CN101964292A - 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
The invention relates to a graphene sheet-carbon nanotube film composite structure which comprises at least one carbon nanotube film structure and a plurality of graphene sheets, wherein the carbon nanotube film structure comprises a plurality of micropores, wherein at least one micropore is covered by one graphene sheet. The invention also relates to a preparation method of the 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 evaporation one deck amorphous carbon-film is made again.Yet in actual applications, 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 is for nano-scale particle, easier acquisition better effects if ground transmission electron microscope high resolution picture.
Compared to prior art, described graphene film-carbon nano-tube film composite construction and preparation method thereof, obtain the carbon nano-tube membrane structure by pulling from carbon nano pipe array, and with this carbon nano-tube membrane structure as a kind of support frame with micropore, by 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 produces in transmission electron microscope observing 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 carbon nano-tube membrane structure of carbon nano-tube 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-carbon nano-tube membrane structure in the embodiment of the invention TEM micro grid.
Fig. 6 is the structural representation of another kind of graphene film-carbon nano-tube 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-carbon nano-tube 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
Below in conjunction with the accompanying drawings and the specific embodiments TEM micro grid provided by the invention and preparation method thereof is described in further detail.
See also Fig. 1, the preparation method of first embodiment of the invention TEM micro grid mainly comprises following step:
Step 1 provides a carbon nano-tube membrane structure, and a graphene film dispersion liquid.
This carbon nano-tube 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 super 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 to each other and that form perpendicular to the growth substrate carbon nanotubes grown as.By above-mentioned control growing condition, do not contain impurity in this carbon nano pipe array that aligns substantially, as 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 described carbon nano-tube is 0.5～50 nanometer, and length is 50 nanometers～5 millimeter.In the present embodiment, the length of carbon nano-tube is preferably 100 microns～900 microns.
Secondly, adopt a stretching tool from described carbon nano pipe array, to pull carbon nano-tube and obtain a carbon nano-tube film, it specifically may further comprise the steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of carbon nano-tube 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 carbon nano-tube of certain width; (b) with certain speed this selected carbon nano-tube that stretches, thereby form end to end a plurality of carbon nano-tube 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 carbon nano-tube 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 carbon nano-tube fragments be drawn out continuously end to end with other carbon nano-tube 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 by a support body supports, also can keep the shape of a film.See also Fig. 2, this carbon nano-tube film comprises and a plurality ofly being arranged of preferred orient and by the end to end carbon nano-tube of Van der Waals force along same direction substantially, and this carbon nano-tube is arranged and is parallel to this carbon nano-tube film surface along draw direction substantially.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 carbon nano-tube membrane structure can further comprise: stacked and intersection is laid a plurality of described 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 be 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 carbon nano-tube membrane structure also is a self supporting structure.The edge of this carbon nano-tube membrane structure is by 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 mutually by the Van der Waals force stable carbon nano-tube membrane structure of formation one of combining closely.In this carbon nano-tube 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 stacked mutually along two orthogonal directions, and the number of plies of carbon nano-tube film is 2～4 layers in the carbon nano-tube membrane structure.
After forming above-mentioned carbon nano-tube membrane structure, can further with an organic solvent handle described carbon nano-tube membrane structure, thereby in the carbon nano-tube 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 carbon nano-tube.This step of with an organic solvent handling is specially: by test tube organic solvent is dropped in the carbon nano-tube film body structure surface that is formed on the described framework and soaks into whole carbon nano-tube membrane structure, perhaps, also above-mentioned carbon nano-tube membrane structure can be immersed in the container that fill organic solvent and soak into.See also Fig. 3 and Fig. 7, described carbon nano-tube membrane structure is after organic solvent soaks into processing, side by side and adjacent carbon nano-tube can gather, thereby be shrunk to carbon nano tube line spaced apart, this carbon nano tube line comprises a plurality of by the end to end carbon nano-tube of Van der Waals force.Substantially between equidirectional carbon nanotubes arranged line, has a gap.Because the carbon nano-tube 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 mutually, thereby forms a plurality of micropores.After organic solvent was handled, the viscosity of carbon nano-tube film reduced.The micropore of this carbon nano-tube 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 mutually of the carbon nano tube line in this carbon nano-tube 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 carbon nano-tube membrane structure can reach more than 60%.Be appreciated that this stacked carbon mitron film quantity is many more, the size of the micropore of this carbon nano-tube membrane structure is more little.Therefore, can obtain the pore size of needs by 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 carbon nano-tube membrane structure be soaked into by this dispersion liquid, reach the effect identical with this step by 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 instrument 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, as 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.Described Graphene is the two-dimensional sheet structure that is formed by 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 described carbon nano-tube film body structure surface with described graphene film dispersion liquid.
This graphene film dispersion liquid can dropwise drop to above-mentioned carbon nano-tube film body structure surface by dropper, and the surface of this carbon nano-tube 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, in graphene film dispersion liquid as described in the whole immersion of whole carbon nano-tube membrane structure, again this carbon nano-tube membrane structure is taken out from the graphene film dispersion liquid.
In the present embodiment, adopt, on framework, form one by the carbon nano-tube 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 soaking into this carbon nano-tube membrane structure by the graphene film dispersion liquid, can further another carbon nano-tube membrane structure be covered in above-mentioned carbon nano-tube membrane structure, form a sandwich structure by the surface that the graphene film dispersion liquid soaks into.
Be appreciated that this another carbon nano-tube membrane structure can comprise the single or multiple lift carbon nano-tube film, can have and the identical or different structure of former carbon nano-tube 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 carbon nano-tube 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 stacked.In the present embodiment, this sandwich structure is the three-layer sandwich structure that two-layer carbon nano-tube 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 carbon nano-tube membrane structure clamping, thus make more firm the fixing of graphene film.This step is for can select step.
Step 3 makes this carbon nano-tube membrane structure drying of being soaked into by graphene film, thereby makes this graphene film and this carbon nano-tube 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 decided on the dropping number of times and the concentration of graphene film dispersion liquid in the continuous or discrete distribution of carbon nano-tube film body structure surface.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 carbon nano-tube membrane structure.
When forming the three-layer sandwich structure, the graphene film in this Graphene lamella of the carbon nano-tube clamping in the two-layer carbon nano-tube membrane structure, thus make more stable being fixed in this three-layer sandwich structure of this graphene film.
After forming described 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 carbon nano-tube bonding in this carbon nano-tube film.
This treatment step specifically can be by 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 by high energy particle (high-energy particle).After treatment, the carbon atom in the carbon atom in this graphene film and the carbon nano-tube forms covalent bond by 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 carbon nano-tube by Van der Waals force.
Step 4 covers a metal grill with described 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 adjacent metal grill of irradiation two, 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, make this graphene film-carbon nano-tube film composite construction and metal grill in conjunction with tight, and, promptly make TEM micro grid along the unnecessary graphene film-carbon nano-tube film composite construction of metal grill edge removal.
Above-mentioned organic solvent is a volatile organic solvent under the normal temperature, as 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, makes this graphene film-carbon nano-tube film composite construction and metal grill in conjunction with tight.In addition, the above-mentioned whole immersion of metal grill that is coated with graphene film-carbon nano-tube film composite construction can 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 by 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 by the film formed carbon nano-tube membrane structure of carbon nano-tube, can lay easily and stacked, in addition, also can easily a carbon nano-tube membrane structure be covered on the carbon nano-tube membrane structure that another surface has graphene film, make two carbon nano-tube membrane structure clampings graphene film therebetween.Secondly, the method that this employing laser, ultraviolet light or high energy particle are handled this graphene film-carbon nano-tube film composite construction can make this graphene film combine more firmly by covalent bond with carbon nano-tube film.Once more, because this carbon nano-tube membrane structure has great specific area, therefore have big viscosity, can be good attach on the described metal grill handled by organic solvent, and this carbon nano-tube membrane structure is more firm with combining of this metal grill.Further, described graphene film-carbon nano-tube membrane structure can once cover on a plurality of metal grills, and method is simple, quick, by the graphene film-carbon nano-tube 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 invention provides a kind of TEM micro grid 100, one graphene film-carbon nano-tube film composite construction 120 that it comprises a metal grill 110 and covers metal grill 110 surfaces.
This graphene film-carbon nano-tube film composite construction 120 comprises that at least one carbon nano-tube membrane structure 122 and a plurality of graphene film 124 are arranged at this carbon nano-tube membrane structure 122 surfaces.This carbon nano-tube membrane structure 122 comprises a plurality of micropores 126, and wherein, at least one micropore 126 is covered by a graphene film 124.
Particularly, see also Fig. 2 and Fig. 3, this carbon nano-tube membrane structure 122 comprises the setting of multilayer carbon nanotube film-stack.This carbon nano-tube film is for to pull acquisition from a carbon nano pipe array, comprises a plurality of substantially along same direction preferred orientation and be parallel to carbon nano-tube film surface carbon nanotubes arranged.Described carbon nano-tube joins end to end by Van der Waals force.The multilayer carbon nanotube film intersects and stacked setting mutually in this carbon nano-tube membrane structure 122.Because in every layer of carbon nano-tube film, carbon nano-tube is arranged of preferred orient along a direction, therefore, has an intersecting angle α between the carbon nano-tube 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 carbon nano-tube that this carbon nano tube line 128 comprises side by side and gathers by Van der Waals force, further, this carbon nano tube line 128 comprises the carbon nano-tube that joins end to end and be arranged of preferred orient along same direction substantially by Van der Waals force.The carbon nano tube line 128 of this intersection defines a plurality of micropores 126 in this carbon nano-tube membrane structure 122.The size of the micropore 126 of this carbon nano-tube 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 carbon nano-tube membrane structure 122, is preferably 2～4 layers.The size of micropore 126 can be 1 nanometer～1 micron in this carbon nano-tube membrane structure 122, and preferably, the following micropore of 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 carbon nano-tube 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 carbon nano-tube can pass through sp3 hydridization bonding, thereby make this graphene film 124 stable being fixed on this carbon nano-tube membrane structure 122.
Further, this graphene film-carbon nano-tube film composite construction 120 can comprise that a plurality of carbon nano-tube membrane structure 122 stacked settings and a plurality of graphene film 124 are arranged between the two adjacent carbon nano-tube membrane structures 122.See also Fig. 6, this graphene film 124 can be arranged between the two carbon nano-tube membrane structures 122, by carbon nano tube line 128 clampings in the two carbon nano-tube membrane structures 122, thereby makes this graphene film 124 stable being fixed on this carbon nano-tube 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 carbon nano-tube 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 (as pottery) to make 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 carbon nano-tube membrane structure 122.This sample 200 can be nano particle, as 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 observe 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 carbon nano-tube 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, (size is more than 1 nanometer because carbon nano-tube membrane structure 122 has nanometer level microporous 126, 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, 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 produces in transmission electron microscope observing 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 by 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 by 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 present embodiment TEM micro grid thereon the pattern for the treatment of observing samples and structural analysis etc. disturb little, very little to the high resolution picture influence of nano particle sample.
Further, because carbon nano-tube membrane structure 122 and graphene film 124 form by carbon atom bonding, and has similar structure, so this carbon nano-tube membrane structure 122 has good matching with graphene film 124, can form the sp3 covalent bond by handling, thereby the formation integrative-structure, easy to use or long-time preservation.
In addition, this graphene film-carbon nano-tube film composite construction 120 can comprise at least two carbon nano-tube 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 carbon nano-tube 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, the variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.
Claims (22)
1. graphene film-carbon nano-tube film composite construction, it is characterized in that: it comprises at least one carbon nano-tube membrane structure and a plurality of graphene film, and this carbon nano-tube 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 described carbon nano-tube membrane structure.
6. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, each micropore of described carbon nano-tube membrane structure is all covered by a graphene film.
7. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this carbon nano-tube membrane structure is a self supporting structure.
8. graphene film as claimed in claim 1-carbon nano-tube film composite construction is characterized in that, this carbon nano-tube membrane structure comprises the cross layered setting of multilayer carbon nanotube film.
9. graphene film as claimed in claim 8-carbon nano-tube film composite construction is characterized in that, this carbon nano-tube film comprises a plurality of by being arranged of preferred orient along same direction substantially, and by the end to end carbon nano-tube of Van der Waals force.
10. 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.
11. graphene film as claimed in claim 10-carbon nano-tube film composite construction is characterized in that, described size accounts for more than 60% of total micropore quantity less than the micropore of 100 nanometers.
12. 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 carbon nano-tube membrane structure is by sp3 hydridization bonding.
13. 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 stacked setting of a plurality of carbon nano-tube film structures and a plurality of graphene film are arranged between the adjacent two carbon nano-tube membrane structures, and by these two adjacent carbon nano-tube membrane structure clampings.
14. graphene film-carbon nano-tube film composite construction, it is characterized in that: it comprises at least one carbon nano-tube membrane structure and a plurality of graphene film, this carbon nano-tube 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.
15. graphene film as claimed in claim 14-carbon nano-tube film composite construction is characterized in that, the carbon nano-tube that this carbon nano tube line comprises side by side and gathers by Van der Waals force.
16. graphene film as claimed in claim 15-carbon nano-tube film composite construction is characterized in that, this carbon nano tube line comprises the carbon nano-tube that joins end to end and be arranged of preferred orient along same direction substantially by Van der Waals force.
17. the preparation method of graphene film-carbon nano-tube film composite construction, it may further comprise the steps: the carbon nano-tube membrane structure of a self-supporting is provided, and a graphene film dispersion liquid, this carbon nano-tube 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 carbon nano-tube membrane structure that should be soaked into by graphene film, thus make this graphene film and this carbon nano-tube membrane structure compound, form one graphene film-carbon nano-tube film composite construction.
18. the preparation method of graphene film as claimed in claim 17-carbon nano-tube film composite construction, it is characterized in that, described this graphene film dispersion liquid is soaked into described carbon nano-tube film body structure surface before, further comprise the step of with an organic solvent handling described at least one carbon nano-tube membrane structure.
19. the preparation method of graphene film as claimed in claim 17-carbon nano-tube film composite construction, it is characterized in that, after this graphene film dispersion liquid soaked into this carbon nano-tube film body structure surface, further comprise another carbon nano-tube membrane structure is covered in above-mentioned carbon nano-tube membrane structure by the surface that described graphene film dispersion liquid soaks into, form the step of a sandwich structure.
20. the preparation method of graphene film as claimed in claim 17-carbon nano-tube film composite construction, it is characterized in that, drying further comprises with laser or this graphene film of UV-irradiation-carbon nano-tube film composite construction after being somebody's turn to do the carbon nano-tube membrane structure of being soaked into by graphene film; Or, make this graphene film and this carbon nano-tube bonding step of connecting with this graphene film of high-energy particle bombardment-carbon nano-tube film composite construction.
21. the preparation method of graphene film as claimed in claim 17-carbon nano-tube film composite construction is characterized in that, this carbon nano-tube 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.
22. the preparation method of graphene film as claimed in claim 21-carbon nano-tube film composite construction, it is characterized in that, the preparation method of this carbon nano-tube 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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