TWI342266B - Carbon nanotube composite film - Google Patents

Description

1342266 IX. Description of the invention: [Technical field to which the invention belongs]

The present invention relates to a composite sheet, and more particularly to a composite film. Nano carbon nanotubes [Previous technology] Since the early 1990s, it has been represented by carbon nanotubes: the unique structure and properties have attracted great attention. Near = the constant deepening of the research of # = nano carbon tube and nano materials, its vast application month, 豕 豕 constantly emerged. For example, due to the unique magnetic, optical, mechanical, and chemical properties of carbon nanotubes, a large number of applications for field emission electron sources, sensors, new optical materials, and soft ferromagnetic materials have been reported. In particular, the combination of carbon nanotubes with other materials such as metals, semiconductors or poly-amps can complement or enhance the advantages of the materials. The carbon nanotubes have a large aspect ratio and a hollow structure, and have excellent mechanical properties. Y can be used as a super fiber to enhance the composite material. In addition, the carbon nanotubes have excellent thermal conductivity, and the thermal conductivity of the carbon nanotubes makes the composite have good thermal conductivity. However, in addition to its excellent thermal conductivity, the carbon nanotubes also have good electrical conductivity, so the composites formed by the carbon nanotubes and other materials such as metals, semiconductors or polymers also have excellent electrical conductivity. . The preparation method of the carbon nanotube composite material generally includes an in-situ polymerization method, a solution blending method, and a melt blending method. The carbon nanotube composite film is an important form of practical application of the carbon nanotube composite material. The carbon nanotube composite film is generally formed by screen printing, spin coating, carbonaceous material pyrolysis or liquid phase chemical deposition. The formed carbon nanotube composite film has the advantages of good compactness and uniform dispersion. However, the preparation method of the prior carbon nanotube composite film is more complicated and the 'nano carbon nanotubes are randomly distributed in the carbon nanotube composite film along various directions. Thus, the carbon nanotubes are unevenly dispersed in the carbon nanotube composite film, so that the obtained carbon nanotube composite film has poor mechanical strength and toughness, and is easily broken, which affects the thermal and electrical properties of the carbon nanotube composite film. A carbon nanotube composite film prepared by chemically modifying a carbon nanotube (see Surface Resistivity and Rheological Behaviors)

Of Carboxylated Multiwall Carbon Nanotube-Filled PET

Composite Film, Dae Ho Shin, Journal of Applied p〇iymer

Science, V 99n3, P900-904 (2006)), although the electrical properties are improved, the type of material compounded with the carbon nanotubes is limited due to the heating conditions. In view of the above, the invention provides a wooden carbon tube composite film and a preparation method thereof, so that the obtained carbon nanotube composite film has good electrical conductivity, good mechanical strength and toughness, and the preparation method is simple and easy to produce. It is really necessary. 'Content of the invention】

The naphtha tube composite film 'includes a f-material and a plurality of tubes, wherein the carbon nanotubes are coated in parallel with the carbon nanotubes to coat the surface of the carbon nanotubes. J Compared with the prior art, this technology is based on the advantages of the following: (4) The tube has a shoulder 1342266. The following advantages: The 'nanocarbon tube composite film contains a plurality of nanocarbons connected by van der Waals force and arranged in a preferred orientation. Tube, so that the carbon nanotube composite film has better mechanical strength and toughness. Second, the surface of each carbon nanotube in the carbon nanotube composite film is formed with a metal conductive layer, compared to the prior art. The disordered carbon nanotube composite film has better conductivity. [Embodiment] Hereinafter, a structure of a carbon nanotube composite film of the embodiment of the present technical solution and a preparation method thereof will be described in detail with reference to the accompanying drawings. Referring to Fig. 1, an embodiment of the present invention provides a carbon nanotube composite film 100'. The carbon nanotube composite film 1 is composed of a carbon nanotube 11 and a conductive material (not shown). The carbon nanotube composite film 100 includes a plurality of carbon nanotubes 11 , and each of the carbon nanotubes is coated with at least one layer of a conductive material. In the carbon nanotube composite film 1 奈, the nano stone back tube 111 is arranged in a preferred orientation in the same direction, and is connected end to end by Van der Waals force. Specifically, in the carbon nanotube composite thin crucible 1, each of the carbon nanotubes 111 has substantially the same length and is arranged in a preferred orientation in the same direction to form a carbon nanotube bundle segment having a certain width, and a plurality of nanometers. The carbon tube bundle segments are connected end to end by van der Waals force to form a carbon nanotube composite film 100. Referring to Fig. 2, the surface of each of the carbon nanotubes 111 in the carbon nanotube composite film is coated with at least one layer of a conductive material. Specifically, the conductive material layer comprises a wetting layer ι2 directly bonded to the surface of the carbon nanotube ln, a transition layer 113 disposed outside the wetting layer, a conductive layer 1342 disposed outside the transition layer 113, and a conductive layer disposed on the conductive layer. Antioxidant layer ιΐ5 outside 114. Since the wettability between the carbon nanotubes m and most of the metals is not good, the above-mentioned wetting layer "2 functions to bond the conductive layer 114 to the carbon nanotubes (1). The material forming the wetting layer 112 may be a metal having a good wettability of the carbon nanotubes (1) or an alloy thereof. The thickness of the bismuth:: is 1 to 10 nm. In this embodiment, the wetting layer (1) has a thickness of about 2 nm. It can be understood that the _ selection structure. The material of the transition layer U3 is such that the material of the wetting layer 112 and the conductive layer 114 to form the transition 113 can be a material which can be better combined with the material of the wetting "2 conductive layer 114. The transition layer (1) is 2 degrees. In the present embodiment, the material of the transition layer 113 has a thickness of 2 nm. It can be understood that the transition layer ι 3 is optional and structural. The conductive layer 114 functions as a carbon nanotube. The composite film (10) has good electrical conductivity. The material forming the conductive layer m can be turned into a metal having a good conductivity or an alloy thereof, and the conductive layer 114 has a U~2G nanometer. In this embodiment, The thickness of the silver of the (4) ιΐ4 is about 5 nm. The role of the above-mentioned antioxidant layer 115 is to prevent the conductive members 14 from being oxidized in the line during the manufacturing process of the nanocarbon crucible, thereby making: j composite thin (four) 0 conductive The performance of the anti-oxidation layer (1) (4) can be gold or a stable metal which is equal to the non-oxidation in the air or their gold. The thickness of the anti-oxidation layer 115 is 1 〇 nanometer. In the example 1342266, The material of the oxidation resistant layer 115 is inscription and has a thickness of 2 nm. It is understood that the anti-oxidation layer 115 is an optional structure. Further, in order to improve the strength of the carbon nanotube composite film 100, a strengthening layer 116 may be further disposed outside the oxidation resistant layer 115. The strengthening layer 116 is formed. The material may be a higher strength polymer such as polyvinyl alcohol (PVA), polyphenylene benzobisoxazole (PBO), polyethylene (PE) or polyethylene oxide (pvc), and the thickness of the strengthening layer 116 is ojq The present embodiment calls for the material of the reinforcing layer 116 to be polyethylene glycol (pVA) having a thickness of 〇5 μm. It is understood that the reinforcing layer 116 is of an alternative structure. Please refer to FIG. 3 and FIG. The preparation method of the carbon nanotube composite film 222 in the embodiment of the technical solution mainly comprises the following steps: Step 1: providing a carbon nanotube array 216, preferably, the array is a super-sequential carbon nanotube array. The carbon nanotube array 216 provided in the embodiment is one or more of a single-walled carbon nanotube array, a double-walled carbon nanotube array, and a multi-walled carbon nanotube array. In this embodiment, the super-aligned row The method of preparing carbon nanotube arrays using chemical vapor deposition In the integrated method, the specific step of the substrate is to flatten the substrate, and the substrate may be a P-type or N-type stone substrate, or (or = a ruthenium substrate having an emulsion layer, and this embodiment preferably uses a 4-inch germanium substrate) (b) A catalyst layer is uniformly formed on the surface of the substrate. The catalyst layer material may be selected from the group consisting of iron (Fe), SG (C), Ni (N) or any combination thereof, and (c) the substrate on which the catalyst layer is formed is 7 〇. 〇~9〇〇. Annealing in the air for about 3G minutes~9G minutes; (d) placing the treated substrate in a reaction furnace, heating to ~ in the protective gas atmosphere, and introducing the carbon source gas in the autumn 1342266 After 5 to 30 minutes, the super-sequential nanocarbon carbon array is grown to a degree of 200 to 400 microns. The super-sequential carbon nanotube array is a pure naphthene carbon nanotube array formed by a plurality of carbon nanotubes that are parallel to each other and perpendicular to the substrate. The super-sequential carbon nanotube array is substantially free of impurities such as amorphous carbon or residual catalyst metal particles by the above controlled growth conditions. The carbon nanotubes in the super-sequential carbon nanotube array are in close contact with each other to form an array by van der Waals forces. The super-sequential carbon nanotube array has substantially the same area as the upper substrate. In the present example, the carbon source gas may be selected from acetylene, ethylene, broth and other chemically active hydrocarbons. The preferred carbon source gas in this embodiment is acetylene; the shielding gas is nitrogen or an inert gas, which is preferred in this embodiment. The shielding gas is argon. Step 2: A carbon nanotube film 214 is taken from the carbon nanotube array 216 by a stretching tool. The preparation method of the carbon nanotube film 214 includes the following steps: (a) selecting a plurality of carbon nanotube bundle segments of a certain width from the carbon nanotube array 216, and the embodiment preferably adopts a certain width. The tape contacts the nanocarbon array 216 to select a plurality of carbon nanotube bundle segments of a certain width; (b) stretching the plurality of carbon nanotube bundles at a constant speed along a growth direction substantially perpendicular to the carbon nanotube array 2丨6 Fragments are formed to form a continuous carbon nanotube film 214. In the above stretching process, the plurality of carbon nanotube bundle segments are gradually separated from the substrate in the stretching direction under the action of the tensile force, and the selected plurality of carbon nanotube bundle segments are respectively associated with the other naphthalenes due to the van der Waals force. The carbon nanotube bundle 1342266 • The segments are continuously pulled out end to end to form a carbon nanotube film 214. The carbon nanotube film 214 comprises a plurality of end-to-end aligned carbon nanotube bundles. The arrangement direction of the carbon nanotubes in the carbon nanotube film 214 is substantially parallel to the stretching direction of the carbon nanotube film 214. See Figure 5 for the microstructure of the carbon nanotube film 214. The preferentially oriented aligned carbon nanotube film 214 obtained by direct stretching has better uniformity than the disordered Nai tube. At the same time, the method of straightening and stretching to obtain the carbon nanotube film 214 is simple and rapid, and is suitable for industrial application. Step 3: forming at least one layer of a conductive material on the surface of the carbon nanotube film 214 to form a carbon nanotube composite thin layer 222 ^ This embodiment uses physical vapor deposition (PVD) such as vacuum evaporation or ion A layer of a conductive material is deposited by sputtering or the like. Preferably, this embodiment deposits at least one layer of a conductive material by vacuum evaporation. The method for forming at least one layer of conductive material by vacuum evaporation includes the following steps: First, a vacuum vessel 210 is provided, the vacuum vessel 210 having a deposition interval, at least one evaporation source 212 disposed at the bottom and the top of the deposition interval, respectively. 'The at least one evaporation source 212 is sequentially disposed along the stretching direction of the carbon nanotube film 214 in the order of forming at least one layer of the conductive material layer, and each evaporation source 212 can pass through a heating device (not shown) heating. The carbon nanotube film 214 is disposed at a distance between the upper and lower evaporation sources 212, wherein the carbon nanotubes 2臈4 are disposed opposite to the upper and lower evaporation sources 212. The vacuum container 2 can be evacuated to a predetermined degree of vacuum by externally pumping a vacuum pump (not shown). The evaporation source 212 material is to be treated

12 1342266 / especially conductive material. Next, by heating the evaporation source 2i2, it is melted and then evaporated or sublimated to form a conductive material vapor. The conductive material vapor meets the cold carbon nanotube film 214 and is placed on the carbon nanotube film 214 on the lower surface. The surface condenses 'forming a layer of conductive material. Since there is a gap between the nanosoils in the carbon nanotube film 214, and the carbon nanotube film 214 is thin, the conductive material can penetrate into the carbon nanotube film 214 and deposit on the carbon nanotube film 214. The surface of each carbon nanotube. Refer to Figures 6 and 7 for the photomicrograph of the carbon nanotube composite film 222 after deposition of the conductive material. It will be appreciated that each evaporation source 2p can have a deposition zone by adjusting the distance between the carbon nanotube film 214 and each evaporation source 212 and the distance between the evaporation sources 212. When it is desired to deposit a plurality of layers of the conductive material, the plurality of evaporation sources 212 may be simultaneously heated to continuously pass the carbon nanotube film 214 through the deposition regions of the plurality of evaporation sources, thereby realizing deposition of the plurality of layers of the conductive material. In order to increase the vapor density of the conductive material and prevent the conductive material from being oxidized, the vacuum in the vacuum vessel 21G should be above # (pa). In the embodiment of the present invention, the degree of vacuum in the vacuum vessel is 4xl - 4Pa. It can be understood that the carbon nanotube array 216 in the first step can also be directly placed in the above-mentioned vacuum trough state 21〇. First, a vacuum tool is used. A stretching tool pulls a nanometer gauze film 214 of a certain width from the array of carbon nanotubes. Then, the at least one evaporation source 212 is heated to deposit at least one layer of conductive material on the surface of the carbon nanotube film 214. The carbon nanotube film 214 is continuously drawn from the carbon nanotube array 216 at a constant speed, and the carbon nanotube film 214 is continuously passed through the deposition zone of the evaporation source 212, thereby realizing the nanometer from the nanometer. Pulling carbon nanotube array 216

(S 13 1342266 The carbon nanotube film 214 and the carbon nanotube composite thin crucible 222 are continuously produced. In the embodiment of the present invention, the step of forming the at least '-layer conductive material layer by the vacuum evaporation method specifically includes the following steps Forming a layer of thirst' layer on the surface of the carbon nanotube film 214; forming a transition layer on the outer surface of the wetting layer; forming a conductive layer on the outer surface of the transition skin; forming an anti-oxidation layer The layer is formed on the outer surface of the conductive layer, wherein the steps of forming the wetting layer, the transition layer and the anti-oxidation layer are all optional steps. Specifically, the carbon nanotube film 214 can be continuously passed through. And a deposition region of the evaporation source formed by the two layers of materials. λ. Further, after the forming the at least one conductive material layer on the surface of the carbon nanotube film 214, further comprising forming a reinforcement outside the conductive material layer. Step of the layer. Specifically, the carbon nanotube thin layer 214 formed with at least one layer of conductive material may be passed through a device 2~2〇 containing a polymer solution to infiltrate the entire carbon nanotube film 2 14. The polymer solution adheres to the outer surface of the conductive material layer by intermolecular force, and forms a strengthening layer after the polymer solidifies. The obtained carbon nanotube composite film 222 can be further collected on the reel 224. The collecting method is to wind the carbon nanotube composite film 222 on the reel 260. Optionally, the step of forming the carbon nanotube film 214, the forming step of the at least one conductive material layer, and the forming of the reinforcing layer The steps can be carried out in the vacuum container to realize the continuous production of the carbon nanotube composite film 222. In the embodiment of the technical solution, the resistance of the nano-carbon 1342266 official film 214 before the deposition of the conductive material is about 1600 ohms. When the conductive material Ni/Au is deposited, the electric resistance of the carbon nanotube composite film 222 can be reduced to about 200 ohms, and the visible light transmittance is 85%-95°/❶. Therefore, the formed nano-carbon composite film 222 is formed. Compared with the prior art, the carbon nanotube composite film provided by the embodiment of the present invention can be used as a transparent conductive film with lower resistance and better visible light transmittance. The preparation method has the following advantages: First, the carbon nanotube composite film contains a plurality of carbon nanotubes that are connected end to end by van der Waals force and arranged in a preferred orientation to make the carbon nanotube composite film have better mechanical properties. The strength and the boring property. Second, the surface of each of the carbon nanotubes in the carbon nanotube composite film is formed with a conductive material layer, which has better conductivity than the disordered nano carbon official composite film in the prior art. In addition, the carbon nanotube composite film also has a good visible light transmittance, so it can be used as a transparent conductive film. The three 'sinus carbon nanotube composite film is directly produced from the carbon nanotube array, The method is simple and low in cost. Fourthly, the steps of stretching the nanocarbon® film and depositing the conductive material can be carried out in a vacuum vessel, which is advantageous for the large-scale production of the carbon nanotube composite film. In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application in accordance with the law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application in this case. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. 15 1342266 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an illustration of a structure of a carbon nanotube composite film according to an embodiment of the present technical solution. 2 is a schematic structural view of a single carbon nanotube in a carbon nanotube composite film according to an embodiment of the present technical solution. Fig. 3 is a flow chart showing a method of manufacturing a carbon nanotube composite film according to an embodiment of the present invention. Fig. 4 is a schematic view showing the structure of a manufacturing apparatus of a carbon nanotube composite film according to an embodiment of the present invention. Fig. 5 is a scanning electron micrograph of a carbon nanotube film of an embodiment of the present technical solution. Fig. 6 is a scanning electron micrograph of a carbon nanotube composite film of the embodiment of the present invention. Fig. 7 is a transmission electron micrograph of a carbon nanotube composite film of the embodiment of the present invention. [Main component symbol description] Carbon nanotube composite film 100, 222 carbon nanotube 111 Wetting layer 112 Transition layer 113 Conductive layer 114 Anti-oxidation layer 115 Strengthening layer 116 1342266 Vacuum vessel 210 Evaporation source 212 Carbon nanotube structure 214 Carbon nanotube array 216 device 220 reel 260

Claims (1)

1342266 X. Patent application scope 1. The composite carbon nanotube composite thin crucible includes a conductive material and a plurality of nanocarbons: the improvement is that the carbon nanotubes are arranged parallel to the surface of the carbon nanotube composite film, The conductive material is coated on the surface of the carbon nanotube. 2. The carbon nanotube composite film according to claim 2, wherein a surface of each of the carbon nanotubes is provided with a conductive layer. 3. The carbon nanotube composite film according to claim 1, wherein the carbon nanotubes are arranged in a preferred orientation in the same direction. 4' The carbon nanotube composite film according to item 1 of claim 4, wherein the non-meter stone squash has an equal length and passes through the sun. 5. The carbon nanotube composite film according to claim i, wherein: the carbonaceous material comprises a single-walled carbon nanotube double-walled carbon nanotube or a multi-walled carbon nanotube. 6. The application of the special carbon nanotube composite film according to item 5, wherein the diameter of the single-walled carbon nanotube is q 5 nm, the diameter of the nanometer, double Φ wall carbon nanotube For 1 Nai, nano, multi-walled carbon tube diameter of 1.5 nm ~ 5 〇 nanometer. 7. The carbon nanotube composite film according to claim 2, wherein the conductive layer is made of copper, silver, gold or an alloy thereof. 8. The carbon nanotube composite film according to Item 7, wherein the conductive layer has a thickness of from 1 to 20 nm. 9. The carbon nanotube composite film according to Item 2, wherein the non-stone composite film further comprises a wetting layer disposed between the conductive layer and the surface of the carbon nanotube.厶厶10, in the ninth aspect of the patent scope, the material of the wetting layer is a carbon nanotube composite film having a wet layer thickness of W0 nano nickel, & titanium or alloy thereof述润11. In the ninth box of the patent scope of the application, the carbon nanotube composite thin Hr m carbon tube composite thin crucible between the conductive layer and the wetting layer comprises a step-transition layer set in the The carbon nanotube composite film according to the U range, wherein the material of the transition layer is steel, silver or an alloy thereof, and the transition layer has a thickness of 1 to 10 nm. 13 = The carbon nanotube composite thin flag of claim 2, wherein the carbon nanotube composite phase comprises a silking layer disposed on an outer surface of the conductive layer. 14. The carbon nanotube composite film according to claim 13, wherein the material of the oxidation resistant layer is gold, a surface or an alloy thereof, and the thickness of the oxidation resistant layer is 1 to 10 nm. . 15. The carbon nanotube composite film according to claim 2, wherein the carbon nanotube composite thin step comprises a reinforcing layer disposed on an outer surface of the conductive layer. 16. The carbon nanotube composite film according to claim 5, wherein the material of the reinforcing layer is polyvinyl alcohol, polyphenylene benzobisoxazole, polyethylene or polyethylene. The thickness of the reinforcing layer is 〇1 to μm.