CN101923912B - Carbon nanotube film and composite film based on same - Google Patents
Carbon nanotube film and composite film based on same Download PDFInfo
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- CN101923912B CN101923912B CN2010102031608A CN201010203160A CN101923912B CN 101923912 B CN101923912 B CN 101923912B CN 2010102031608 A CN2010102031608 A CN 2010102031608A CN 201010203160 A CN201010203160 A CN 201010203160A CN 101923912 B CN101923912 B CN 101923912B
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Abstract
The invention relates to a carbon nanotube film. The carbon nanotube film comprises a plurality of carbon nanotubes which are basically parallel with one another and are arranged basically parallel to the surface of the carbon nanotube film, wherein the carbon nanotube film has resistance anisotropy, and the sheet resistance of the carbon nanotube film is of megohm level in the direction vertical to the carbon nanotube arrangement. The invention also provides a carbon nanotube composite film, which comprises a polymer substrate and the carbon nanotube film in the polymer substrate, wherein the carbon nanotube film comprises a plurality of carbon nanotubes which are basically parallel with one another and are arranged basically parallel to the surface of the carbon nanotube film; the carbon nanotube film has resistance anisotropy, and the sheet resistance of the carbon nanotube film is of megohm level in the direction vertical to the carbon nanotube arrangement. The megohm level carbon nanotube film or the carbon nanotube composite film can be applied in the fields of transparent electrodes, thin film transistors, touch screens and the like.
Description
Technical field
The present invention relates to a kind of film, relate in particular to a kind of carbon nano-tube film and the composite membrane based on this carbon nano-tube film.
Background technology
Since finding first carbon nano-tube (Carbon Nanotube, CNT), the structure that the nano material that the carbon nano-tube of take is representative is unique with it and character have caused that people pay close attention to greatly.In recent years, along with deepening continuously of carbon nano-tube and nano materials research, its broad prospect of application constantly displays (" Carbon Nanotube-the Route to Applications ", Ray H.Baughman, et a1.Science297,787 (2002)).The electromagnetism of the uniqueness had due to carbon nano-tube, optics, mechanics, chemical property etc., a large amount of relevant its application studies in fields such as field emitting electronic source, transducer, novel optical material, soft ferromagnetic materials constantly are in the news.
Carbon nano-tube film (Carbon Nanotube Film, CNT Film) is one of concrete form of carbon nano-tube practical application, and because carbon nano-tube has excellent electric conductivity, carbon nano-tube film can be applied to transparent conductive film.In prior art, the preparation of carbon nano-tube film, except can obtaining by the direct growth method, also can obtain carbon nano-tube film by carbon nanotube powder.For example: point solvent drips seasoning, L B film method, print process, electrophoresis, and filter membrane method etc.In prior art, carbon nano-tube film can also obtain by the method directly pulled from carbon nano pipe array.
Yet, in the carbon nano-tube film that the preparation method of above-mentioned carbon nano-tube film obtains, the skewness of carbon nano-tube has distribution on all directions, make this carbon nano-tube film substantially even at the resistance of all directions, there is the isotropic characteristics of resistance; And a plurality of carbon nano-tube mutually are wound around and form large diameter carbon nano-tube bundle, in application, due to the formation of these large diameter carbon nano-tube bundles good conductive channel, the square resistance of this carbon nano-tube film is lower.
Summary of the invention
In view of this, necessaryly provide a kind of have resistance anisotropy character and the higher carbon nano-tube film of square resistance.
A kind of carbon nano-tube film, this carbon nano-tube film comprises that a plurality of each carbon nano-tube film comprise a plurality of carbon nano-tube that substantially are parallel to each other and are basically parallel to the carbon nano-tube film surface alignment, this carbon nano-tube film there is resistance anisotropy, it is mega-ohms at the square resistance perpendicular in the carbon nano-tube orientation.
A kind of carbon nano-tube compound film, this carbon nano-tube compound film comprises a macromolecule matrix and is arranged at the carbon nano-tube film in macromolecule matrix, this carbon nano-tube film comprises that a plurality of each carbon nano-tube film comprise a plurality of carbon nano-tube that substantially are parallel to each other and are basically parallel to the carbon nano-tube film surface alignment, this carbon nano-tube film there is resistance anisotropy, it is mega-ohms at the square resistance perpendicular in the carbon nano-tube orientation.
Compared to prior art, because the carbon nano-tube in described carbon nano-tube film is arranged parallel to each other substantially, because carbon nano-tube has extraordinary resistance anisotropy, carbon nano-tube has conductivity preferably in the axial direction, there is very large resistance on direction perpendicular to axial direction, make this carbon nano-tube film there is extraordinary resistance anisotropy, and the negligible amounts of the large diameter carbon nano-tube bundle in this carbon nano-tube film, thereby this carbon nano-tube film has larger resistance on perpendicular to the carbon nano-tube orientation, this carbon nano-tube film is mega-ohms at the square resistance perpendicular in the carbon nano-tube orientation.
The accompanying drawing explanation
Fig. 1 is the schematic diagram that the embodiment of the present invention prepares the carbon nano-tube film method.
Fig. 2 is that the embodiment of the present invention adopts mobile substrate to prepare the schematic diagram of carbon nano-tube film method.
Fig. 3 is the stereoscan photograph without the carbon nano-tube film of crossing laser treatment that the embodiment of the present invention obtains.
Fig. 4 is the schematic diagram that embodiment of the present invention fixed laser prepares the carbon nano-tube film method.
The stereoscan photograph of the carbon nano-tube film after laser treatment that Fig. 5 is embodiment of the present invention acquisition.
The stereoscan photograph of the carbon nano-tube film of pulling out in the carbon nano pipe array from plasma treatment that Fig. 6 is embodiment of the present invention acquisition.
The main element symbol description
Carbon nano pipe array 116
Carbon nano-tube film 118
The first objective table 120
The first base bar 124
The second objective table 130
The second base bar 134
Embodiment
The invention provides a kind of carbon nano-tube film or the carbon nano-tube compound film based on making on this carbon nano-tube film basis.This carbon nano-tube film comprises a plurality of carbon nano-tube that substantially are parallel to each other and are basically parallel to the carbon nano-tube film surface alignment.Particularly, described carbon nano-tube film comprises and a plurality ofly by Van der Waals force, joins end to end and be arranged of preferred orient substantially in the same direction.Described carbon nano-tube film is can, by directly pull acquisition from carbon nano pipe array, be a self supporting structure.So-called " self supporting structure " i.e. this carbon nano-tube film, without by a support body supports, also can keep self specific shape.Because carbon nano-tube in the carbon nano-tube film of this self supporting structure attracts each other by Van der Waals force, thereby make carbon nano-tube film there is specific shape, form a self supporting structure.In this carbon nano-tube film, carbon nano-tube all aligns in the same direction, because carbon nano-tube has electric anisotropy, (electric anisotropy of carbon nano-tube refers to that carbon nano-tube has high conductivity on it is axial, there is very little conductivity in the direction axial perpendicular to it), make this carbon nano-tube film also there is electric anisotropy, thereby this carbon nano-tube film or carbon nano-tube compound film have resistance anisotropy.Described carbon nano-tube film is that the carbon nano-tube film that pulls acquisition in super in-line arrangement carbon nano pipe array is processed rear the acquisition.The carbon nano-tube aligned in the carbon nano-tube film of directly pulling out in super in-line arrangement carbon nano pipe array mutually combines and forms carbon nano-tube bundle, because thickness and the density of this carbon nano-tube film are relatively large, therefore need to adopt laser treatment be somebody's turn to do directly pulls carbon nano-tube bundle larger in the carbon nano-tube film of acquisition and removes in super in-line arrangement carbon nano pipe array, thereby it is less to obtain density, the larger carbon nano-tube film in gap between carbon nano-tube.The square resistance of this carbon nano-tube film (be defined as foursquare conductor thin layer, the resistance presented at the sense of current is square resistance) is larger.The square resistance of this carbon nano-tube film in the orientation of carbon nano-tube can reach several kilohms, and the square resistance on the direction of arranging perpendicular to carbon nano-tube can reach several megohms.
In addition, after above-mentioned carbon nano-tube film can also adopt the super in-line arrangement carbon nano pipe array of direct processing, more directly pull acquisition in the carbon nano pipe array after processing.Adopt the super in-line arrangement carbon nano pipe array of plasma treatment, the reduced thickness of this carbon nano pipe array, in carbon nano pipe array, the height of each root carbon nano-tube shortens.Thereby on the basis of the carbon nano pipe array after processing, the gap in the carbon nano-tube film directly pulled out between adjacent carbon nano-tube is larger, thereby the carbon nano-tube film obtained has higher square resistance.Because carbon nano-tube film is directly from carbon nano pipe array, to pull acquisition, the carbon nano-tube in carbon nano-tube film still has essentially identical orientation.
Carbon nano-tube compound film provided by the invention is with macromolecular material, to be composited on the basis of carbon nano-tube film, and the carbon nano-tube in this carbon nano-tube compound film has identical orientation.Can directly be layed in liquid polymer-based surface by the carbon nano-tube film by the present invention, make carbon nano-tube film and polymer-based bluk recombination.Also can first from carbon nano pipe array, pull out carbon nano-tube film, after again this carbon nano-tube film being layed in to polymer-based surface, with laser, it is processed again, the carbon nano-tube bundle in carbon nano-tube film is removed, thereby obtained the carbon nano-tube compound film with mega-ohms square resistance.Described macromolecular material can be one or more in the materials such as Merlon (PC), polymethyl methacrylate (PMMA), PETG (PET), polyether sulfone (PES), pi (PI), cellulose esters (SE), benzocyclobutene (BCB), polyvinyl chloride (PVC) and acrylic resin.This carbon nano-tube compound film comprises that a carbon nano-tube film is compounded in the macromolecular material matrix, because this carbon nano-tube film resistance on the direction of arranging perpendicular to carbon nano-tube can reach mega-ohms, so the square resistance of this carbon nano-tube compound film on the direction of arranging perpendicular to carbon nano-tube can reach several megohms.
Mega-ohms carbon nano-tube film provided by the invention or carbon nano-tube compound film, it also has higher light transmittance, can be greater than 95%.And have extraordinary resistance anisotropy, it is 1 kilohm to 5 kilohms along the resistance in the carbon nano-tube orientation, in the resistance perpendicular in the carbon nano-tube orientation is 1 megohm to 5 megohm scope.This carbon nano-tube film or carbon nano-tube compound film can be applied to the conductive layer in touch-screen, also can be applicable in transparency electrode, thin-film transistor.Except above-mentioned field, this carbon nano-tube film or carbon nano-tube compound film, can also be for antistatic film.
Describe the preparation method of embodiment of the present invention carbon nano-tube film in detail below with reference to accompanying drawing.
Adopt the method preparation of laser treatment to there is the method for the carbon nano-tube film of mega-ohms square resistance:
Refer to Fig. 1 and Fig. 2, the embodiment of the present invention provides a kind of preparation method of transparent carbon nanotube membrane, and it comprises the following steps:
Step 1: prepare a carbon nano-tube film, the embodiment of the present invention specifically comprises the following steps with the method for the standby carbon nano-tube film of membrane legal system:
(1) prepare a carbon nano pipe array 116 in a substrate 114.
In the present embodiment, described carbon nano pipe array 116 is one to surpass the in-line arrangement carbon nano pipe array, the preparation method of being somebody's turn to do super in-line arrangement carbon nano pipe array 116 adopts chemical vapour deposition technique, its concrete steps comprise: a smooth substrate 114 (a) is provided, this substrate can be selected P type or N-type silicon base, or select the silicon base that is formed with oxide layer, the present embodiment to be preferably the silicon base that adopts 4 inches; (b) form a catalyst layer at substrate 114 surface uniforms, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any; (c) the above-mentioned substrate 114 that is formed with catalyst layer is annealed approximately 30 minutes～90 minutes in the air of 700～900 ℃; (d) substrate 114 that will process is placed in reacting furnace, under the protective gas environment, is heated to 500～740 ℃, then passes into carbon-source gas and reacts approximately 5～30 minutes, and growth obtains super in-line arrangement carbon nano pipe array, and it is highly 200 microns～400 microns.Should super in-line arrangement carbon nano pipe array 116 be a plurality of parallel to each other and perpendicular to the pure nano-carbon tube array of the carbon nano-tube formation of substrate grown.By above-mentioned control growth conditions, substantially do not contain impurity in this super in-line arrangement carbon nano pipe array 116, as agraphitic carbon or residual catalyst metal particles etc.Carbon nano-tube in this carbon nano pipe array 116 forms array by the Van der Waals force close contact each other.In the present embodiment, carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, and protective gas can be selected nitrogen, ammonia or inert gas.
In the present embodiment, the above-mentioned substrate 114 that is formed with carbon nano pipe array 116 can be fixed on sample stage 110.Can select particularly adhesive tape, binding agent or mechanical system anchoring base 114 on sample stage 110.
(2) adopt a stretching tool 100 to pull from carbon nano pipe array 116 and obtain a carbon nano-tube film 118.
The described method that obtains carbon nano-tube film 118 that pulls specifically comprises the following steps: a plurality of carbon nano-tube segments of selected one fixed width from above-mentioned carbon nano pipe array 116, the plurality of carbon nano-tube fragment is fixed on stretching tool 100, and the present embodiment is preferably and adopts the adhesive tape contact carbon nano pipe array 116 with one fixed width to select a plurality of carbon nano-tube segments of one fixed width; With certain speed along being basically perpendicular to the carbon nano pipe array 116 directions of growth the plurality of carbon nano-tube segment that stretches, to form a continuous carbon nano-tube film 118.
In above-mentioned drawing process, when the plurality of carbon nano-tube segment breaks away from gradually substrate 114 along draw direction under the pulling force effect, due to van der Waals interaction, a plurality of carbon nano-tube segments that should be selected are drawn out end to end continuously with other carbon nano-tube segments respectively, thereby form a carbon nano-tube film 118.Refer to Fig. 3, the carbon nano-tube film with one fixed width 118 that carbon nano-tube film 118 joins end to end and forms for a plurality of carbon nano-tube bundles that align.In this carbon nano-tube film 118, the orientation of carbon nano-tube is basically parallel to the draw direction of this carbon nano-tube film 118.In the step of above-mentioned selected a plurality of carbon nano-tube fragments stretching, because the thickness of the plurality of carbon nano-tube fragment is very difficult, control, carbon nano-tube film 118 thickness evenness that stretching obtains are not good, there is more large diameter carbon nano-tube bundle in this carbon nano-tube film 118, thereby make this carbon nano-tube film 118 obtained that stretches there is lower square resistance.In the present embodiment, the size of the substrate 114 that the width of this carbon nano-tube film 118 is grown with carbon nano pipe array 116 is relevant, and the length of this carbon nano-tube film 118 is not limit, and can make according to the actual requirements.Adopt the super in-line arrangement carbon nano pipe array of substrate 114 growth of 4 inches in the present embodiment, the width of this carbon nano-tube film 118 can be 1 centimetre～10 centimetres, and thickness is 0.01 micron～100 microns.
Step 2: with power density, be greater than 0.1 * 10
4watt/square metre this carbon nano-tube film of Ear Mucosa Treated by He Ne Laser Irradiation, remove the larger carbon nano-tube bundle of diameter in carbon nano-tube film.Step 2 can be carried out in aerobic environment, and preferably, step 2 is carried out at air ambient.
Step 2 can realize by following two kinds of methods:
Method one: the fixed carbon nanotube films, then moving laser device irradiates the method for this carbon nano-tube film, and it specifically comprises the following steps: the fixed carbon nanotube films; One laser aid movably is provided; And mobile this laser aid scans this carbon nano-tube film.
Method two: fixed laser, mobile carbon nano-tube film makes the method for this carbon nano-tube film of Ear Mucosa Treated by He Ne Laser Irradiation, and it specifically comprises the following steps: a fixing laser aid is provided, and this laser aid forms a laser scanning district in a fixed area; One carbon nano-tube film is provided, makes this carbon nano-tube film with certain this laser scanning district of speed process.
In the present embodiment, can in sample stage 110 spaced around, one first objective table 120 and one second objective table 130 be set along the draw direction of carbon nano-tube film 118, and a removable substrate 160.The first objective table 120 arranges near sample stage 110, and the second objective table 130 arranges away from sample stage 110, and sample stage 110, the first objective table 120, the second objective table 130 are on same straight line.The first objective table 120 and the second objective table 130 surfaces are respectively arranged with the first base bar 124 and the second base bar 134, this the first base bar 124 and the second base bar 134 are cuboid, the first base bar 124 and the second base bar 134 all can break away from the first objective table 120 and the second objective table 130 moves freely, and the length of the first base bar 124 and the second base bar 134 is more than or equal to the width of carbon nano-tube film.The material of described the first base bar 124 and the second base bar 134 comprises the materials such as metal, glass, rubber or plastics, and preferably, in the present embodiment, the first base bar 124 and the second base bar 134 materials are metal.The width of removable substrate 160 is more than or equal to the width of carbon nano-tube film, and length is not limit, and the material of removable substrate 160 is not limit, and can comprise the materials such as metal, glass, rubber or plastics, and preferably, in the present embodiment, the material of removable substrate 160 is metal.
In the present embodiment, method one specifically can realize in the following manner:
At first, use stretching tool 100 to stretch from carbon nano pipe array 116 and obtain a carbon nano-tube film 118, this carbon nano-tube film 118 is fixed on the first base bar 124 and the second base bar 134, or this carbon nano-tube film 118 is fixed in to removable substrate 160 surfaces.
Secondly, provide a laser aid 140 movably.
Finally, in air ambient, mobile described laser aid 140, scan between the first base bar 124 and the second base bar 134 or the carbon nano-tube film 118 on removable substrate 160 surfaces with certain speed.
The method of laser treatment carbon nano-tube film 118 is specially: get a laser aid 140, at the uniform velocity mobile this laser aid 140 between the first base bar 124 and the second base bar 134, make between the laser Uniform Scanning first base bar 124 of this laser aid 140 emissions and the second base bar 134 or the carbon nano-tube film 118 on removable substrate 160 surfaces, because carbon nano-tube has better absorption characteristic to laser, there is larger-diameter carbon nano-tube bundle in this carbon nano-tube film 118 and will absorb more heat, thereby be burned, in this carbon nano-tube film 118, the density of carbon nano-tube also significantly reduces, thereby make the square resistance of this carbon nano-tube film 118 significantly rise, carbon nano-tube film 118 after Ear Mucosa Treated by He Ne Laser Irradiation in the present embodiment can reach 5 megaohm mothers at the square resistance perpendicular in the carbon nano-tube orientation.
Described laser aid 140 comprises at least one laser 142, and when this laser aid 140 comprises a laser 142, this laser aid 140 irradiates and forms a hot spot, and the diameter of this hot spot is 1 millimeter～5 millimeters.When this laser aid 140 comprises a plurality of laser 142, this laser aid 140 irradiates and forms a continuous laser scanning district 144, this laser scanning district 144 is the ribbon hot spot be comprised of a plurality of continuous laser faculas, the width of this ribbon hot spot is 1 millimeter～5 millimeters, and length is more than or equal to the width of carbon nano-tube film 118.
The method that is appreciated that above-mentioned laser scanning carbon nano-tube film 118 is not limit, as long as can this carbon nano-tube film 118 of uniform irradiation.Laser scanning can be carried out line by line along the orientation of carbon nano-tube in parallel carbon nano-tube film 118, also can carry out by column along the orientation perpendicular to carbon nano-tube in carbon nano-tube film 118.The speed of laser scanning carbon nano-tube film 118 with constant power, fixed wave length is slower, the heat that carbon nano-tube bundle in carbon nano-tube film 118 absorbs is more, corresponding destroyed carbon nano-tube bundle is more, and the light transmission of the carbon nano-tube film 118 after laser treatment is stronger.But, if laser scanning speed is too slow, carbon nano-tube film 118 is burnt the hyperabsorption heat.In the present embodiment, the power density of laser is greater than 0.053 * 1012 watt/square metre, and the diameter of laser facula is in 1 millimeter～5 millimeters scopes, and the laser scanning irradiation time is less than 1.8 seconds.Preferably, laser 142 is carbon dioxide laser, and the power of this laser is 30 watts, and wavelength is 10.6 microns, and spot diameter is 3 millimeters, and laser aid 140 is less than 10 mm/second with the speed of related movement of carbon nano-tube film 118.
Refer to Fig. 4, method two specifically can be realized in the following manner:
At first, fix a laser aid 140 above sample stage 110, and form a laser scanning district 144 between sample stage 110 and the first objective table 120.
Wherein, this laser aid 140 comprises a plurality of lasers 142, a plurality of continuous hot spots of described laser scanning district 144 laser beam irradiations by a plurality of lasers 142 rearrange, this laser scanning district 144 is a band shape, this laser scanning zone 144 is formed between sample stage 110 and the first objective table 120, width is 1 millimeter～5 millimeters, and length is more than or equal to the width of this carbon nano-tube film 118.
Secondly, use stretching tool 100 to stretch from carbon nano pipe array 116 and obtain a carbon nano-tube film 118, under this stretching tool 100 draws, make this carbon nano-tube film 118 with certain speed by laser scanning district 144, make this carbon nano-tube film of laser scanning.
When stretching tool 100 these carbon nano-tube films 118 of drive pass through this laser scanning district 144 with certain speed, because carbon nano-tube has good absorption characteristic to laser, and the carbon nano-tube bundle that the diameter in carbon nano-tube film 118 is larger will absorb more heat, can be by controlling these carbon nano-tube film 118 speed by the speed in this laser scanning district 144, control the time of Ear Mucosa Treated by He Ne Laser Irradiation carbon nano-tube film, thereby control the energy that in carbon nano-tube film 118, carbon nano-tube bundle absorbs, make and there is larger-diameter carbon nano-tube bundle in this carbon nano-tube film 118 and just burnt out, carbon nano-tube film 118 after laser treatment only comprises the carbon nano-tube bundle of small diameter, and it is large that the gap between adjacent carbon nano-tube becomes, and the thickness of the carbon nano-tube film 118 after this processing also can attenuation.Thereby the carbon nano-tube film 118 after this processing has less density, and larger square resistance, except the gap between the adjacent carbons nanotube in the carbon nano-tube film 118 after reason is in 500 nanometer to 2000 nanometer range.Refer to Fig. 5, the large diameter carbon nano-tube bundle of the carbon nano-tube film 118 after this laser treatment is partly removed, thereby less in the density perpendicular in the carbon nano-tube orientation, so it has higher resistance in the orientation perpendicular to carbon nano-tube.Carbon nano-tube film 118 after this laser treatment along the square resistance of carbon nano-tube orientation in 1 kilohm to 5 kilohms scope, its at the square resistance perpendicular to the carbon nano-tube side of arrangement phase in 0.5 megohm to 5 megohm scope, and because the quantity of the carbon nano-tube bundle in the carbon nano-tube film after laser treatment tails off, the light transmittance of this carbon nano-tube film is corresponding being improved also, can reach 95%, thereby be conducive to practical application.The thickness of the carbon nano-tube film 118 after this processing is in 10 nanometer to 500 nanometer range, and its density in the carbon nano-tube perpendicular in the carbon nano-tube orientation is less than 2 pieces/micron.
Be appreciated that, for the laser aid 140 with fixed power density, fixed wave length, carbon nano-tube film 118 is less by the speed in laser scanning district 144, carbon nano-tube film 118 is illuminated that the time is longer, the energy that carbon nano-tube bundle in carbon nano-tube film 118 absorbs is more, and corresponding destroyed carbon nano-tube bundle is just more, and the density of this carbon nano-tube film 118 is also just less, thereby the light transmittance of the carbon nano-tube film after laser treatment 118 is also just higher, its square resistance is also just higher.But carbon nano-tube film 118 is too little by the speed in laser scanning district 144, can cause carbon nano-tube film 118 because the hyperabsorption heat is burnt.
In the present embodiment, this laser aid 140 comprises solid state laser, liquid laser, gas laser and semiconductor laser.The power density of laser is greater than 0.053 * 1012 watt/square metre, and the diameter of laser facula is in 1 millimeter～5 millimeters scopes, and the irradiation time of laser is less than 1.8 seconds.Preferably, laser aid 140 is carbon dioxide laser, and the power of this laser is 30 watts, and wavelength is 10.6 microns, and spot diameter is 3 millimeters, and laser 142 is 10 mm/second with the speed of related movement of carbon nano-tube film 118.
Then, the carbon nano-tube film 118 after Ear Mucosa Treated by He Ne Laser Irradiation is adhered to respectively on the first base bar 124 and the second base bar 134 or removable substrate 160 surfaces.
Because the carbon nano-tube in the super in-line arrangement carbon nano pipe array 116 provided in the present embodiment step () is very pure, and because the specific area of carbon nano-tube itself is very large, so this carbon nano-tube film 118 all has stronger viscosity before laser treatment and after laser treatment, therefore carbon nano-tube film 118 can utilize the viscosity of itself directly to adhere to Ji Tiaoshang.
In the present embodiment, carbon nano-tube film 118 blocks with mechanical means at the first base bar 124 close place relative to the second base bar 134.Then, an end of carbon nano-tube film 118 still sticks on the first base bar 124, this carbon nano-tube film 118 can be adhered on stretching tool 100, and further repeating step (two), thus can realize the continuous production of carbon nano-tube film 118.
Carbon nano pipe array after the ex vivo treatment such as the present invention can also adopt obtains the method for carbon nano-tube film.
Step 1: be used in method identical in embodiment mono-, prepare a carbon nano pipe array, preferably, this array is super in-line arrangement carbon nano pipe array.
Step 2: using plasma is processed this carbon nano pipe array.The method that using plasma is processed this carbon nano pipe array specifically comprises the following steps: at first, carbon nano pipe array is put into to a vacuum cavity together with substrate; Secondly, pass into reacting gas in vacuum cavity, form the plasma of this reacting gas, this plasma is reacted with carbon nano pipe array.
Particularly, above-mentioned steps two can be carried out in a reactive ion etching machine.At first, carbon nano pipe array is put into to the vacuum cavity of reactive ion etching machine together with substrate, and will be evacuated in this vacuum cavity.Secondly, in the vacuum cavity of reactive ion etching machine, pass into reacting gas, this reacting gas may be selected to be oxygen, hydrogen or carbon tetrafluoride etc.Finally, react by glow discharge the plasma that produces reacting gas in above-mentioned vacuum cavity, and reacted with carbon nano pipe array.Particularly, above-mentioned reacting gas forms plasma by glow discharge, and this plasma comprises charged ion and electronics.Above-mentioned charged ion carries out physical etchings by clashing into carbon nano tube surface to carbon nano-tube, or reacts by the carbon atom with in carbon nano-tube volatile product such as generating carbon dioxide carbon nano-tube is carried out to chemical etching.According to the difference of reacting gas, this plasma comprises the plasmas commonly used such as oxygen plasma, hydrogen plasma or carbon tetrafluoride plasma.Preferably, this reacting gas is oxygen, and this plasma is oxygen plasma.The power of above-mentioned glow discharge reaction can be 20～300 watts, is preferably 150 watts.Reaction gas flow is 10～100 standard state ml/min (sccm), is preferably 50sccm.In vacuum cavity, gas pressure intensity is 1～100 handkerchief, is preferably 10 handkerchiefs.Plasma and carbon nano pipe array reaction time are 10 seconds～1 hour, are preferably 15 seconds～8 minutes.
Because carbon nano-pipe array is classified a close-packed arrays structure as, by gas pressure intensity and reaction time in suitable control chamber, plasma only with the carbon nano pipe array surface reaction, be difficult to be penetrated into array inside, thereby can not affect the structure of inner carbon nanotube.After reaction, the reduced thickness of carbon nano pipe array, in carbon nano pipe array, the height of each root carbon nano-tube shortens.The above-mentioned reaction time can not be oversize or too short.When the above-mentioned reaction time is oversize, carbon nano pipe array and plasma reaction are excessive, thereby make the thickness of carbon nano pipe array excessively thin, are unfavorable for pulling of carbon nano-tube film.When the above-mentioned reaction time too in short-term, carbon nano pipe array and plasma reaction are inadequate, carbon nano pipe array thickness is still thicker, can't reach the purpose that improves the carbon nano-tube film transparency.Preferably, the thickness of the carbon nano pipe array after described using plasma processing is 20～200 microns.
In step 2, oxygen plasma is reacted with the carbon nano pipe array surface, thereby makes the carbon nano pipe array attenuate.Therefore, by controlling the time of oxygen plasma treatment, can control the height of carbon nano pipe array.Further, at the early growth period of step 1 carbon nano pipe array, due to the impact of initial growth condition, the carbon nano pipe array of growing is more unstable, and carbon nano-tube is arranged relatively mixed and disorderly.When various growth conditions stabilize and after a period of time of growing, the carbon nano-tube in carbon nano pipe array all, along the direction growth of vertical substrate, forms and one surpasses the in-line arrangement carbon nano pipe array.Therefore, process this carbon nano pipe array by using plasma in step 2, can remove above-mentioned carbon nano pipe array top and arrange comparatively mixed and disorderly carbon nano-tube, obtain a neat super in-line arrangement carbon nano pipe array, thereby more be conducive to pulling of carbon nano-tube film in step 3.
Step 3: adopt a stretching tool to pull from carbon nano pipe array and obtain a carbon nano-tube film.It specifically comprises the following steps: (a) a plurality of carbon nano-tube segments of selected one fixed width from above-mentioned carbon nano pipe array, and the present embodiment is preferably and adopts the adhesive tape contact carbon nano pipe array with one fixed width to select a plurality of carbon nano-tube segments of one fixed width; (b) with certain speed along being basically perpendicular to the carbon nano pipe array direction of growth the plurality of carbon nano-tube segment that stretches, to form a continuous carbon nano-tube film.
In above-mentioned drawing process, when the plurality of carbon nano-tube segment breaks away from substrate gradually along draw direction under the pulling force effect, due to van der Waals interaction, a plurality of carbon nano-tube segments that should be selected are drawn out end to end continuously with other carbon nano-tube segments respectively, thereby form a carbon nano-tube film.This carbon nano-tube film is the carbon nano-tube film with one fixed width that a plurality of carbon nano-tube bundles of aligning join end to end and form.In this carbon nano-tube film, the orientation of carbon nano-tube is basically parallel to the draw direction of carbon nano-tube film.The microstructure of this carbon nano-tube film refers to Fig. 6.
The carbon nano-tube film be arranged of preferred orient obtained that should directly stretch has better uniformity and transparency than unordered carbon nano-tube film, and the light transmission of this carbon nano-tube film can reach 90%.Should directly stretch and obtain the method Simple fast of carbon nano-tube film, the suitable industrial applications of carrying out simultaneously.
In the present embodiment, the size of the substrate that the width of this carbon nano-tube film is grown with carbon nano pipe array is relevant, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.Adopt the super in-line arrangement carbon nano pipe array of substrate grown of 4 inches in the present embodiment, the width of this carbon nano-tube film can be 0.01cm～10cm, and the thickness of this carbon nano-tube film is 10 nanometers～500 nanometers.
Refer to Fig. 6, the carbon nano-tube film that the carbon nano pipe array that carbon nano-tube film is is 15 minutes from growth time pulls.150 watts of power, air pressure 10 handkerchiefs, under the condition of oxygen flow 50sccm, adopt the carbon nano pipe array that the oxygen plasma treatment growth time is 15 minutes.And, along with the variation in processing time, the density that the carbon nano pipe array from above-mentioned processing pulls the carbon nano-tube film obtained diminishes gradually, square resistance increases gradually.Wherein, after carbon nano pipe array is processed to 8 minutes, the square resistance maximum of the carbon nano-tube film obtained by this array.Carbon nano-tube film can reach 5 megaohm mothers at the square resistance perpendicular in the carbon nano-tube orientation.
Be appreciated that because the carbon nano-tube in the super in-line arrangement carbon nano pipe array of the present embodiment is very pure, and because the specific area of carbon nano-tube itself is very large, so this carbon nano-tube film itself has stronger viscosity.Therefore, this carbon nano-tube film can directly stick on various matrixes as required.
In addition, can with an organic solvent process the above-mentioned carbon nano-tube film sticked on matrix.Particularly, can organic solvent be dropped in to the whole carbon nano-tube film of carbon nano-tube film surface infiltration by test tube.This organic solvent is volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.This carbon nano-tube film is after organic solvent infiltrate to be processed, and under the capillary effect of volatile organic solvent, this carbon nano-tube film can be attached to matrix surface securely, and the surface volume ratio reduces, and viscosity reduces, and has good mechanical strength and toughness.
Compared to prior art, because the carbon nano-tube in described carbon nano-tube film is arranged parallel to each other substantially, because carbon nano-tube has extraordinary resistance anisotropy, carbon nano-tube has conductivity preferably in the axial direction, there is very large resistance on direction perpendicular to axial direction, make this carbon nano-tube film there is extraordinary resistance anisotropy.And this carbon nano-tube film is mega-ohms at the square resistance perpendicular in the carbon nano-tube orientation.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and these variations of doing according to spirit of the present invention certainly, all should be included in the present invention's scope required for protection.
Claims (4)
1. a carbon nano-tube compound film, it comprises:
One carbon nano-tube film, this carbon nano-tube film comprises a plurality of carbon nano-tube that substantially are parallel to each other and are basically parallel to the carbon nano-tube film surface alignment; And
One macromolecule matrix, described carbon nano-tube film is arranged in this macromolecule matrix, it is characterized in that, this carbon nano-tube compound film has resistance anisotropy, in carbon nano-tube orientation upper block resistance is 1 kilohm to 5 kilohms scope, at the square resistance perpendicular to the carbon nano-tube side of arrangement phase, it is 0.5 megohm to 5 megohm scope, the thickness of this carbon nano-tube film is in 10 nanometer to 500 nanometer range, there is gap between the adjacent carbon nano-tube of this carbon nano-tube film, described carbon nano-tube film is less than 2 every micron in the density of the carbon nano-tube perpendicular in the carbon nano-tube orientation.
2. carbon nano-tube compound film as claimed in claim 1, is characterized in that, described macromolecule matrix is a planar film, and described carbon nano-tube film is parallel to this planar film and is arranged in this macromolecule matrix.
3. carbon nano-tube compound film as claimed in claim 2, it is characterized in that, the material of described macromolecule matrix is one or more in Merlon, polymethyl methacrylate, PETG, polyether sulfone, pi, cellulose esters, benzocyclobutene, polyvinyl chloride and acrylic resin.
4. carbon nano-tube compound film as claimed in claim 1, is characterized in that, described carbon nano-tube film comprises that a plurality of described carbon nano-tube join end to end and are arranged of preferred orient substantially in the same direction by Van der Waals force.
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| TWI510975B (en) * | 2010-12-30 | 2015-12-01 | Hon Hai Prec Ind Co Ltd | Finger-stall for touch panel |
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| CN103359719B (en) * | 2012-04-05 | 2015-01-21 | 清华大学 | Preparation method of narrow graphene nanoribbons |
| CN103359722B (en) * | 2012-04-05 | 2015-01-21 | 清华大学 | Preparation method of narrow graphene nanoribbons |
| CN103359717B (en) * | 2012-04-05 | 2015-06-03 | 清华大学 | Preparation method of narrow graphene nanoribbons |
| CN103359718B (en) * | 2012-04-05 | 2015-07-01 | 清华大学 | Preparation method of narrow graphene nanoribbons |
| CN103359723B (en) * | 2012-04-05 | 2015-01-21 | 清华大学 | Preparation method of narrow graphene nanoribbons |
| CN103373719B (en) * | 2012-04-25 | 2015-11-25 | 北京富纳特创新科技有限公司 | The preparation method of carbon nano-tube film |
| CN103377755B (en) * | 2012-04-25 | 2015-12-09 | 北京富纳特创新科技有限公司 | Conducting element |
| CN103928637B (en) * | 2013-01-14 | 2016-05-04 | 北京阿格蕾雅科技发展有限公司 | The preparation method of carbon nano tube transparent combination electrode |
| CN103264223B (en) * | 2013-05-14 | 2015-12-23 | 东华大学 | A kind ofly improve the method that yard of material causes emitting performance |
| CN109427983B (en) * | 2017-08-30 | 2020-08-11 | 清华大学 | Organic light emitting diode |
| CN112429718B (en) * | 2019-08-26 | 2023-11-17 | 鸿富锦精密工业（深圳）有限公司 | Film laying system for carbon nano tube film |
| CN110823009B (en) * | 2019-11-12 | 2022-03-15 | 中国工程物理研究院化工材料研究所 | Exploding foil exploder with adjustable exploding current |
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