CN101923912A - 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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- CN101923912A CN101923912A CN2010102031608A CN201010203160A CN101923912A CN 101923912 A CN101923912 A CN 101923912A CN 2010102031608 A CN2010102031608 A CN 2010102031608A CN 201010203160 A CN201010203160 A CN 201010203160A CN 101923912 A CN101923912 A CN 101923912A
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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 based on the composite membrane of this carbon nano-tube film.
Background technology
From find first carbon nano-tube (Carbon Nanotube, CNT) since, be that the nano material of representative has caused that with its particular structure and character people pay close attention to greatly with the carbon nano-tube.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)).Because the electromagnetism of the uniqueness that carbon nano-tube had, 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, because carbon nano-tube has excellent electric conductivity, carbon nano-tube film can be applied to transparent conductive film.In the prior art, the preparation of carbon nano-tube film also can obtain carbon nano-tube film by carbon nanotube powder except that can obtaining by the direct growth method.For example: point solvent drips seasoning, L B film method, print process, electrophoresis, and filter membrane method etc.In the prior art, carbon nano-tube film can also obtain by the method that directly pulls 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 all has distribution on all directions, makes this carbon nano-tube film even substantially at the resistance of all directions, has the isotropic characteristics of resistance; And a plurality of carbon nano-tube are twined mutually and are formed large diameter carbon nano-tube bundle, in application since the formation of these large diameter carbon nano-tube bundles the favorable conductive passage, the square resistance of this carbon nano-tube film is lower.
Summary of the invention
In view of this, necessaryly provide a kind of and have resistance anisotropic properties and square resistance than higher carbon nano-tube film.
A kind of carbon nano-tube film, this carbon nano-tube film comprises that a plurality of each carbon nano-tube film comprise and a plurality ofly is parallel to each other substantially and is basically parallel to carbon nano-tube film surface carbon nanotubes arranged, this carbon nano-tube film have a resistance anisotropy, it is being a mega-ohms perpendicular to the square resistance 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 carbon nano-tube film in the macromolecule matrix, this carbon nano-tube film comprises that a plurality of each carbon nano-tube film comprise and a plurality ofly is parallel to each other substantially and is basically parallel to carbon nano-tube film surface carbon nanotubes arranged, this carbon nano-tube film have a resistance anisotropy, it is being a mega-ohms perpendicular to the square resistance in the carbon nano-tube orientation.
Compared to prior art, because the carbon nano-tube in the 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, on direction perpendicular to axial direction, has very large resistance, make this carbon nano-tube film have 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 bigger resistance on perpendicular to the carbon nano-tube orientation, and this carbon nano-tube film is being a mega-ohms perpendicular to the square resistance in the carbon nano-tube orientation.
Description of drawings
Fig. 1 is the schematic diagram that the embodiment of the invention prepares the carbon nano-tube film method.
Fig. 2 is the schematic diagram that the embodiment of the invention adopts mobile substrate preparation carbon nano-tube film method.
The stereoscan photograph that Fig. 3 obtains for the embodiment of the invention without the carbon nano-tube film of crossing laser treatment.
Fig. 4 is the schematic diagram that embodiment of the invention fixed laser prepares the carbon nano-tube film method.
The stereoscan photograph of the carbon nano-tube film after the process laser treatment that Fig. 5 obtains for the embodiment of the invention.
The stereoscan photograph of the carbon nano-tube film of pulling out the carbon nano pipe array after plasma treatment of Fig. 6 for embodiment of the invention acquisition.
The main element symbol description
Carbon nano pipe array 116
Carbon nano-tube film 118
First objective table 120
The first basic bar 124
Second objective table 130
The second basic bar 134
Embodiment
The invention provides a kind of carbon nano-tube film or based on the carbon nano-tube compound film of making on this carbon nano-tube film basis.This carbon nano-tube film comprises and a plurality ofly is parallel to each other substantially and is basically parallel to carbon nano-tube film surface carbon nanotubes arranged.Particularly, described carbon nano-tube film comprises and a plurality ofly joins end to end and be arranged of preferred orient along same direction substantially by Van der Waals force.Described carbon nano-tube film is can be a self supporting structure by directly pull acquisition from carbon nano pipe array.So-called " self supporting structure " i.e. this carbon nano-tube film need not by a support body supports, also can keep self specific shape.Because carbon nano-tube attracts each other by Van der Waals force in the carbon nano-tube film of this self supporting structure, thereby makes carbon nano-tube film have specific shape, forms a self supporting structure.Carbon nano-tube all aligns along same direction in this carbon nano-tube film, (electric anisotropy of carbon nano-tube is meant that carbon nano-tube has high conductivity on it is axial because carbon nano-tube has electric anisotropy, has very little conductivity perpendicular to its axial direction), make this carbon nano-tube film also have electric anisotropy, thereby this carbon nano-tube film or carbon nano-tube compound film have the resistance anisotropy.Described carbon nano-tube film is to handle the back by the carbon nano-tube film that pulls acquisition in the super in-line arrangement carbon nano pipe array to obtain.Mutually combine by the carbon nano-tube that aligns in the carbon nano-tube film of directly pulling out in the super in-line arrangement carbon nano pipe array and to form carbon nano-tube bundle, because the thickness and the density of this carbon nano-tube film are relatively large, therefore needing to adopt laser treatment will be somebody's turn to do directly removes by pulling carbon nano-tube bundle bigger in the carbon nano-tube film of acquisition in the super in-line arrangement carbon nano pipe array, thereby it is less to obtain density, the bigger carbon nano-tube film in gap between the carbon nano-tube.The square resistance of this carbon nano-tube film (being defined as foursquare conductor thin layer, is square resistance at the resistance that the sense of current presented) is bigger.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, above-mentioned carbon nano-tube film can also adopt after the super in-line arrangement carbon nano pipe array of direct processing, again by directly pulling acquisition in the carbon nano pipe array after handling.Adopt the super in-line arrangement carbon nano pipe array of plasma treatment, the reduced thickness of this carbon nano pipe array, the height of each root carbon nano-tube shortens in the carbon nano pipe array.Thereby on the basis of the carbon nano pipe array after the processing, the gap in the carbon nano-tube film that directly pulls out between the adjacent carbon nano-tube is bigger, thereby the carbon nano-tube film that obtains has higher square resistance.Because carbon nano-tube film is directly to pull acquisition from carbon nano pipe array, the carbon nano-tube in the carbon nano-tube film still has essentially identical orientation.
Carbon nano-tube compound film provided by the invention is to be composited with macromolecular material on the basis of carbon nano-tube film, and the carbon nano-tube in this carbon nano-tube compound film has identical orientation.Can make carbon nano-tube film and polymer-based bluk recombination by the carbon nano-tube film among the present invention directly being layed in liquid polymer-based surface.Also can pull out carbon nano-tube film from carbon nano pipe array earlier, after again this carbon nano-tube film being layed in polymer-based surface, with laser it is handled again, the carbon nano-tube bundle in the carbon nano-tube film is removed, thereby acquisition has the carbon nano-tube compound film of mega-ohms square resistance.Described macromolecular material can be 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 one or more.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, is being in 1 megohm to the 5 megohm scope perpendicular to the resistance in the carbon nano-tube orientation.This carbon nano-tube film or carbon nano-tube compound film can be applied to the conductive layer in the touch-screen, also can be applicable in transparency electrode, the thin-film transistor.Except that above-mentioned field, this carbon nano-tube film or carbon nano-tube compound film can also be used for antistatic film.
Describe the preparation method of embodiment of the invention carbon nano-tube film in detail below with reference to accompanying drawing.
Adopt the method preparation of laser treatment to have the method for the carbon nano-tube film of mega-ohms square resistance:
See also Fig. 1 and Fig. 2, the embodiment of the invention provides a kind of preparation method of transparent carbon nanotube membrane, and it may further comprise the steps:
Step 1: prepare a carbon nano-tube film, the embodiment of the invention specifically may further comprise the steps with the method that the membrane method prepares a carbon nano-tube film:
(1) preparation one carbon nano pipe array 116 is 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 for use, or select for use the silicon base that is formed with oxide layer, present embodiment to be preferably and adopt 4 inches silicon base; (b) evenly form a catalyst layer on substrate 114 surfaces, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any for use; (c) the above-mentioned substrate 114 that is formed with catalyst layer was annealed in 700～900 ℃ air about 30 minutes～90 minutes; (d) substrate 114 that will handle places reacting furnace, is heated to 500～740 ℃ under the protective gas environment, feeds carbon-source gas then and reacts about 5～30 minutes, and growth obtains super in-line arrangement carbon nano pipe array, and it highly is 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 growing condition, do not contain impurity substantially 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 closely contacts the formation array by Van der Waals force each other.Carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene for use in the present embodiment, and protective gas can be selected nitrogen, ammonia or inert gas for use.
In the present embodiment, the above-mentioned substrate 114 that is formed with carbon nano pipe array 116 can be fixed on the sample stage 110.Can select for use adhesive tape, binding agent or mechanical system anchoring base 114 particularly on sample stage 110.
(2) adopt a stretching tool 100 from carbon nano pipe array 116, to pull and obtain a carbon nano-tube film 118.
The described method that obtains carbon nano-tube film 118 that pulls specifically may further comprise the steps: a plurality of carbon nano-tube segments of selected certain width from above-mentioned carbon nano pipe array 116, should a plurality of carbon nano-tube fragments be fixed on the stretching tool 100, present embodiment is preferably and adopts the adhesive tape contact carbon nano pipe array 116 with certain width to select a plurality of carbon nano-tube segments of certain width; Be basically perpendicular to these a plurality of carbon nano-tube segments of carbon nano pipe array 116 directions of growth stretching with the certain speed edge, to form a continuous carbon nano tube film 118.
In above-mentioned drawing process, these a plurality of carbon nano-tube segments are when tension lower edge draw direction breaks away from substrate 114 gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube segments be drawn out continuously end to end with other carbon nano-tube segments respectively, thereby form a carbon nano-tube film 118.See also Fig. 3, the carbon nano-tube film with certain width 118 that carbon nano-tube film 118 joins end to end and forms for a plurality of carbon nano-tube bundles that align.The orientation of carbon nano-tube is basically parallel to the draw direction of this carbon nano-tube film 118 in this carbon nano-tube film 118.In the step of above-mentioned selected a plurality of carbon nano-tube fragments and stretching, because the thickness of these a plurality of carbon nano-tube fragments is difficult to control, carbon nano-tube film 118 thickness evenness that stretching obtains are not good, have more large diameter carbon nano-tube bundle in this carbon nano-tube film 118, thereby this carbon nano-tube film 118 that makes stretching obtain has lower square resistance.In the present embodiment, the width of this carbon nano-tube film 118 is relevant with the size of the substrate 114 that carbon nano pipe array 116 is grown, and the length of this carbon nano-tube film 118 is not limit, and can make according to the actual requirements.Adopt 4 inches the super in-line arrangement carbon nano pipe array of substrate 114 growths 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 greater than 0.1 * 10
4Watt/square metre this carbon nano-tube film of laser radiation is removed the bigger carbon nano-tube bundle of diameter in the 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, moving laser device shines the method for this carbon nano-tube film then, and it specifically may further comprise the 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 laser radiation, and it specifically may further comprise the 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.First objective table 120 is provided with near sample stage 110, and second objective table 130 is provided with away from sample stage 110, and sample stage 110, first objective table 120, second objective table 130 are on same straight line.First objective table 120 and second objective table, 130 surfaces are respectively arranged with the first basic bar 124 and the second basic bar 134, this the first basic bar 124 and the second basic bar 134 are cuboid, the first basic the bar 124 and second basic bar 134 all can break away from first objective table 120 and second objective table 130 moves freely, the length of the first basic bar 124 and the second basic bar 134 is more than or equal to the width of carbon nano-tube film.The material of the described first basic bar 124 and the second basic bar 134 comprises materials such as metal, glass, rubber or plastics, and preferably, the first basic bar 124 and second basic bar 134 materials are metal in the present embodiment.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 materials such as metal, glass, rubber or plastics, and preferably, the material of removable substrate 160 is a metal in the present embodiment.
In the present embodiment, method one specifically can realize in the following manner:
At first, use stretching tool 100 from carbon nano pipe array 116, to stretch and obtain a carbon nano-tube film 118, this carbon nano-tube film 118 is fixed on the first basic bar 124 and the second basic bar 134, perhaps this carbon nano-tube film 118 is fixed in removable substrate 160 surfaces.
Secondly, provide a laser aid 140 movably.
At last, in air ambient, move described laser aid 140, scan between the first basic bar 124 and the second basic 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, between the first basic bar 124 and the second basic bar 134, at the uniform velocity move this laser aid 140, make these laser aid 140 emitted laser evenly scan between the first basic bar 124 and the second basic bar 134 or the carbon nano-tube film 118 on removable substrate 160 surfaces, because carbon nano-tube has better absorption characteristic to laser, have larger-diameter carbon nano-tube bundle in this carbon nano-tube film 118 and will absorb more heat, thereby burnt out, the density of carbon nano-tube also significantly reduces in this carbon nano-tube film 118, thereby make the square resistance of this carbon nano-tube film 118 rise significantly, the carbon nano-tube film 118 after the laser radiation in the present embodiment can reach 5 megaohm mothers perpendicular to the square resistance in the carbon nano-tube orientation.
Described laser aid 140 comprises at least one laser 142, and when this laser aid 140 comprised a laser 142, these laser aid 140 irradiations formed 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, these laser aid 140 irradiations form a continuous laser scanning district 144, this laser scanning district 144 is the ribbon hot spot of being made up 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 the parallel carbon nano-tube film 118, also can be undertaken by row along the orientation perpendicular to carbon nano-tube in the carbon nano-tube film 118.The speed of laser scanning carbon nano-tube film 118 with constant power, fixed wave length is slow more, the heat that carbon nano-tube bundle in the carbon nano-tube film 118 absorbs is many more, corresponding ruined carbon nano-tube bundle is many more, and the light transmission of the carbon nano-tube film 118 after the laser treatment is strong more.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 was less than 1.8 seconds.Preferably, laser 142 is a 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 the speed of related movement of laser aid 140 and carbon nano-tube film 118 is less than 10 mm/second.
See also Fig. 4, method two specifically can be realized in the following manner:
At first, at sample stage 110 upper fixed one laser aid 140, and between the sample stage 110 and first objective table 120, form a laser scanning district 144.
Wherein, this laser aid 140 comprises a plurality of lasers 142, described laser scanning district 144 is rearranged by a plurality of continuous hot spot of the laser beam irradiation of a plurality of lasers 142, this laser scanning district 144 is a strip-type, this laser scanning zone 144 is formed between the sample stage 110 and 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 from carbon nano pipe array 116, to stretch 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 the carbon nano-tube film 118 is bigger will absorb more heat, can be by the speed of these carbon nano-tube film 118 speed of control by this laser scanning district 144, control the time of laser radiation carbon nano-tube film, thereby the energy that carbon nano-tube bundle absorbed in the controlling carbon nanotube film 118, make that having larger-diameter carbon nano-tube bundle in this carbon nano-tube film 118 is burnt out just, carbon nano-tube film 118 after the laser treatment only comprises the carbon nano-tube bundle than minor diameter, and it is big that the gap between the adjacent carbon nano-tube becomes, and the thickness of the carbon nano-tube film 118 after should handling also can attenuation.Thereby the carbon nano-tube film 118 after this processing has less density, and bigger square resistance, and the gap of removing between the adjacent carbons nanotube in the carbon nano-tube film 118 after managing is in 500 nanometer to 2000 nanometer range.See also 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 perpendicular to the density 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 perpendicular to the square resistance of 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 the laser treatment tails off, the light transmittance of this carbon nano-tube film is also corresponding to be improved, can reach 95%, thereby help practical application.The thickness of the carbon nano-tube film 118 after this is handled in 10 nanometer to 500 nanometer range, its perpendicular to the density of the carbon nano-tube in the carbon nano-tube orientation less than 2 pieces/micron.
Be appreciated that, for laser aid 140 with fixed power density, fixed wave length, carbon nano-tube film 118 is more little by the speed in laser scanning district 144, carbon nano-tube film 118 is illuminated that the time is long more, the energy that carbon nano-tube bundle in the carbon nano-tube film 118 absorbs is many more, and corresponding ruined carbon nano-tube bundle is just many more, and the density of this carbon nano-tube film 118 is also just more little, thereby the light transmittance of the carbon nano-tube film after the laser treatment 118 is also just high more, and its square resistance is also just high more.But carbon nano-tube film 118 is too little by the speed in laser scanning district 144, then 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 was less than 1.8 seconds.Preferably, laser aid 140 is a 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 after the laser radiation 118 is adhered on the first basic bar 124 and the second basic bar 134 respectively or removable substrate 160 surfaces.
Because the carbon nano-tube in the super in-line arrangement carbon nano pipe array 116 that is provided in the present embodiment step () is very pure, and because the specific area of carbon nano-tube itself is very big, so this carbon nano-tube film 118 all has stronger viscosity before laser treatment and after the laser treatment, so carbon nano-tube film 118 can utilize the viscosity of itself directly to adhere to Ji Tiaoshang.
Carbon nano-tube film 118 blocks with mechanical means with the second basic bar, 134 relative close places at the first basic bar 124 in the present embodiment.Then, an end of carbon nano-tube film 118 still sticks on the first basic bar 124, this carbon nano-tube film 118 can be adhered on the 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 among the embodiment one, prepare a carbon nano pipe array, preferably, this array is super in-line arrangement carbon nano pipe array.
Step 2: using plasma is handled this carbon nano pipe array.The method that using plasma is handled this carbon nano pipe array specifically may further comprise the steps: at first, carbon nano pipe array is put into a vacuum cavity together with substrate; Secondly, in vacuum cavity, feed reacting gas, form the plasma of this reacting gas, make the reaction of this plasma and 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 the vacuum cavity of reactive ion etching machine together with substrate, and will be evacuated in this vacuum cavity.Secondly, feed reacting gas in the vacuum cavity of reactive ion etching machine, this reacting gas may be selected to be oxygen, hydrogen or carbon tetrafluoride etc.At last, in above-mentioned vacuum cavity, produce the plasma of reacting gas, and react with carbon nano pipe array by the glow discharge reaction.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 the bump carbon nano tube surface to carbon nano-tube, perhaps by with carbon nano-tube in carbon atom reaction generate volatile product such as carbon dioxide carbon nano-tube carried out chemical etching.According to the difference of reacting gas, this plasma comprises the plasma that oxygen plasma, hydrogen plasma or carbon tetrafluoride plasma etc. are commonly used.Preferably, this reacting gas is an oxygen, and this plasma is an 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.Gas pressure intensity is 1～100 handkerchief in the vacuum cavity, 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 classifies a tight arrangement architecture as, by gas pressure intensity and reaction time in the suitable control chamber, plasma and carbon nano pipe array surface reaction are difficult to be penetrated into array inside, thereby can not influence the structure of inner carbon nanotube.After the reaction, the reduced thickness of carbon nano pipe array, the height of each root carbon nano-tube shortens in the carbon nano pipe array.The above-mentioned reaction time can not be oversize or too short.When the above-mentioned reaction time was oversize, carbon nano pipe array and plasma reaction were excessive, thereby made the thickness of carbon nano pipe array thin excessively, were 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 not enough, carbon nano pipe array thickness is still thicker, can't reach the purpose that improves the carbon nano-tube film transparency.The thickness of the carbon nano pipe array after preferably, described using plasma is handled is 20～200 microns.
In step 2, react on oxygen plasma and carbon nano pipe array surface, thereby make the carbon nano pipe array attenuate.Therefore, by the time of control oxygen plasma treatment, height that can the controlling carbon nanotube array.Further, at the early growth period of step 1 carbon nano pipe array, because the initial growth condition effect, institute's carbon nanometer tube array growing is unstable, and carbon nano-tube is arranged mixed and disorderly relatively.When various growth conditions stabilize and after a period of time of growing, all along the direction growth of vertical substrate, formation one surpasses the in-line arrangement carbon nano pipe array to the carbon nano-tube in the carbon nano pipe array.Therefore, handle this carbon nano pipe array by using plasma in the 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 help pulling of carbon nano-tube film in the step 3.
Step 3: adopt a stretching tool from carbon nano pipe array, to pull and obtain a carbon nano-tube film.It specifically may further comprise the steps: (a) a plurality of carbon nano-tube segments of selected certain width from above-mentioned carbon nano pipe array, present embodiment are preferably and adopt the adhesive tape contact carbon nano pipe array with certain width to select a plurality of carbon nano-tube segments of certain width; (b) be basically perpendicular to these a plurality of carbon nano-tube segments of carbon nano pipe array direction of growth stretching with the certain speed edge, to form a continuous carbon nano tube film.
In above-mentioned drawing process, these a plurality of carbon nano-tube segments are when tension lower edge draw direction breaks away from substrate gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube segments be drawn out continuously end to end 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 certain width that a plurality of carbon nano-tube bundles of aligning join end to end and form.The orientation of carbon nano-tube is basically parallel to the draw direction of carbon nano-tube film in this carbon nano-tube film.The microstructure of this carbon nano-tube film sees also Fig. 6.
The carbon nano-tube film that is arranged of preferred orient that obtains 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%.Directly the method for stretching acquisition carbon nano-tube film is simply quick simultaneously, the suitable industrial applications of carrying out.
In the present embodiment, the width of this carbon nano-tube film is relevant with the size of the substrate that carbon nano pipe array is grown, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.Adopt 4 inches the super in-line arrangement carbon nano pipe array of substrate grown 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.
See also Fig. 6, carbon nano-tube film is for being the carbon nano-tube film that 15 minutes carbon nano pipe array pulls from growth time.150 watts of power, air pressure 10 handkerchiefs, under the condition of oxygen flow 50sccm, employing oxygen plasma treatment growth time is 15 minutes a carbon nano pipe array.And along with the variation in processing time, the density that the carbon nano pipe array after the above-mentioned processing pulls the carbon nano-tube film that obtains diminishes gradually, and square resistance increases gradually.Wherein, carbon nano pipe array handled 8 minutes after, the square resistance maximum of the carbon nano-tube film that obtains by this array.Carbon nano-tube film can reach 5 megaohm mothers perpendicular to the square resistance 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 present embodiment is very pure, and because the specific area of carbon nano-tube itself is very big, so this carbon nano-tube film itself has stronger viscosity.Therefore, this carbon nano-tube film can directly stick on the various matrixes as required.
In addition, can with an organic solvent handle the above-mentioned carbon nano-tube film that sticks on the matrix.Particularly, can organic solvent be dropped in the whole carbon nano-tube film of carbon nano-tube film surface infiltration by test tube.This organic solvent is a 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 soak into to be handled, 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 excellent mechanical intensity and toughness.
Compared to prior art, because the carbon nano-tube in the 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, on direction perpendicular to axial direction, have very large resistance, make this carbon nano-tube film have extraordinary resistance anisotropy.And this carbon nano-tube film is being a mega-ohms perpendicular to the square resistance 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 (10)
1. carbon nano-tube film, it is characterized in that, this carbon nano-tube film comprises and a plurality ofly is parallel to each other substantially and is basically parallel to carbon nano-tube film surface carbon nanotubes arranged that this carbon nano-tube film has the resistance anisotropy, is being mega-ohms perpendicular to the square resistance in the carbon nano-tube orientation.
2. carbon nano-tube 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 by Van der Waals force and are arranged of preferred orient along same direction substantially.
3. carbon nano-tube film as claimed in claim 1 is characterized in that, in carbon nano-tube orientation upper block resistance is 1 kilohm to 5 kilohms scope.
4. carbon nano-tube film as claimed in claim 3 is characterized in that, is 0.5 megohm to 5 megohm scope at the square resistance perpendicular to the carbon nano-tube side of arrangement phase.
5. carbon nano-tube film as claimed in claim 1 is characterized in that, has the gap between adjacent carbon nano-tube.
6. carbon nano-tube film as claimed in claim 4 is characterized in that, described carbon nano-tube film perpendicular to the density of the carbon nano-tube in the carbon nano-tube orientation less than 2 every micron.
7. carbon nano-tube film as claimed in claim 1 is characterized in that, the thickness of this carbon nano-tube film is in 10 nanometer to 500 nanometer range.
8. carbon nano-tube compound film, it comprises:
One as any described carbon nano-tube film of claim in the claim 1 to 7; And
One macromolecule matrix, described carbon nano-tube film is arranged in this macromolecule matrix, it is characterized in that, and this carbon nano-tube compound film has the resistance anisotropy, is being mega-ohms perpendicular to the square resistance in the carbon nano-tube orientation.
9. carbon nano-tube compound film as claimed in claim 8 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.
10. carbon nano-tube compound film as claimed in claim 9, 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 the acrylic resin.
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