this graphene film-carbon nano-tube film composite construction, this graphene film is connected with CNT bonding in this carbon nano-tube film.
This treatment step specifically can be through laser or this graphene film of UV-irradiation-carbon nano-tube film composite construction; Or bombard this graphene film-carbon nano-tube film composite construction through high energy particle (high-energy particle).After treatment, the carbon atom in the carbon atom in this graphene film and the CNT forms covalent bond through sp3 hydridization and is connected, thus make graphene film more stable be fixed in this carbon nano-tube film body structure surface.This step is for can select step, and when this method did not comprise this step, this graphene film combined with this CNT through Van der Waals force.
Step 4 covers a metal grill with said graphene film-carbon nano-tube film composite construction.
This metal grill has at least one through hole, and this graphene film-carbon nano-tube film composite construction covers the unsettled setting of part of this through hole.
When this graphene film-carbon nano-tube film composite construction area is big, can further comprise: a plurality of metal grills are spaced; With this graphene film-these a plurality of metal grills of the whole covering of carbon nano-tube film composite construction; And from disconnection this graphene film-carbon nano-tube film composite construction between two adjacent metal grills, thereby a plurality of surface coverage of disposable formation have the metal grill of graphene film-carbon nano-tube film composite construction.
Particularly, can adopt laser beam to focus between the irradiation two adjacent metal grids, blow this graphene film-carbon nano-tube film composite construction.In the present embodiment, this laser beam power is 5～30 watts (W), is preferably 18W.
Further; Can with an organic solvent handle the graphene film-carbon nano-tube film composite construction that covers on the metal grill; This graphene film-carbon nano-tube film composite construction and metal grill are combined closely; And remove unnecessary graphene film-carbon nano-tube film composite construction along the metal grill edge, promptly process TEM micro grid.
Above-mentioned organic solvent is a volatile organic solvent under the normal temperature, like ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.This organic solvent can directly drop in graphene film-carbon nano-tube film composite structure surface, and this graphene film-carbon nano-tube film composite construction and metal grill are combined closely.In addition, can the above-mentioned whole immersion of metal grill that is coated with graphene film-carbon nano-tube film composite construction be filled in the container of organic solvent and soak into.The step of unnecessary graphene film-carbon nano-tube film composite construction can be through a laser beam and focuses on beyond this removal metal grill; And shine a week along this metal grill edge; This graphene film-carbon nano-tube film composite construction of ablating, thus remove the outer unnecessary graphene film-carbon nano-tube film composite construction of metal grill.This step is for can select step.
The preparation method of the TEM micro grid that the embodiment of the invention provided has the following advantages.At first; Because reaching, carbon nano-tube film has self-supporting property by the film formed CNT membrane structure of CNT; Can lay easily and range upon range of; In addition, also can be easily a CNT membrane structure be covered on the CNT membrane structure that another surface has graphene film, make two CNT membrane structure clampings graphene film therebetween.Secondly, the method for this employing laser, ultraviolet light or high energy particle processing this graphene film-carbon nano-tube film composite construction can make this graphene film combine more firmly through covalent bond with carbon nano-tube film.Once more, because this CNT membrane structure has great specific area, therefore have big viscosity, can be good attach on the said metal grill handled through organic solvent, and combining of this CNT membrane structure and this metal grill is more firm.Further, said graphene film-CNT membrane structure can once cover on a plurality of metal grills, and method is simple, quick, through the graphene film-CNT membrane structure beyond the removal metal grill, but the TEM micro grid of prepared in batches stable in properties.
See also Fig. 4, Fig. 5 and Fig. 7, the present invention provides a kind of TEM micro grid 100, and it comprises a metal grill 110 and covers the one graphene film-carbon nano-tube film composite construction 120 on metal grill 110 surfaces.
This graphene film-carbon nano-tube film composite construction 120 comprises that at least one CNT membrane structure 122 and a plurality of graphene film 124 are arranged at this CNT membrane structure 122 surfaces.This CNT membrane structure 122 comprises a plurality of micropores 126, and wherein, at least one micropore 126 is covered by a graphene film 124.
Particularly, please consult Fig. 2 and Fig. 3 in the lump, this CNT membrane structure 122 comprises the setting of multilayer carbon nanotube film-stack.This carbon nano-tube film comprises the same direction preferred orientation in a plurality of basic edges and is parallel to carbon nano-tube film surface carbon nanotubes arranged for to pull acquisition from a carbon nano pipe array.Said CNT joins end to end through Van der Waals force.The multilayer carbon nanotube film intersects and range upon range of setting each other in this CNT membrane structure 122.Because in every layer of carbon nano-tube film, CNT is arranged of preferred orient along a direction, therefore, has an intersecting angle α between the CNT in the adjacent two layers carbon nano-tube film, 0 °＜α≤90 °.Present embodiment is preferably α=90 °.
See also Fig. 5 and Fig. 7; This carbon nano tube structure 122 comprises the carbon nano tube line 128 of a plurality of intersections; The CNT that this carbon nano tube line 128 comprises side by side and gathers through Van der Waals force; Further, this carbon nano tube line 128 comprises the CNT through Van der Waals force joins end to end and the same direction in basic edge is arranged of preferred orient.The carbon nano tube line 128 of this intersection defines a plurality of micropores 126 in this CNT membrane structure 122.The size of the micropore 126 of this CNT membrane structure 122 is relevant with the number of plies of carbon nano-tube film.The number of plies of carbon nano-tube film is not limit in this CNT membrane structure 122, is preferably 2～4 layers.The size of micropore 126 can be 1 nanometer～1 micron in this CNT membrane structure 122, and preferably, the micropore below 100 nanometers can reach more than 60%.
This graphene film 124 comprises one or more layers Graphene, and the size of this graphene film 124 is greater than the size of micropore 126 in this CNT membrane structure 122, and covers this micropore 126 fully.This graphene film 124 is of a size of 2 nanometers～10 micron.Preferably, this graphene film is of a size of 2 nanometers～1 micron.In the present embodiment, this graphene film 124 comprises 1 layer～3 layer graphenes.
Further, carbon atom in this graphene film 124 and the carbon atom in this CNT can pass through sp3 hydridization bonding, thereby make this graphene film 124 stable being fixed on this CNT membrane structure 122.
Further, this graphene film-carbon nano-tube film composite construction 120 can comprise that a plurality of CNT membrane structure 122 range upon range of settings and a plurality of graphene film 124 are arranged between the two adjacent CNT membrane structures 122.See also Fig. 6, this graphene film 124 can be arranged between the two CNT membrane structures 122, by carbon nano tube line 128 clampings in the two CNT membrane structures 122, thereby makes this graphene film 124 stable being fixed on this CNT membrane structure 122.
This metal grill 110 is one to be formed with the sheet metal of one or more through holes 112.This metal grill 110 can be a used in transmission electron microscope metal grill 110.The material of this metal grill 110 is copper or other metal materials.This graphene film-carbon nano-tube film composite construction 120 basic these metal grills 110 that cover; Thereby make this graphene film-carbon nano-tube film composite construction 120 can pass through the unsettled setting of these metal grill 110 parts; In the present embodiment; This graphene film-carbon nano-tube film composite construction 120 has area and the shape that equates with this metal grill 110, and covers all through holes 112 of this metal grill 110 fully.In addition, the size of the micropore 126 that the aperture of the through hole 112 of this metal grill 110 has much larger than CNT membrane structure 122, and greater than the size of this graphene film 124.In the present embodiment, the diameter of the through hole 112 of this metal grill is 10 microns～2 millimeters.
Be appreciated that the grid that this TEM micro grid 100 also can adopt other materials (like pottery) to process replaces this metal grill 110.
Present embodiment TEM micro grid 100 is when using, and sample 200 to be observed is set at this TEM micro grid 100 surfaces.Particularly, see also Fig. 8 and Fig. 9, this sample 200 is arranged at graphene film 124 surfaces of the micropore 126 that covers this CNT membrane structure 122.This sample 200 can be nano particle, like nano wire, nanosphere or nanotube etc.The size of this sample 200 can be preferably below 10 nanometers less than 1 micron.See also Fig. 9 and Figure 10, it is for adding to a nm of gold dispersant liquid drop on the surface of above-mentioned TEM micro grid 100, the transmission electron microscope photo of dry back observable different resolution under transmission electron microscope.Black particle is a nanogold particle to be observed among the figure.
The TEM micro grid 100 that the embodiment of the invention provides has the following advantages.
At first, this graphene film 124 plays 200 effects of carrying sample, and a large amount of samples 200 can be uniformly distributed in graphene film 124 surfaces, can be used for the Distribution Statistics of measuring samples 200 particle diameters, and observes the self assembly characteristic of these a large amount of samples 200 on the graphene film surface.Because this graphene film 124 covers this micropore 126, this sample 200 can be carried by this graphene film 124, thereby is uniformly distributed in micropore 126 tops of this CNT membrane structure 122, thereby has improved the carrying probability of 100 pairs of samples of this TEM micro grid.And the particle diameter of this testing sample 200 is unrestricted, and is for example only slightly little than this micropore 126.
Secondly, prepare comparatively difficulty of large-sized graphene film 124, with the size of the graphene film 124 of existing method preparation less than 10 microns; Therefore; Because that CNT membrane structure 122 has is nanometer level microporous 126 (size more than 1 nanometer, and less than 1 micron), so the size of this graphene film 124 need not be too big; Also can cover this micropore 126 fully; It is maximum that thereby the effective area that makes these little grid 100 can be used for observing reaches, and avoided causing graphene film 124 can't cover the situation of micropore fully because micropore is excessive.
The 3rd, this graphene film has thickness as thin as a wafer, about 0.335 nanometer of the thickness of single-layer graphene, and the contrast noise that in transmission electron microscope observing, produces is less, thereby can obtain the higher transmission electron microscope photo of resolution.In addition, have the metal grill of minor diameter (as below 2 microns) through hole must be through photoetching or other complicated and expensive prepared.And in the present embodiment, it is very little that the aperture of this metal grill 110 need not, so the cost of this metal grill 110 reduces greatly.
The 4th, owing to be used for pulling the carbon nano-tube film high purity of acquisition, need not to remove impurity through heat treatment from carbon nano pipe array.It is simple that this pulls the method for preparing carbon nano-tube film, helps reducing the cost of this TEM micro grid 10.10 pairs of carryings of the present embodiment TEM micro grid pattern of treating observing samples and structural analysis on it etc. disturbed little, and be very little to the high resolution picture influence of nano particle sample.
Further; Because CNT membrane structure 122 and graphene film 124 form by carbon atom bonding; And have similar structure,, can form the sp3 covalent bond through handling so this CNT membrane structure 122 has good matching with graphene film 124; Thereby the structure of being integrally formed, easy to use or long-time preservation.
In addition, this graphene film-carbon nano-tube film composite construction 120 can comprise at least two CNT membrane structures 122, and clamping is arranged at the graphene film 124 between this two graphene films-carbon nano-tube film composite construction 120.This kind structure can make this TEM micro grid 100 have more stable structure, is convenient to reuse or long-time the preservation.
It will be appreciated by those skilled in the art that; Micropore in above-mentioned graphene film and the CNT membrane structure is rectangle or irregular polygon structure; The size of above-mentioned this graphene film all refers to from this graphene film edge some the maximum linear distance to another point, the size of this micropore all refer to from this micropore a bit to the maximum linear distance of another point.
In addition, those skilled in the art also can do other variations in spirit of the present invention, and certainly, these all should be included within the present invention's scope required for protection according to the variation that the present invention's spirit is done.
Claims (21)
1. graphene film-carbon nano-tube film composite construction, it is characterized in that: it comprises at least one CNT membrane structure and a plurality of graphene film, and this CNT membrane structure comprises a plurality of micropores, and wherein, at least one micropore is covered by a graphene film.
2. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this graphene film is of a size of 2 nanometers～10 micron.
3. graphene film as claimed in claim 2-carbon nano-tube film composite construction is characterized in that, this graphene film is of a size of 2 nanometers～1 micron.
4. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this graphene film comprises 1 layer～3 layer graphenes.
5. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, at least one graphene film covers a plurality of micropores of said CNT membrane structure.
6. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this CNT membrane structure is a self supporting structure.
7. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this CNT membrane structure comprises the cross layered setting of multilayer carbon nanotube film.
8. graphene film as claimed in claim 7-carbon nano-tube film composite construction is characterized in that, this carbon nano-tube film comprises and a plurality ofly being arranged of preferred orient through the same direction in basic edge, and through the end to end CNT of Van der Waals force.
9. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this micropore is of a size of 1 nanometer～1 micron.
10. graphene film as claimed in claim 9-carbon nano-tube film composite construction is characterized in that, said size accounts for more than 60% of total micropore quantity less than the micropore of 100 nanometers.
11. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, the carbon atom in the carbon atom in this graphene film and this CNT membrane structure is through sp3 hydridization bonding.
12. graphene film as claimed in claim 1-carbon nano-tube film composite construction; It is characterized in that; This graphene film-carbon nano-tube film composite construction comprises that the range upon range of setting of a plurality of carbon nano-tube film structures and a plurality of graphene film are arranged between the adjacent two CNT membrane structures, and through these two adjacent CNT membrane structure clampings.
13. graphene film-carbon nano-tube film composite construction; It is characterized in that: it comprises at least one CNT membrane structure and a plurality of graphene film; This CNT membrane structure comprises a plurality of carbon nano tube lines a plurality of micropores arranged in a crossed manner and that formed by these a plurality of carbon nano tube lines arranged in a crossed manner; Wherein, at least one micropore is covered by a graphene film.
14. graphene film as claimed in claim 13-carbon nano-tube film composite construction is characterized in that, the CNT that this carbon nano tube line comprises side by side and gathers through Van der Waals force.
15. graphene film as claimed in claim 14-carbon nano-tube film composite construction is characterized in that, this carbon nano tube line comprises the CNT through Van der Waals force joins end to end and the same direction in basic edge is arranged of preferred orient.
16. the preparation method of graphene film-carbon nano-tube film composite construction, it may further comprise the steps: the CNT membrane structure of a self-supporting is provided, and a graphene film dispersion liquid, this CNT membrane structure comprises a plurality of micropores;
This graphene film dispersion liquid is soaked into this carbon nano-tube film body structure surface; And
The dry CNT membrane structure of being soaked into of being somebody's turn to do by graphene film; Thereby make this graphene film and this CNT membrane structure compound; Form one graphene film-carbon nano-tube film composite construction, wherein, at least one graphene film covers at least one micropore in this CNT membrane structure.
17. the preparation method of graphene film as claimed in claim 16-carbon nano-tube film composite construction; It is characterized in that; Said this graphene film dispersion liquid is soaked into said carbon nano-tube film body structure surface before, further comprise the step of with an organic solvent handling said at least one CNT membrane structure.
18. the preparation method of graphene film as claimed in claim 16-carbon nano-tube film composite construction; It is characterized in that; Behind this this carbon nano-tube film body structure surface of graphene film dispersion liquid infiltration; Further comprise another CNT membrane structure is covered in above-mentioned CNT membrane structure through the surface that said graphene film dispersion liquid soaks into, form the step of a sandwich structure.
19. the preparation method of graphene film as claimed in claim 16-carbon nano-tube film composite construction; It is characterized in that; Dry should further being comprised with laser or this graphene film of UV-irradiation-carbon nano-tube film composite construction by after the CNT membrane structure of graphene film infiltration; Or, make this graphene film and this CNT bonding step of connecting with this graphene film of high-energy particle bombardment-carbon nano-tube film composite construction.
20. the preparation method of graphene film as claimed in claim 16-carbon nano-tube film composite construction is characterized in that, this CNT membrane structure comprises the carbon nano-tube film that multilayer is cross layered, and this carbon nano-tube film is for to pull acquisition from a carbon nano pipe array.
21. the preparation method of graphene film as claimed in claim 20-carbon nano-tube film composite construction; It is characterized in that; The preparation method of this CNT membrane structure comprises: earlier a carbon nano-tube film is covered to a framework along a direction; Again another carbon nano-tube film is covered to previous carbon nano-tube film surface along other direction, repeat above-mentioned steps, on this framework, lay a plurality of carbon nano-tube films.
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| CN102724615B (en) * | 2011-03-29 | 2015-03-11 | 清华大学 | A thermal sounding device and an electronic device |
| US8811632B2 (en) | 2011-03-29 | 2014-08-19 | Tsinghua University | Thermoacoustic device |
| CN102724613B (en) * | 2011-03-29 | 2015-04-01 | 清华大学 | A thermal sounding device and an electronic device |
| CN102724620B (en) * | 2011-03-29 | 2015-06-03 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724614B (en) * | 2011-03-29 | 2015-06-03 | 清华大学 | A thermal sounding device and an electronic device |
| CN102724618B (en) * | 2011-03-29 | 2015-04-01 | 清华大学 | Thermoacoustic device and electronic device |
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| CN102724619A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
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| CN102795613B (en) * | 2011-05-27 | 2014-09-10 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| CN102417176A (en) * | 2011-09-06 | 2012-04-18 | 天津大学 | Preparation method of graphene-carbon nanotube composite film based on three-dimensional network morphology |
| CN102339699B (en) * | 2011-09-30 | 2014-03-12 | 东南大学 | Field emission triode structure based on graphene |
| CN105197874B (en) * | 2014-06-17 | 2017-01-25 | 清华大学 | Preparation method of carbon nanotube composite wire |
| CN105140083B (en) * | 2015-06-24 | 2017-05-10 | 中国科学院生物物理研究所 | Preparation method of grid for transmission electron microscope |
| CN106183316B (en) * | 2016-07-08 | 2018-08-14 | 东华大学 | A kind of compliant conductive compound fabric and its preparation and application |
| US10091916B2 (en) * | 2016-09-29 | 2018-10-02 | The Boeing Company | Fabrication of ceramic matrix composites with carbon nanotubes and graphene |
| CN106477564A (en) * | 2016-10-18 | 2017-03-08 | 深圳丹邦科技股份有限公司 | Multi-layer graphene quantum carbon-based with carbon nanotube structure composite and preparation method |
| CN107089653A (en) * | 2017-04-02 | 2017-08-25 | 浙江大学 | A kind of redox graphene carbon supports film transmission electron microscope carrier net and preparation method thereof |
| CN110676341B (en) * | 2018-07-03 | 2021-06-25 | 清华大学 | Semiconductor structures, optoelectronic devices, photodetectors and photodetectors |
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