CN103373718B - Carbon nano tube film - Google Patents
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- CN103373718B CN103373718B CN201210122626.0A CN201210122626A CN103373718B CN 103373718 B CN103373718 B CN 103373718B CN 201210122626 A CN201210122626 A CN 201210122626A CN 103373718 B CN103373718 B CN 103373718B
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- 239000002238 carbon nanotube film Substances 0.000 title claims abstract description 296
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 224
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 203
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 201
- 238000005411 Van der Waals force Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 34
- 229910052799 carbon Inorganic materials 0.000 description 22
- 239000002904 solvent Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 238000013532 laser treatment Methods 0.000 description 12
- 150000001721 carbon Chemical class 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000010247 heart contraction Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D9/00—Open-work fabrics
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- D—TEXTILES; PAPER
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- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
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- D03D15/33—Ultrafine fibres, e.g. microfibres or nanofibres
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a carbon nano tube film. The carbon nano tube film comprises a plurality of carbon nano tube lines and a plurality of carbon nano tube clusters, wherein the carbon nano tube lines are arranged at intervals; the carbon nano tube clusters are separated from one another through the carbon nano tube lines; the carbon nano tube clusters which are positioned between two adjacent carbon nano tube lines are arranged at intervals.
Description
Technical field
The present invention relates to a kind of carbon nano-tube film.
Background technology
Nesa coating refers to the light transmission rate of visible ray higher, the film that electrical conductivity is high.Reporting by sputtering cadmium from Badker in 1907 and make it thermal oxide has been formed since cadmium oxide prepares transparent conductive film, and the research of transparent conductive film is subject to most attention.Along with the development of science, transparent conductive film plays an important role in fields such as liquid crystal display, touch-screen, electrochromic device, the hot window of aircraft, defrosting glass.
At present, the conventional metal-oxide film such as nesa coating tin indium oxide, zinc oxide, the preparation method of these nesa coatings mainly comprises the method such as evaporation, sputtering method.Evaporation, sputtering method belong to glass post-processing method, and equipment is complicated, cost is higher, be not suitable for large-scale production.And, when forming nesa coating owing to adopting said method, all need, through a higher annealing process, to cause damage to the substrate of nesa coating, cannot be formed in the substrate that fusing point is lower, limit the application of nesa coating.
People study and find that CNT has excellent conductive characteristic, and people can by adopting the method for stretching to prepare a kind of carbon nano-tube film from carbon nano pipe array, and this carbon nano-tube film not only has electric conductivity, but also has certain light transmittance.But this carbon nano-tube film directly pulls to obtain from a carbon nano pipe array, gap between adjacent CNT in this carbon nano-tube film is smaller, thus make the light transmittance of this carbon nano-tube film not high enough, be unfavorable for the extensive use of this carbon nano-tube film.
Summary of the invention
In view of this, necessaryly provide a kind of and prepare the carbon nano-tube film had compared with high-transmittance.
A kind of carbon nano-tube film, it comprises multiple carbon nano tube line and multiple carbon nano tube cluster, and the plurality of carbon nano tube line interval is arranged; The plurality of carbon nano tube cluster is separated by the plurality of carbon nano tube line, and the multiple carbon nano tube cluster intervals between adjacent carbon nano tube line are arranged.
A kind of carbon nano-tube film, it comprises multiple CNT and multiple hole, and the plurality of CNT forms multiple carbon nano tube line and multiple carbon nano tube cluster; The area ratio of the plurality of CNT and the plurality of hole is greater than 0, and is less than or equal to 1: 19.
Compared with prior art, multiple spaced carbon nano tube line and multiple carbon nano tube cluster is comprised by carbon nano-tube film provided by the invention, and the plurality of carbon nano tube cluster is separated by the plurality of carbon nano tube line, carbon nano tube cluster between adjacent carbon nano tube line is also spaced, so form multiple hole in this carbon nano-tube film, therefore, this carbon nano-tube film has higher light transmittance.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of carbon nano-tube film provided by the invention.
Fig. 2 is the stereoscan photograph of initial carbon nanotube films provided by the invention.
Fig. 3 is the planar structure schematic diagram being formed with the initial carbon nanotube films of a line through hole provided by the invention.
Fig. 4 is the planar structure schematic diagram being formed with the initial carbon nanotube films of multirow through hole provided by the invention.
The structural representation of the carbon nano-tube film that Fig. 5 provides for first embodiment of the invention, and carbon nano tube cluster in this carbon nano-tube film is arranged into an array.
The structural representation of the carbon nano-tube film that Fig. 6 provides for first embodiment of the invention, and the carbon nano tube cluster in this carbon nano-tube film is staggered.
Fig. 7 is preparation technology's flow chart of the carbon nano-tube film that first embodiment of the invention provides.
Fig. 8 is the planar structure schematic diagram being formed with the initial carbon nanotube films of through hole that first embodiment of the invention provides.
Fig. 9 is the partial optical microphotograph being formed with the initial carbon nanotube films of through hole shown in Fig. 8.
The optical microscope photograph of the carbon nano-tube film that Figure 10 provides for this first bright embodiment.
The light transmittance comparison diagram of the carbon nano-tube film that Figure 11 provides for first embodiment of the invention and various film.
Figure 12 is the structural representation of the carbon nano-tube film that second embodiment of the invention provides.
Figure 13 is the optical microscope photograph of the carbon nano-tube film that second embodiment of the invention provides.
Main element symbol description
| Carbon nano-tube film | 10；20 |
| Carbon nano pipe array | 110 |
| Substrate | 112 |
| Adhesive tape | 114 |
| Carbon nano tube line | 12 |
| Initial carbon nanotube films | 120 |
| Through hole | 122 |
| Connecting portion | 124 |
| Extension | 126 |
| Fixed body | 128 |
| Drop bottle | 130 |
| Ethanol | 132 |
| Carbon nano tube cluster | 14；24 |
| Second CNT | 242 |
Following detailed description of the invention will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Detailed description of the invention
The invention provides a carbon nano-tube film, this carbon nano-tube film comprises multiple spaced carbon nano tube line and multiple carbon nano tube cluster, and the plurality of carbon nano tube line and multiple carbon nano tube cluster are interconnected by Van der Waals force.The plurality of carbon nano tube cluster is separated by the plurality of carbon nano tube line, and the carbon nano tube cluster interval between adjacent two carbon nano tube lines is arranged.
Described multiple carbon nano tube line extends and spaced setting along first direction substantially.Preferably, the plurality of CNT line parallel and spaced set, the plurality of carbon nano tube line is arranged in a plane.The diameter of each carbon nano tube line is more than or equal to 0.1 micron, and is less than or equal to 100 microns.Preferably, the diameter of each carbon nano tube line is more than or equal to 5 microns, and is less than or equal to 50 microns.Interval between the plurality of carbon nano tube line is not limit, and preferably, the spacing between adjacent carbon nano tube line is greater than 0.1 millimeter.Diameter and the interval of described multiple carbon nano tube line can be determined according to actual needs.Preferably, the diameter of the plurality of carbon nano tube line is substantially equal.Each carbon nano tube line comprises multiple first CNT, and the plurality of first CNT is arranged of preferred orient along described first direction substantially, that is, the plurality of first CNT arranges along the axial preferred orientation of described carbon nano tube line.The the first adjacent CNT being axially positioned at described carbon nano tube line is joined end to end by Van der Waals force.Preferably, the plurality of CNT is axially basic parallel with the axis of this carbon nano tube line.Wherein, described first direction is basically parallel to the axis of described carbon nano tube line and the axis of described first CNT.
Described multiple carbon nano tube cluster interval is arranged, and is overlapped between adjacent carbon nano tube line, and making this carbon nano-tube film have self-supporting characteristic, is a self supporting structure.So-called " self-supporting " refers to that this carbon nano-tube film does not need support body supports just can keep its intrinsic shape.The plurality of carbon nano tube cluster in a second direction interval is arranged, and is distinguished by described multiple carbon nano tube line.Alternatively, the multiple carbon nano tube clusters be positioned in this second direction are linked together by the plurality of carbon nano tube line.The multiple carbon nano tube clusters be positioned in second direction can be staggered, not arrangement in a row, thus, connect by described multiple carbon nano tube line the conductive path forming non-linear in a second direction.The multiple carbon nano tube cluster proper alignment be positioned in this second direction are embarked on journey, and form a continuous print linear conductive path by the plurality of carbon nano tube line.Preferably, the plurality of carbon nano tube cluster is arranged in array in this carbon nano-tube film.Wherein, this second direction is crossing with described first direction to be arranged, and preferably, this second direction is vertical with first direction to be arranged.Each carbon nano tube cluster length is in this second direction substantially equal with the spacing of the carbon nano tube line that this carbon nano tube cluster is connected.So this carbon nano tube cluster length is in a second direction preferably more than 0.1 millimeter.In addition, the multiple carbon nano tube cluster intervals between adjacent carbon nano tube line are arranged, that is, the plurality of carbon nano tube cluster is arranged at interval in said first direction.Preferably, adjacent carbon nano tube cluster spacing is in a first direction more than or equal to 1 millimeter.
Described carbon nano tube cluster comprises multiple second CNT, and the plurality of second CNT is interacted together by Van der Waals force.The axis of the plurality of second CNT can be basically parallel to described first direction, that is, the axis of the plurality of second CNT can be basically parallel to the axis of described carbon nano tube line.The axis of the plurality of second CNT also can crossingly with described first direction be arranged, and therefore, the second CNT in this carbon nano tube cluster can formation network structure arranged in a crossed manner.
As can be seen here, described carbon nano-tube film comprises multiple CNT, and the plurality of CNT forms described multiple carbon nano tube line and multiple carbon nano tube cluster respectively.Preferably, this carbon nano-tube film is only made up of CNT.This carbon nano-tube film also comprises multiple hole, and the plurality of hole is mainly arranged by the multiple carbon nano tube line in this carbon nano-tube film and multiple carbon nano tube cluster interval and formed.So when the plurality of carbon nano tube line and multiple carbon nano tube cluster have rule rate to arrange, the plurality of hole is regular arrangement also.As, when described multiple carbon nano tube cluster and carbon nano tube line are arranged in array, the plurality of hole also can be arranged in array thereupon.The ratio of the area sum of the carbon nano tube line in this carbon nano-tube film and carbon nano tube cluster and the area of described multiple hole is greater than 0, and is less than or equal to 1: 19.Alternatively, the area ratio of the multiple CNT in this carbon nano-tube film and described multiple hole is greater than 0, and is less than or equal to 1: 19.Preferably, the area of the CNT in this carbon nano-tube film and the area ratio of the plurality of hole are greater than 0, and are less than or equal to 1: 49.So the light transmittance of this carbon nano-tube film is more than or equal to 95%, preferably, the light transmittance of this carbon nano-tube film is more than or equal to 98%.The plurality of carbon nano tube line extends along first direction, thus makes this carbon nano-tube film form one first conductive path in a first direction; The plurality of carbon nano tube cluster can form one second conductive path in a second direction; Thus make this carbon nano-tube film for conduction anisotropic membrane, and there is on first direction and second direction different conduction anisotropy.The ratio of this carbon nano-tube film resistance in a second direction and its resistance is in a first direction more than or equal to 10.Preferably, this carbon nano-tube film resistance is in a second direction more than or equal to 20 times of its resistance in a first direction.As, this carbon nano-tube film resistance in a second direction can higher than 50 of its resistance in a first direction times.In addition, the carbon nano tube line in this carbon nano-tube film is connected by carbon nano tube cluster wherein, thus makes this carbon nano-tube film have good intensity and stability, survivable.
It should be noted that, the carbon nano tube line in this carbon nano-tube film and the surrounding of carbon nano tube cluster also have a small amount of CNT, but the existence of these CNTs can not affect the character of this carbon nano-tube film substantially.
Refer to Fig. 1, the preparation method of the above-mentioned carbon nano-tube film of the present invention comprises the following steps:
S10, provides an initial carbon nanotube films, and this initial carbon nanotube films comprises multiple CNT, and the plurality of CNT is joined end to end by Van der Waals force and extends along first direction preferred orientation;
S20, initial carbon nanotube films described in patterning, makes described initial carbon nanotube films form at least a line through hole in said first direction, and has two spaced through holes at least on often going; And
S30, adopts the initial carbon nanotube films being formed with at least one hole of working described in solvent process, and the initial carbon nanotube films making this be formed with at least one hole of working shrinks.
Refer to Fig. 2, the CNT in the initial carbon nanotube films in step S10 extends along first direction preferred orientation.This initial carbon nanotube films can obtain by stretching from a carbon nano pipe array.Particularly, the preparation method of this initial carbon nanotube films comprises the following steps: S11, provides a carbon nano pipe array, and this carbon nano pipe array comprises multiple CNT parallel to each other; And S12, the CNT fragment of selected one fixed width from described carbon nano pipe array, and pull this CNT fragment with one fixed width and obtain described initial carbon nanotube films.
Wherein, preferably, described carbon nano-pipe array is classified as and one surpasses in-line arrangement carbon nano pipe array, and namely this carbon nano pipe array comprises multiple CNT be substantially parallel to each other.This carbon nano pipe array is formed at a substrate, and the CNT in this carbon nano pipe array is substantially perpendicular to this substrate.In above-mentioned drawing process, while selected CNT in this carbon nano pipe array departs from substrate gradually along draw direction under a stretching force, due to van der Waals interaction, this selected CNT is drawn out continuously end to end by Van der Waals force with other CNTs in carbon nano pipe array respectively and forms described initial carbon nanotube films.The bearing of trend of the CNT in this initial carbon nanotube films is basically parallel to the draw direction of carbon nano-tube film.Therefore, this initial carbon nanotube films is made up of CNT, and passes through the effect of the Van der Waals force between CNT, and making this initial carbon nanotube films have self-supporting characteristic, is a self-supported membrane.Can form multiple micropore between CNT in this initial carbon nanotube films, the effective diameter of this micropore is less than 100 nanometers.
The object that described step S20 carries out patterned process to initial carbon nanotube films is along first direction forming arrangement in a row and spaced through hole on described initial carbon nanotube films.This step can adopt the method such as laser treatment with irradiation or electron beam irradiation process to form described multiple through hole on described initial carbon nanotube films.When this step S20 adopts laser irradiation to carry out patterned process to this prefabricated CNT, this step S20 specifically can comprise step by step following: first, provides a laser instrument, and the exposure pathways of the laser beam of this laser instrument controls by computer program.Secondly, by the shaping input computer program of the carbon nano-tube film of described multiple through hole to be formed, to control the exposure pathways of the laser beam in laser instrument, on described initial carbon nanotube films, ablation forms multiple through hole.Then, open laser instrument, adopt initial carbon nanotube films described in laser beam irradiation, this initial carbon nanotube films forms described multiple through hole.Being appreciated that can also by fixed laser bundle, and mobile described initial carbon nanotube films makes the surface of this initial carbon nanotube films of laser beam irradiation, and control the motion path of this initial carbon nanotube films, on this initial carbon nanotube films, ablation forms multiple through hole.Wherein, the power density of described laser beam is 10000-100000 watt/square millimeter, and sweep speed is 800-1500 mm/second.Preferably, the power density of this laser beam is 70000-80000 watt/square millimeter, and sweep speed is 1000-1200 mm/second.
The shape of the through hole formed in described step S20 can be the figures such as quadrangle, circle, ellipse or triangle.Preferably, this quadrangle has at least one pair of parallel edges, e.g., and parallelogram, trapezoidal, rectangle, rhombus etc.More preferably, this through hole be formed as rectangle.When rectangular width is smaller, can think that this rectangle is a straight line, namely can think that the shape of this through hole is linear.The effective diameter of described through hole is greater than the effective diameter of the micropore in described initial carbon nanotube films.Preferably, the effective diameter of this through hole is more than or equal to 0.1 millimeter.Spacing between adjacent through hole is greater than the effective diameter of the micropore in described initial carbon nanotube films.Preferably, the spacing between this adjacent through-holes is more than or equal to 0.1 millimeter.Spacing between the shape of described through hole, effective diameter and adjacent through hole can be determined according to actual needs.
Carry out patterned process to described initial carbon nanotube films in this step S20, the through hole that this initial carbon nanotube films is formed can distribute according to several modes below:
(1) refer to Fig. 3, described initial carbon nanotube films 120 forms multiple spaced through hole 122, the plurality of spaced through hole 122 is arranged in a line along described first direction X in this initial carbon nanotube films.Wherein, this first direction X is basically parallel to the axial bearing of trend of the CNT in this initial carbon nanotube films 120.This initial carbon nanotube films 120 is divided into multiple connecting portion 124 and two extensions 126 by the plurality of through hole, the connecting portion 124 of this initial carbon nanotube films is the part between through hole 122 adjacent in same a line, that is, connecting portion 124 interval of this initial carbon nanotube films 120 is arranged and is separated by through hole 122, and alternately arranges with the plurality of through hole 122.Two extensions 126 of this initial carbon nanotube films 120 refer to the other parts in this initial carbon nanotube films 120 except described connecting portion 124, and lay respectively at the both sides of described multiple connecting portion 124.Alternatively, on the second direction Y crossing with first direction X, these two extensions 126 are separated by the plurality of connecting portion 124.So the plurality of connecting portion 124 and two extensions 126 are integrative-structures, these two extensions 126 are linked together by the plurality of connecting portion 124.Preferably, this second direction Y is perpendicular to first direction X.Each extension 126 extends continuously along described first direction X substantially.
(2) refer to Fig. 4, described initial carbon nanotube films 120 forms multiple through hole 122, the plurality of through hole 122 is arranged in multirow along described first direction X, and the through hole 122 being arranged in same a line is spaced along described first direction X.The plurality of through hole 122 can be crisscross arranged on described second direction Y.So-called " being crisscross arranged " refers to the plurality of through hole 122 does not have arrangement in column on second direction Y.Be appreciated that described multiple through hole 122 also can be arranged in multiple row along this second direction Y, and the through hole 122 be positioned on same row is spaced along this second direction Y, so the plurality of through hole 122 is in array-like, and ranks are arranged.That is, the plurality of through hole 122 is arranged in multiple lines and multiple rows on this initial carbon nanotube films 120.
This initial carbon nanotube films 120 is divided into multiple connecting portion 124 and multiple extension 126 by the plurality of through hole 122.Between the through hole 122 that the plurality of connecting portion 124 is adjacent in same a line, the arrangement mode of the plurality of connecting portion 124 is identical with the arrangement mode of the plurality of through hole 122, connecting portion 124 with a line is arranged along first direction X interval, and is separated by the through hole 122 with a line.The length of each connecting portion 124 on second direction Y equals the length of its adjacent through hole 122 on second direction Y, and each connecting portion 124 equals and its spacing in same a line and between be adjacent two through holes 122 substantially along the length on first direction.Described multiple extension 126 is that a continuous print is overall on first direction X, and between the through hole 122 of adjacent lines and the connecting portion 124 of described initial carbon nanotube films 120.The length of each extension 126 on second direction Y is the spacing of through hole 122 on second direction Y of its adjacent rows, and is separated by the multiple connecting portions 124 in two row be adjacent.Similarly, the plurality of connecting portion 124 is structure as a whole with the plurality of extension 126, and the plurality of extension 126 is linked together by the plurality of connecting portion 124.Preferably, the effective length of each through hole 122 on first direction X is greater than the spacing of its adjacent through hole 122 on second direction Y.
It should be noted that, so-called " being arranged in the through hole of same a line " refers to and has at least a straight line being basically parallel to described first direction X can run through the through hole that this is positioned at same a line simultaneously herein; So-called " being arranged in the through hole of same row " refers to and has at least a straight line being basically parallel to described second direction Y can run through the through hole that this is arranged in same row simultaneously herein.The arrangement mode of the connecting portion 124 in described initial carbon nanotube films 120 is substantially identical with the arrangement mode of the through hole in this initial carbon nanotube films.Owing to being subject to the impact of preparation technology, the surrounding of each through hole may have a small amount of CNT burr to be existed, thus makes the uneven phenomenon of the marginal existence of through hole.
In step s 30, the initial carbon nanotube films of described patterning preferably unsettled setting.This step S30 can be, by described solvent drippage or the surface being formed with the initial carbon nanotube films of multiple through hole being sprayed at unsettled setting, to infiltrate the initial carbon nanotube films that this has at least one hole of working, the initial carbon nanotube films making this have at least one hole of working shrinks.Because the CNT head and the tail in each extension in this initial carbon nanotube films are adjacent and substantially arrange along first direction, and each extension is a continuous print entirety in a first direction, so, under capillary effect, multiple extensions in this initial carbon nanotube films shrink and form multiple carbon nano tube line respectively, that is, each extension heart contraction formation carbon nano tube line wherein of this initial carbon nanotube films, make the effective diameter of the through hole being positioned at these extension both sides increase simultaneously, thus form multiple spaced carbon nano tube line.Simultaneously, each extension can produce a pulling force by the connecting portion contiguous to it in the process being shrunk to carbon nano tube line, this connecting portion is made to form described carbon nano tube cluster, thus form described carbon nano-tube film, this carbon nano-tube film is made to comprise the carbon nano tube line at multiple interval, and by multiple carbon nano tube clusters that the plurality of carbon nano tube line separates.Therefore, the spacing between carbon nano tube line adjacent in this carbon nano-tube film is greater than the through hole length in a second direction clamped between extension adjacent on the initial carbon nanotube films of its correspondence, is greater than 0.1 millimeter; And each carbon nano tube line to be joined end to end by Van der Waals force and the CNT extended substantially is in the same direction formed by multiple, the plurality of CNT extends along first direction substantially.Adjacent carbon nano tube line is joined together to form described carbon nano-tube film by Van der Waals force by the plurality of carbon nano tube cluster.
According to volatile difference of described solvent, the surface tension of this solvent to described initial carbon nanotube films is also different, the extension of this initial carbon nanotube films is also different to the size of the pulling force that its adjacent connecting portion produces in the process being shrunk to carbon nano tube line, thus make the arrangement mode of the CNT in the connecting portion of this initial carbon nanotube films different, and then make the structure of described carbon nano tube cluster also different.
When described solvent is organic solvent, when ethanol, methyl alcohol, acetone, dichloroethanes or chloroform etc. have more high-volatile solvent, just larger to the surface tension of this initial carbon nanotube films, the pulling force that the extension of this initial carbon nanotube films produces its adjacent connecting portion in the process being shrunk to carbon nano tube line is just larger, being changed into the direction crossing with this first direction extended by basic to extend along first direction of the CNT in this connecting portion can be made, form the second CNT; Simultaneously under capillary effect, the CNT in each connecting portion can shrink formation one network structure, and this network structure is described carbon nano tube cluster.So the plurality of connecting portion is formed multiplely has cancellated carbon nano tube cluster.Preferably, the axis of this second CNT and described first direction have the first larger angle, and this first angle is more than or equal to 45 degree, and are less than or equal to 90 degree.
When described solvent is water, or when there is the mixed solution of certain density water and organic solvent, this solvent is relatively little to the surface tension of this initial carbon nanotube films, the pulling force that the extension of this initial carbon nanotube films produces its adjacent connecting portion in the process being shrunk to carbon nano tube line is relatively little, just smaller to the pulling force of the CNT in the connecting portion of this initial carbon nanotube films, thus make the axis of the CNT in the plurality of connecting portion substantially not change or change less, form multiple carbon nano tube cluster, now, the axis of the CNT in this carbon nano tube cluster is basically parallel to the axis of the CNT in described carbon nano tube line and described first direction, or CNT in the axis of CNT in this carbon nano tube cluster and this carbon nano tube line and first direction have the second less angle, and this second angle is less than or equal to 30 degree.Preferably, this angle is less than or equal to 15 degree.As, when solvent is water, the orientation of the CNT in the connecting portion of described initial carbon nanotube films does not change substantially, thus makes the orientation of the CNT in this carbon nano tube cluster be basically parallel to described first direction.
Be appreciated that when the through hole in step S20 is multirow arrangement, in described carbon nano-tube film, the substantially parallel setting of multiple carbon nano tube lines formed by the extension of described initial carbon nanotube films.Separately, when the through hole in this initial carbon nanotube films is multiple lines and multiple rows arrangement, multiple extensions in described initial carbon nanotube films can form multiple carbon nano tube line, and the plurality of carbon nano tube line axially extends along first direction, and are parallel to each other and interval setting along second direction; And the multiple connecting portions in this initial carbon nanotube films can form multiple carbon nano tube cluster, this carbon nano tube cluster can be overlapped along described second direction by described carbon nano tube line, and arranges along first direction interval.So now, the multiple carbon nano tube lines in this carbon nano-tube film extend along first direction in parallel to each other and arrange along second direction interval, form multiple spaced first conductive path; Multiple carbon nano tube clusters in this carbon nano-tube film are arranged along described first direction interval, and are connected to form described multiple spaced second conductive path along described second direction by carbon nano tube line.
Be appreciated that spacing between the through hole by controlling along second direction arrangement and the shape of through hole can control the diameter of described carbon nano tube line; The spacing between adjacent carbon nano tube line can be controlled by the width controlling spacing between the adjacent through-holes in second direction and through hole.When described through hole is rectangle, the length in second direction of this through hole is equal respectively, and when spacing between adjacent through-holes on same row is equal, the equal diameters of described multiple carbon nano tube line, and spacing between adjacent carbon nano tube line is also equal; Further, when the length at first direction of the plurality of through hole is equal respectively, described multiple carbon nano tube cluster is substantially along second direction arrangement, and the shape of even the plurality of carbon nano tube cluster is substantially identical.Therefore, the preparation method of the carbon nano-tube film provided by the invention diameter that can control wherein between carbon nano tube line spacing and carbon nano tube line effectively, simply.
Identical in other condition, number of openings in a first direction does not affect described carbon nano-tube film resistance in a first direction substantially.Number of openings is in a first direction more, and described carbon nano-tube film resistance in a second direction may be higher; Number of openings is in a second direction fewer, and this carbon nano-tube film resistance in a second direction may be lower.Identical in other condition, number of openings in a second direction does not affect this carbon nano-tube film resistance in a second direction substantially.Number of openings is in a second direction more, and described carbon nano-tube film resistance is in a first direction higher; When the number of openings in second direction is fewer, described carbon nano-tube film resistance is in a first direction lower.Therefore, the resistance of described carbon nano-tube film can be changed by the quantity adjusting described through hole, especially change the conduction anisotropy of this carbon nano-tube film, that is, step S20 can be carried out according to the demand of the resistance to described carbon nano-tube film.
It should be noted that, the relevant parameter of through hole affects the electric conductivity of this carbon nano-tube film.Wherein, assuming that the through hole on described initial carbon nanotube films is uniformly distributed, and each through hole is rectangle, each through hole length is in a first direction a, each through hole length is in a second direction b, adjacent through hole spacing is in a first direction c, and adjacent through hole spacing is in a second direction d.Preferably, parameter a is greater than parameter d.Wherein, suitable relative to parameter a hour of described parameter b, parameter b can think 0, and this through hole can be considered to as straight line.Particularly, through hole relevant parameter on the resistance of carbon nano-tube film and anisotropic impact of conducting electricity as follows:
(1) when the parameter c of through hole and d fixes, when changing parameter a and b, the ratio of the resistance of this carbon nano-tube film in second direction and first direction becomes large along with the increase of the ratio (a/b) of parameter a and b.That is, the conduction anisotropy of this carbon nano-tube film is directly proportional to the ratio of parameter a and b.
(2) when the parameter a of through hole and c fixes, when changing parameter b and d, this carbon nano-tube film becomes large along with the increase of the ratio (b/d) of parameter b and d substantially at the resistance of first direction.
(3), when the parameter b of through hole and d fixes, when changing parameter a and c, this carbon nano-tube film resistance in a second direction increases along with the ratio (a/c) of parameter a and parameter c and increases; Separately, the conduction anisotropy of this carbon nano-tube film can be improved by the method for the ratio reducing parameter a and c.
Be appreciated that initial carbon nanotube films in described step S20 is before patterned process, should fix this initial carbon nanotube films in advance, preferably, be unsettled setting by this initial carbon nanotube films.As, when this initial carbon nanotube films directly pull from a carbon nano pipe array obtain time, first can fix this initial carbon nanotube films one end away from this carbon nano pipe array in a fixed body, and then this initial carbon nanotube films of patterned process forms described multiple through hole, afterwards again with the initial carbon nanotube films of this patterning of organic solvent process.In addition, when collecting this carbon nano-tube film, when especially adopting a rotating collection axle to collect this carbon nano-tube film, rotate this collection axle, can while the carbon nano-tube film prepared be collected on this collection axle, continuous pulling from described carbon nano pipe array obtains described prefabricated carbon nano-tube film on one side, thus can realize carbon nano-tube film described in automated production.
Carbon nano-tube film provided by the invention and preparation method thereof will be further illustrated below with specific embodiment.
Refer to Fig. 5, first embodiment of the invention provides a carbon nano-tube film 10, this carbon nano-tube film 10 is a self supporting structure, and comprise multiple carbon nano tube line 12 and multiple carbon nano tube cluster 14, the plurality of carbon nano tube cluster 14 is overlapped between adjacent carbon nano tube line 12 by Van der Waals force, and the plurality of carbon nano tube line 12 separates.
The plurality of carbon nano tube line 12 is parallel to each other and spacing side by side setting substantially along second direction Y, and the axis of the plurality of carbon nano tube line 12 is basic to be extended along first direction X, forms one first conductive path.Wherein, second direction Y is perpendicular to first direction X.Each carbon nano tube line 12 to be joined end to end by Van der Waals force by multiple and formed along the CNT that first direction X arranges.The diameter of each carbon nano tube line 12 is approximately 10 microns.And the spacing between adjacent carbon nano tube line 12 is greater than 1 millimeter.
The plurality of carbon nano tube cluster 14 is in arrayed.Particularly, the plurality of carbon nano tube cluster 14 is arranged along first direction X interval, and the proper alignment be connected to form linear second conductive path by the plurality of carbon nano tube line 12 of embarking on journey on second direction Y.CNT in each carbon nano tube cluster 14 formation network structure arranged in a crossed manner.The axial bearing of trend of the CNT in each carbon nano tube cluster is crossing with first direction X, and angle is more than or equal to 60 degree, and is less than or equal to 90 degree.
Separately, between adjacent in a first direction carbon nano tube cluster 14 and the surrounding of carbon nano tube line 12 all there is a small amount of CNT.That is, the CNT of a small amount of random arrangement is also had in this carbon nano-tube film 10.
As can be seen here, the different in kind of this carbon nano-tube film 10 on first direction X and second direction Y, especially its this both direction has and conducts electricity anisotropy preferably.The resistance of this carbon nano-tube film 10 on second direction Y is approximately 50 times of its resistance on first direction X.This carbon nano-tube film 10 also has higher light transmittance, and its light transmittance reaches 98.43% at visible region.
Be appreciated that the carbon nano tube cluster 14 in carbon nano-tube film 10 provided by the invention also can be staggered in a second direction, as shown in Figure 6.
Refer to Fig. 7, first embodiment of the invention provides the preparation method of above-mentioned carbon nano-tube film 10, and the preparation method of this carbon nano-tube film 10 comprises the following steps:
One carbon nano pipe array 110 is provided, this carbon nano pipe array 110 is grown on a substrate 112, adopt an adhesive tape 114 stretched initial carbon nanotube films 120 from this carbon nano pipe array 110, this initial carbon nanotube films 120 comprises multiple CNT, and the plurality of CNT is joined end to end by Van der Waals force and arranges in the same direction.Wherein, the bearing of trend of the CNT in this initial carbon nanotube films 120 is first direction X.
Remove described adhesive tape 114, and by described initial carbon nanotube films 120 away from one end of described carbon nano pipe array 110 in a fixed body 128, meanwhile, ensure the unsettled setting of initial carbon nanotube films 120 between this fixed body 128 and carbon nano pipe array 110; Then, power density is adopted to be approximately 70000 watts/square millimeter, the laser beam that sweep speed is approximately 1100 mm/second carries out patterned process to this initial carbon nanotube films 120, this initial carbon nanotube films 120 forms multiple rectangular through hole 122, the plurality of through hole 122 is uniformly distributed and is arranged in multiple lines and multiple rows, and this initial carbon nanotube films 120 is divided into multiple connecting portion 124 and multiple extension 126, as can be seen from figures 8 and 9.The arrangement mode of the plurality of connecting portion 124 is basic the same with the arrangement mode of described multiple through hole 122, and in array-like, multiple lines and multiple rows arranges.Wherein, the plurality of through hole 122 is 1 millimeter along the spacing on first direction X and second direction Y, and each through hole 122 is approximately 3 millimeters along the length of first direction X, and each through hole 122 is approximately 1 millimeter along the length of second direction Y; The parameter a of the plurality of through hole 122, b, c, d are respectively 3 millimeters, 1 millimeter, 1 millimeter, 1 millimeter.Therefore, the connecting portion 124 of this initial carbon nanotube films 120 is 1 millimeter substantially along the length of second direction Y, and the length along first direction X is 1 millimeter substantially.The extension 126 of this initial carbon nanotube films 120 equals the adjacent length of two through holes 122 on second direction Y be positioned on same row along the length of second direction Y, so this extension 126 is 1 millimeter substantially along the length on second direction Y.
One drop bottle 130 is positioned over the described top through the initial carbon nanotube films 120 of laser treatment, and ethanol 132 drips in this surface through the initial carbon nanotube films 120 of laser treatment from this drop bottle 130.Under capillary effect, each extension 126 of described initial carbon nanotube films 120 forms carbon nano tube line 12 in position therebetween.Meanwhile, the contraction of the extension 126 of this initial carbon nanotube films 120 can produce a pulling force to this connecting portion 124, and the most of CNT in this connecting portion 124 is arranged from arranging to become along first direction along the direction crossing with this first direction; Simultaneously under the capillary effect of the plurality of connecting portion 124 self, the plurality of connecting portion 124 forms multiple carbon nano tube cluster 14, and the plurality of carbon nano tube cluster 14 is connected along second direction by described multiple carbon nano tube line, and arrange along first direction interval.Form described carbon nano-tube film 10 thus.
Because laser is formed in the process of through hole 122 at process initial carbon nanotube films 120, the restriction of the edge Stimulated Light self-condition of the through hole 122 in this initial carbon nanotube films 120, the edge of this through hole 122 may be uneven.So after solvent process, the carbon nano tube line 12 in the carbon nano-tube film 10 obtained and the surrounding of carbon nano tube cluster 14 may have the CNT of a small amount of irregular alignment to exist, e.g., the microphotograph of this carbon nano-tube film 10 shown in Figure 10.
Be appreciated that when described through hole as shown in Figure 4 at second direction Y alternate time, the carbon nano tube cluster in the carbon nano-tube film finally prepared also can be staggered, just carbon nano-tube film as shown in Figure 6.
This carbon nano-tube film 10 has good light transmittance and electrical conductivity.The present embodiment is by measuring sample 1-initial carbon nanotube films 120, the initial carbon nanotube films of the initial carbon nanotube films 120(laser treatment of sample 2-laser treatment refers to the above-mentioned initial carbon nanotube films 120 being formed with multiple through hole 122 through laser treatment), the initial carbon nanotube films 120 of sample 3-ethanol postincubation and the light transmittance of sample 4-described carbon nano-tube film 10 and represent the electric anisotropy of each sample with their resistance on first direction X and second direction Y.Light transmittance under the resistance of this carbon nano-tube film 10 and each wavelength, shown in table specific as follows.Wherein, the resistance of each sample in following table 1 is by be fixed on each sample on PET sheet and the square making 3 millimeters × 3 millimeters records, the wherein resistance of not working sample 3, and each sample is by being that the UV glue of 1: 1 and the mixed solution of butyl acetate are coated on PET sheet and realize being fixed on PET sheet by volume ratio.The light transmittance of each sample records under vacant state at each sample.
The resistance of the various film of table 1 and light transmittance
Although the resistance of initial carbon nanotube films crossed than described initial carbon nanotube films 120 and laser treatment of described carbon nano-tube film 10 resistance is in all directions large as can be seen from the above table, but this carbon nano-tube film 10 is still a conduction anisotropic membrane, and its resistance in the two directions still differs more than 50 times.Refer to Figure 11 and upper table 1, the light transmittance of sample 4 under each wavelength is all greater than the light transmittance of sample 2 and sample 3, so the light transmittance of described carbon nano-tube film 10 under each wavelength is all better than the light transmittance of the initial carbon nanotube films that described initial carbon nanotube films 120 and laser treatment are crossed.Separately, under each wavelength, the light transmittance of sample 4 is close to the light transmittance of sample 1, and this illustrates that this carbon nano-tube film 10 has higher light transmittance.Calculate by analysis, can find, this carbon nano-tube film 10 can reach more than 98% in the light transmittance of visible region.
Refer to Figure 12, second embodiment of the invention provides a carbon nano-tube film 20, and this carbon nano-tube film 20 comprises multiple carbon nano tube line 12 and multiple carbon nano tube cluster 24.The plurality of carbon nano tube line 12 and multiple carbon nano tube cluster 24 are in arrayed.The structure of this carbon nano-tube film 20 is substantially identical with the structure of the carbon nano-tube film 10 that the first embodiment provides, difference is: each carbon nano tube cluster 24 comprises multiple second CNT 242, and the axial bearing of trend of the plurality of second CNT 242 is basically parallel to the bearing of trend of described carbon nano tube line 12.That is, the CNT in this carbon nano-tube film 20 is arranged of preferred orient substantially in the same direction.Because this carbon nano-tube film 20 exists error in preparation process, so the carbon nano tube line 12 of this carbon nano-tube film 20 and the surrounding of carbon nano tube cluster 24 have a small amount of CNT to exist.The concrete structure of this carbon nano-tube film 20 can be shown in Figure 13 microphotograph.
The preparation method of this carbon nano-tube film 20 is substantially identical with the preparation method of the carbon nano-tube film 10 that the first embodiment provides, and difference is: this carbon nano-tube film 20 adopts water to process the initial carbon nanotube films being formed with through hole as solvent.
Because relevant parameter a, b, c and d various performances on described carbon nano-tube film being formed in the through hole on initial carbon nanotube films have impact, above-mentioned each parameter compares the impact of described carbon nano-tube film experiment below, in each experiment below, multiple through hole is the surface that array-like is evenly distributed on described initial carbon nanotube films.
(1) under the fixing condition of the parameter a of through hole and c, parameter b and d is on the impact of carbon nano-tube film provided by the invention
Experiment condition is: first, carries out different process to described initial carbon nanotube films.Then, mix 6636 according to the ratio that volume ratio is 1: 1 with butyl acetate solvent; Carry out being mixed to form a mixed solution with UV glue again; The solution this being mixed with UV glue is coated on PET sheet; Then, the initial carbon nanotube films through different disposal is fixed on to obtain the sample of this experiment on PET sheet, and makes the square of 3 millimeters × 3 millimeters, for measuring its resistance.Wherein, each sample measures its light transmittance twice respectively.Specific experiment condition and result are see table 2, and the light transmittance in table 2 refers to the light transmittance of each sample when wavelength is 550 nanometer; Parallel resistance-each sample is parallel to the resistance on the bearing of trend of CNT wherein i.e. the resistance on first direction; Namely vertical resistor is parallel to the resistance of the bearing of trend of CNT wherein, the resistance namely in second direction.
Table 2
Note: the light transmittance of PET sheet when wavelength is 550 nanometer being solidified with UV glue is 91.40%.
Table 2 can prove: (1) described initial carbon nanotube films after laser treatment, then shrinks the described carbon nano-tube film obtained, namely carbon nano-tube film provided by the invention through solvent, can improve the light transmittance of carbon nano-tube film largely.(2) whether fix at the parameter a of through hole and c, when changing parameter b and d, the parallel resistance of sample 1-8 becomes large along with the increase of the ratio (b/d) of parameter b and d, shrink have nothing to do with sample through solvent.Preferably, the ratio of parameter b and d is less than or equal to 2, and parallel resistance is more than or equal to 1 kilo-ohm.(3) fix at the parameter a of through hole and c, when changing parameter b and d, the impact that carbon nano-tube film provided by the invention shrinks owing to being subject to solvent, its vertical resistor has relative to the vertical resistor of the carbon nano-tube film only adopting laser treatment and reduces largely, thus, the conduction anisotropy of carbon nano-tube film provided by the invention is made to decline relative to the conduction anisotropy of the carbon nano-tube film under other conditions.(4) carbon nano-tube film provided by the invention when the increase of resistance minimum degree, can improve its light transmittance.
(2) under the fixing condition of the parameter b of through hole and d, parameter a and c is on the impact of carbon nano-tube film provided by the invention
Experiment condition is: first, carries out different process to described initial carbon nanotube films.Then, mix 6636 according to the ratio that volume ratio is 1: 1 with butyl acetate solvent; Carry out being mixed to form a mixed solution with UV glue again; The solution this being mixed with UV glue is coated on PET sheet; Then, the initial carbon nanotube films through different disposal is fixed on to obtain the sample of this experiment on PET sheet, and makes the square of 3 millimeters × 3 millimeters, for measuring its resistance.Wherein, each sample measures its light transmittance twice respectively.Specific experiment condition and result are see table 3, and the light transmittance in table 3 refers to the light transmittance of each sample when wavelength is 550 nanometer; Parallel resistance-each sample is parallel to the resistance on the bearing of trend of CNT wherein i.e. the resistance on first direction; Namely vertical resistor is parallel to the resistance of the bearing of trend of CNT wherein, the resistance namely in second direction.
Table 3
Note: the light transmittance of PET sheet when wavelength is 550 nanometer being solidified with UV glue is 91.40%.
Whether table 3 can prove: (1) is fixed at the parameter b of through hole and d, and when changing parameter a and c, the vertical resistor of sample 1-8 increases along with the ratio (a/c) of parameter a and parameter c and increases, shrink have nothing to do with sample through solvent.Preferably, the ratio of parameter a and parameter c is more than or equal to 0.5, and is less than or equal to 4.Vertical resistor is preferably more than 30 kilo-ohms.(2) the conduction anisotropy of carbon nano-tube film provided by the invention can be improved by the method for the ratio increasing parameter a and parameter c.(3) solvent shrinks the conduction anisotropy being unfavorable for improving carbon nano-tube film.
(3) strength ratio of carbon nano tube structure comparatively
The maximum pull that various carbon nano tube structure can bear herein represents with " intensity ".The initial carbon nanotube film strength that width is approximately 15 millimeters is approximately 150 milli newton; The initial carbon nanotube film strength that this width of laser treatment is approximately 15 millimeters is approximately 47 milli newton; CNT film strength provided by the invention be approximately 105 milli newton, wherein, this carbon nano-tube film be by width be approximately 15 millimeters initial carbon nanotube films prepare get.Wherein, the initial carbon nanotube films of laser treatment and carbon nano-tube film provided by the invention, all make the parameter a of the through hole that described initial carbon nanotube films is formed, b, c and d be respectively 3 millimeters, 0.35 millimeter, 0.8 millimeter and 0.35 millimeter in the process of laser process.Preferably, when the width of initial carbon nano-tube film is approximately 15 millimeters, CNT film strength provided by the invention is more than or equal to 90 milli newton.
The carbon nano-tube film that the preparation method of the carbon nano-tube film provided by the embodiment of the present invention prepares comprises multiple spaced carbon nano tube line and carbon nano tube cluster, so this carbon nano-tube film has more hole, thus make this carbon nano-tube film have higher light transmittance, and the light transmittance of this carbon nano-tube film is more than or equal to 95% at visible region, even can more than 98% be reached.Carbon nano tube line in this carbon nano-tube film extends to form the first conductive path along first direction, and the carbon nano tube cluster in this carbon nano-tube film is connected to form the second conductive path along second direction by carbon nano tube line; So this carbon nano-tube film has conduction anisotropy, it is conduction anisotropic membrane.The resistance of this carbon nano-tube film in second direction and first direction can differ more than 50 times.Separately, the carbon nano tube line in this carbon nano-tube film is fixed together by multiple carbon nano tube cluster, forms membrane structure, makes this carbon nano-tube film have good intensity and stability, not easily break.
The embodiment of the present invention is by forming at least a line through hole the method that this is formed with the initial carbon nanotube films of through hole in conjunction with solvent process prepares described carbon nano-tube film on the surface of this initial carbon nanotube films, simultaneously, the spacing that can also control between the diameter of the carbon nano tube line in carbon nano-tube film and adjacent carbon nano tube line by the through hole relevant parameter controlled on initial carbon nanotube films, namely the structure of this carbon nano-tube film is controlled, and then this carbon nano-tube film resistance in all directions can be controlled, therefore the preparation method of this carbon nano-tube film is fairly simple, be easy to the resistance controlling this carbon nano-tube film, be conducive to suitability for industrialized production.In addition, preparing the process of carbon nano-tube film, described through hole is formed in described initial carbon nanotube films regularly, regularly, carbon nano tube line in carbon nano-tube film prepared by the method provided by the embodiment of the present invention and carbon nano tube cluster is regular is arranged in multiple lines and multiple rows, also has conduction anisotropy while having compared with high-transmittance.
In addition, those skilled in the art can also do other change in spirit of the present invention, and these changes done according to the present invention's spirit all should be included in the present invention's scope required for protection.
Claims (20)
1. a carbon nano-tube film, it comprises multiple carbon nano tube line and multiple carbon nano tube cluster, and the plurality of carbon nano tube line interval is arranged; The plurality of carbon nano tube cluster is separated by the plurality of carbon nano tube line, and the multiple carbon nano tube cluster intervals between adjacent carbon nano tube line are arranged.
2. carbon nano-tube film as claimed in claim 1, it is characterized in that, the multiple carbon nano tube lines in described carbon nano-tube film be arranged in parallel, and extend to form one first conductive path along a first direction.
3. carbon nano-tube film as claimed in claim 2, it is characterized in that, described multiple carbon nano tube cluster is arranged along described first direction interval, and be connected to form one second conductive path along a second direction by described multiple carbon nano tube line, wherein this second direction and described first direction arranged in a crossed manner.
4. carbon nano-tube film as claimed in claim 3, is characterized in that, described multiple carbon nano tube cluster arrangement in a row in this second direction.
5. carbon nano-tube film as claimed in claim 3, it is characterized in that, described multiple carbon nano tube cluster is staggered in this second direction.
6. carbon nano-tube film as claimed in claim 1, it is characterized in that, each carbon nano tube line is made up of multiple CNT, and the plurality of CNT is substantially extended along the axial direction of carbon nano tube line and joined end to end by Van der Waals force.
7. carbon nano-tube film as claimed in claim 6, is characterized in that, the axis being axially parallel to this carbon nano tube line of the CNT in described carbon nano tube line.
8. carbon nano-tube film as claimed in claim 6, it is characterized in that, the diameter of described carbon nano tube line is more than or equal to 0.1 micron, and is less than or equal to 100 microns.
9. carbon nano-tube film as claimed in claim 1, it is characterized in that, each carbon nano tube cluster comprises multiple CNT, the axis being axially parallel to described multiple carbon nano tube line of the plurality of CNT.
10. carbon nano-tube film as claimed in claim 1, it is characterized in that, each carbon nano tube cluster comprises multiple CNT, and the axis of the plurality of CNT is crossing with the axis of described multiple carbon nano tube line to be arranged.
11. carbon nano-tube films as claimed in claim 1, it is characterized in that, the spacing between adjacent carbon nano tube line is greater than 0.1 millimeter.
12. carbon nano-tube films as claimed in claim 1, it is characterized in that, the spacing between the adjacent carbon nano tube cluster in the carbon nano tube cluster between adjacent carbon nano tube line is greater than 1 millimeter.
13. carbon nano-tube films as claimed in claim 1, be is characterized in that, be interconnected between described carbon nano tube line and carbon nano tube cluster by Van der Waals force.
14. 1 kinds of carbon nano-tube films, it comprises: multiple CNT and multiple hole, the plurality of CNT composition multiple parallel and apart from one another by carbon nano tube line and multiple carbon nano tube cluster between adjacent CNT; The area ratio of the plurality of CNT and the plurality of hole is greater than 0, and is less than or equal to 1:19.
15. carbon nano-tube films as claimed in claim 14, it is characterized in that, the area ratio of described multiple CNT and the plurality of hole is greater than 0, and is less than or equal to 1:49.
16. carbon nano-tube films as claimed in claim 14, it is characterized in that, the diameter of described carbon nano tube line is more than or equal to 0.1 micron, and is less than or equal to 100 microns, and the spacing between adjacent described carbon nano tube line is greater than 0.1 millimeter.
17. carbon nano-tube films as claimed in claim 16, it is characterized in that, described multiple carbon nano tube line extends along a first direction, and in a second direction parallel arrangement, wherein this second direction and this first direction arranged in a crossed manner.
18. carbon nano-tube films as claimed in claim 17, it is characterized in that, described carbon nano tube cluster between adjacent carbon nano tube line is arranged along described first direction interval, and described multiple carbon nano tube cluster is connected by described multiple carbon nano tube line in a second direction.
19. carbon nano-tube films as claimed in claim 18, it is characterized in that, each carbon nano tube cluster comprises multiple CNT, and the axis of the plurality of CNT is crossing with described first direction to be arranged.
20. carbon nano-tube films as claimed in claim 18, it is characterized in that, each carbon nano tube cluster comprises multiple CNT, the plurality of CNT be axially parallel to described first direction.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210122626.0A CN103373718B (en) | 2012-04-25 | 2012-04-25 | Carbon nano tube film |
| TW101115681A TWI464113B (en) | 2012-04-25 | 2012-05-02 | Carbon nanotube film |
| US13/740,267 US20130287997A1 (en) | 2012-04-25 | 2013-01-14 | Carbon nanotube film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210122626.0A CN103373718B (en) | 2012-04-25 | 2012-04-25 | Carbon nano tube film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103373718A CN103373718A (en) | 2013-10-30 |
| CN103373718B true CN103373718B (en) | 2015-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210122626.0A Active CN103373718B (en) | 2012-04-25 | 2012-04-25 | Carbon nano tube film |
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| Country | Link |
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| US (1) | US20130287997A1 (en) |
| CN (1) | CN103373718B (en) |
| TW (1) | TWI464113B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105329841B (en) * | 2014-06-17 | 2017-02-15 | 清华大学 | Preparation method of carbon nanotube film |
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| CN105696139B (en) * | 2004-11-09 | 2019-04-16 | 得克萨斯大学体系董事会 | The manufacture and application of nano-fibre yams, band and plate |
| US8329135B2 (en) * | 2006-01-06 | 2012-12-11 | National Institute Of Advanced Industrial Science And Technology | Aligned carbon nanotube bulk structure having portions different in density |
| KR20080106102A (en) * | 2007-05-30 | 2008-12-04 | 주식회사 엘지화학 | Dispersant containing metal complex for carbon nanotube |
| JP5030057B2 (en) * | 2007-07-04 | 2012-09-19 | 国立大学法人九州大学 | Fabrication of conductive carbon nanotube honeycomb film |
| CN101470558B (en) * | 2007-12-27 | 2012-11-21 | 清华大学 | Touch screen and display equipment |
| CN101458598B (en) * | 2007-12-14 | 2011-06-08 | 清华大学 | Touch screen and display device |
| WO2009107229A1 (en) * | 2008-02-29 | 2009-09-03 | 富士通株式会社 | Sheet structure, semiconductor device and method of growing carbon structure |
| CN101556885B (en) * | 2008-04-09 | 2011-03-23 | 鸿富锦精密工业（深圳）有限公司 | Electronic transmitting device and display device |
| CN101734645B (en) * | 2008-11-14 | 2015-09-30 | 清华大学 | carbon nano-tube film |
| TWI375737B (en) * | 2009-08-21 | 2012-11-01 | Hon Hai Prec Ind Co Ltd | Carbon nanotube fabric and heater adopting the same |
| CN102086035B (en) * | 2009-12-03 | 2013-06-19 | 北京富纳特创新科技有限公司 | Carbon-nano-tube film and preparation method thereof |
| CN101894720B (en) * | 2010-04-14 | 2013-06-19 | 北京富纳特创新科技有限公司 | Preparation method for micro-grids of transmission electron microscope (TEM) |
-
2012
- 2012-04-25 CN CN201210122626.0A patent/CN103373718B/en active Active
- 2012-05-02 TW TW101115681A patent/TWI464113B/en active
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2013
- 2013-01-14 US US13/740,267 patent/US20130287997A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CN103373718A (en) | 2013-10-30 |
| TWI464113B (en) | 2014-12-11 |
| US20130287997A1 (en) | 2013-10-31 |
| TW201343546A (en) | 2013-11-01 |
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