Source: http://www.google.com/patents/US20020172639?dq=patent:+7360079
Timestamp: 2016-02-12 12:38:25
Document Index: 569869236

Matched Legal Cases: ['art 76', 'arts 10', 'arts 10', 'arts 10', 'arts 10', 'Application No. 2001']

Patent US20020172639 - Carbon nanotube structures, carbon nanotube devices using the same and ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsCarbon nanotube structures are provided, in which the networks with a desired area and volume, where the carbon nanotubes are electrically or magnetically connected, are formed and the method for easily manufacturing the carbon nanotube structures with less carbon nanotube structures. Carbon nanotube...http://www.google.com/patents/US20020172639?utm_source=gb-gplus-sharePatent US20020172639 - Carbon nanotube structures, carbon nanotube devices using the same and method for manufacturing carbon nanotube structuresAdvanced Patent SearchPublication numberUS20020172639 A1Publication typeApplicationApplication numberUS 10/014,560Publication dateNov 21, 2002Filing dateDec 14, 2001Priority dateMay 21, 2001Also published asUS6921575, US20060062924Publication number014560, 10014560, US 2002/0172639 A1, US 2002/172639 A1, US 20020172639 A1, US 20020172639A1, US 2002172639 A1, US 2002172639A1, US-A1-20020172639, US-A1-2002172639, US2002/0172639A1, US2002/172639A1, US20020172639 A1, US20020172639A1, US2002172639 A1, US2002172639A1InventorsKazunaga Horiuchi, Masaaki Shimizu, Hisae YoshizawaOriginal AssigneeFuji Xerox Co., Ltd.Export CitationBiBTeX, EndNote, RefManReferenced by (90), Classifications (22), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetCarbon nanotube structures, carbon nanotube devices using the same and method for manufacturing carbon nanotube structures
[0169] The carbon nanotube structures manufactured by the method of manufacturing the carbon nanotube structures mentioned above are described including the carbon nanotube devices, which are applicable embodiments. [0170] First of all, the method of preparing the high-viscosity dispersing liquid W used in the embodiments described below. [0171] A water solution, which is prepared by adding 0.01 g of dodecyl sodium sulfate in 10 ml of water is used as the dispersion medium and the carbon nanotubes are added little by little while the dispersion medium is stirring in an ultrasonic distributor (output 11W). For the carbon nanotubes, SWNTs with 4 nm of thickness and 5 μm of average length are used. [0172] The viscosity of the liquid becomes higher as the amount of the added carbon nanotubes increases. At the density of the carbon nanotubes corresponding to the critical point X shown in FIG. 1, the viscosity of the liquid rapidly increases. This is verified by measuring the viscosity of the liquid in a bath at constant temperature of 20� C. using an Ubbelohde viscometer (the rate of the liquid flowing through capillary columns). [0173] While stirring is continued, the carbon nanotubes are further added until the density of the carbon nanotubes reaches 2 g/liter. In this way, the high-viscosity dispersing liquid W with about 2 mPa?2s of viscosity is prepared. [0174] (First Embodiment) [0175] [0175]FIG. 8 is a schematic perspective view showing a first embodiment of the carbon nanotube structure of the invention. A carbon nanotube structure 68 made of the carbon nanotubes 64 is fixed on almost the whole surface of a planar board 62. The carbon nanotubes 64 with several μm to several-ten μm in length are in contact with each other to form an electric conductive network. For this reason, conductivity is attained on the surface of the planar board 62. FIG. 9 is an electronic microscopic picture (magnified by a factor of 30000) showing the carbon nanotube structures 68, which is an embodiment of the invention. Note that some error has occurred in the magnification of the picture because of its large scale. [0176] The carbon nanotube structures 68, which is an embodiment of the invention, can be attained by applying the high-viscosity dispersion medium W to the surface of the planar board 62 by spin coating and drying it. [0177] If any of transparent materials such as glass sheets, mica sheets, or polymer sheets (for example, polyester, polystyrene or nylon) are used for the planar board 62, vary high transparency can be attained as a whole. The methods, by which electric conductivity is given on the surface of the board by carbon evaporation or metal evaporation, have been known. Compared with these methods, if the carbon nanotube structures 68 are used to make the surface of the planar board 62 conductive as indicated in the embodiment, very high light transmittance can be attained because the surface of the planar board has the gaps with no need for covering as a whole with the carbon nanotubes. [0178] Thus, the carbon nanotube structures 68 of the embodiment can be used not only as the carbon nanotube devices such as electric conductive boards and electrodes but also as the carbon nanotube devices such as transparent electrodes and transparent boards. [0179] In the embodiment, electric conductivity can be freely controlled and electric conductivity can be locally varied by controlling the amount of carbon nanotubes forming into a bundle (the thickness of the bundle) and the density of the networks (the branch density). For this reason, the carbon nanotube structures of the embodiment can be used not only for single devices such as LEDs but also for the devices, which are closely packed, such as displays, on the surfaces of which, various types of treatments are applied. [0180] Further, in the embodiment, any objects other than the carbon nanotubes may be inserted at the gaps among at least some of the carbon nanotubes 64 in the network. By dispersing the objects other than the carbon nanotubes, the functions corresponding to that of the objects other than the carbon nanotubes to be added can be given to the carbon nanotube structure. The functions of the objects other than those of the carbon nanotubes include, for example, the function similar to that of spacers and the functions which are involved in electric and/or magnetic conductivity. For the objects using these functions, the objects mentioned as the “other objects” in the section <Method of manufacturing the carbon nanotubes>can be used with no change. [0181] To insert the objects other than the carbon nanotubes, as mentioned in the section <Method of manufacturing the carbon nanotubes>, the other objects may be simply added in the high-viscosity dispersing liquid W. Alternately, the objects other than the carbon nanotubes may be arranged at the gaps among and/or in the vicinity of the carbon nanotubes using any of the methods (for example, 1) the method by which the materials are exposed an vapor, for example, by vacuum evaporation, 2) the method by which a solution containing the material intended to for example, dye solution is dropped, or the material is soaked into the solution, 3) the method by which the temperature is raised and dropped repeatedly to make fine cracks due to difference in expansion coefficients, allowing the other objects to enter into them, and 4) the method by which electrons, atoms, ions, molecules, or particles are accelerated and implanted) after the carbon nanotube structures have been formed. [0182] When the electrical conductivity of the carbon nanotube structures 68 is directly observed through a current detection SPM with a probe coated with metal (scanning probe microscope), electric conductivity working in the whole carbon nanotube structures 68 of the invention can be verified. Further, electric conductivity of larger area than that of the network structure verifiable by an SEM can be verified. [0183] Furthermore, FIG. 10 shows an example of the carbon nanotube devices using the carbon nanotube structure 68 of the invention. The carbon nanotube devices shown in FIG. 10 are made by attaching input terminals 66A to 66D and output terminals 66A′ to 66D′ at the ends of the same carbon nanotube structure 68 as that shown in FIG. 8. [0184] The carbon nanotube devices of the embodiment can be used for multi-branch devices, in which the input into any of the input terminals 66A to 66D is multi-branched and output from four output terminals 66A′ to 66D′. [0185] When values for electric conductivity are examined between the input terminals 66A to 66D and the output terminals 66A′ to 66D′ by increasing the electrodes on the both sides, initially no difference is found. When a voltage (5V) is applied only to a certain pair of input/output terminals (66B and 66C′) ten times, the current values for the pair of input/output terminals are increased. Since no difference is observed in other pairs of input/output terminals, the carbon nanotube network mainly involved in the electric conduction for the certain pair of input/output terminals is certified. [0186] Second, when a voltage (10V) is applied only to a certain pair of input terminals (66B and 66C′) ten times, the current values for the pair of input terminals is decreased. At that time, an increase in the current values for the other pairs of input terminals (66C and 66A′) can be verified. An interaction is observed between the carbon nanotube network mainly involved in electric conduction of the certain pair of input/output terminals and the carbon nanotube network mainly involved in electric conduction of the other pair of input terminals. [0187] By applying the carbon nanotube devices of the embodiment, a learning function can be attained in multi-channel input and output devices. [0188] Note that by integrating other objects having the functionality mentioned before or by reforming contact parts among the carbon nanotubes each other, input signals can be variously modulated. Alternately, by applying a magnetic field from one or both of the sides of the planar board 62, the input signals can be modulated. [0189] (Second Embodiment) [0190] [0190]FIG. 11 is a schematic plan view showing the second embodiment of the carbon nanotube structure of the invention. On a surface of a given planar board 72, a carbon nanotube structure 78 made of carbon nanotubes 74 is fixed. In the embodiment, the carbon nanotube structure 78 in which the carbon nanotubes 74 are arranged along the desired patterning, is formed. [0191] The carbon nanotube structure 78 of the embodiment can be manufactured as follows. [0192] Using any of materials such as glass sheets and mica sheets, a hydrophobic surface is formed by applying the water-repellent treatment at the parts other than the patterning 76 on the surface of the planar board 72 to achieve the patterning 76 as shown in FIG. 11B. Then, only the patterning part 76 has hydrophobicity. Note that in the embodiment, using a silane coupling agent, the water-repellent treatment is applied. [0193] Using the high-viscosity dispersing liquid W, in which a water-soluble medium is used for the dispersion medium and by dipping it on the planar board patterned shown in FIG. 11B, the carbon nanotubes 74 fix only to the patterning 76 of which the surface is hydrophobic, and the carbon nanotube structure 78 of a shape shown in FIG. 11A is manufactured. [0194] Like the first embodiment, in the second embodiment, the objects other than the carbon nanotubes may be inserted in the carbon nanotube structure 78 or plural terminals may be attached. [0195] Thus, according to the embodiment, the carbon nanotube structure, which is patterned into the desired shape, can be formed on the surface of the planar board and can be used as a wiring part and a device by adding the function mentioned above to the carbon nanotube structure itself. [0196] (Third Embodiment) [0197] [0197]FIG. 12 is a schematic perspective view showing the third embodiment of the carbon nanotube structure of the invention. In the figure, convex parts 10 made of gold fine particles formed on the given planar board 12 are bound on the carbon nanotube structure 88 made of the carbon nanotubes 84. [0198] In the third embodiment, first the convex parts 10 made of gold fine particles are formed on the planar board 12 as shown in FIG. 4A. Specifically, the convex parts 10 distributed like islands are formed by evaporating 20 nm of gold on the surface of the glass sheet, which is the planar board 12 and heating it. By spin-coating the high-viscosity dispersion medium to linked among and cover the whole gold fine particles like islands, the carbon nanotube structure 88 is formed. [0199] In the embodiment, the convex parts 10 of gold fine particles like islands which are separated from each other, are electrically connected by the carbon nanotube structure 88. [0200] (Fourth Embodiment) [0201] [0201]FIG. 13 is a schematic sectional view showing the fourth embodiment of the carbon nanotubes of the invention. With respect to the carbon nanotube structure of the embodiment, on the surface of insulated planar board 92, a carbon nanotube structure layer 98A similar to that of the first embodiment, a copper phthalocyanine evaporated layer 96A (0.1 μm), the carbon nanotube structure layer 98B, a copper phthalocyanine evaporated layer 96B (0.1 μm), and a carbon nanotube structure layer 98C similar to that of the first embodiment are formed in that order. [0202] The carbon nanotube structure of the embodiment is manufactured as follows. [0203] On an insulated planar board 92 made of glass, one side of which a metal electrode 94S is disposed, a carbon nanotube structure layer 98A in the same manner as that for the first embodiment. In addition, on it, the copper phthalocyanine evaporated layer 96A by evaporating copper phthalocyanine, the carbon nanotube structure layer 98B in the same manner as that for the first embodiment, the copper phthalocyanine evaporated layer 96B, and a carbon nanotube structure layer 98C similar to that of the first embodiment are formed in that order. The insulated planar board 92 made of glass, on one side of which a metal electrode 94S is disposed, is overlapped on the carbon nanotube structure 98C with the metal electrode 94S oppositely faced to the metal electrode 94D (5 mm distant each other) to manufacture a laminated structure made of the carbon nanotube structure layers and the phthalocyanine evaporated layers. [0204] The resultant laminated structure has conductivity lower (1 MΩ/m) than that of three-layer carbon nanotube structure with no phthalocyanine contained (0.001 Ω/m) and electric conductivity of the carbon nanotube structures contained in different nanotube structure layers can be verified. [0205] Furthermore, as shown in FIG. 14, a silicone wafer is used instead of the insulated planar board 92 made of glass to manufacture the similar laminated structure. In addition, the carbon nanotube device is manufactured by attaching a gate electrode 94G on the board side on the resultant laminated structure. By applying a voltage to the gate electrode 94G and measuring source drain current flowing across the metal electrodes 95S and 94D, the behavior as a field effect transistor is verified. The device has a semiconductor characteristic because of its phthalocyanine layers and by applying a voltage, an increase in conductance is confirmed. [0206] (Fifth Embodiment) [0207] [0207]FIG. 15 is a schematic enlarged perspective view showing the fifth embodiment of the carbon nanotube device of the invention. The carbon nanotube device of the embodiment is manufactured by the carbon nanotube structure 108A similar to that of the first embodiment, a electron transport layer 110 (0.2 μm), a light emission layer 106 (0.05 μm), a hole transport layer 104 (0.2 μm), a carbon nanotube structure layer 108B similar to the of the first embodiment, and a second transparent board 100B (500 μm) are formed on a surface of a first transparent board 100A (500 μm) in that order. The carbon nanotube device of the embodiment indicates the function of a laminated diode. [0208] Silica glass is used for the first and second transparent boards 100A and 100B. Note that in the invention, there is no special limitation and the transparent boards made of various materials such as soda glass, quartz glass, sapphire, mica, and polyacryl plate may be used. [0209] With respect to the electron transport layer 110, a thin film is formed by spin-coating an oxadiazol (PBD) solution. Note that in the invention, there is no special limitation and the electron transport layers made of various materials used for the electron transport layers in such fields, as electrophotography, diode element, LED element, EL element, and transistor element may be used. [0210] With respect to the light emission layer 106, a film is formed by spin-coating a tris (8-hydroxyquinolinora-aluminum complex (A1Q3)) solution. Note that in the invention, there is no special limitation and the light emission layers made of various materials used for the light emission layers in such fields, as LED element, EL element, and semiconductor laser may be used. [0211] With respect to the hole transport layer 104, a film is made by spin-coating N,N′-bis (3-methylphenyl), N,N′-diphenyl (1,1′-biphenyl), and 4,4′-diamine (TPD) solutions. Note that in the invention, there is no special limitation and the hole transport layers made of various materials used for the hole transport layers in fields regarding electrophotography, diode element, LED element, EL element, and transistor element may be used. [0212] When a voltage (10 V) is applied between the carbon nanotube structure layers 108A and 108B of the resultant carbon nanotube device, light is emitted from both the sides of the device. [0213] A carbon nanotube device for comparison is made using commercially available transparent electrodes (ITO thin film made by magnetron spattering on a silica glass: 1.4�10−4Ω?4 cm) instead of the first transparent board 100A and the carbon nanotube structure layer 108A, as well as the second transparent board 100B and the carbon nanotube structure layer 108B. With respect to the device for comparison, light is emitted by applying a voltage as well, although light emitted from the carbon nanotube device of the invention is brighter than that of the device for comparison, which proves that the carbon nanotube structure of the invention is useful as the transparent electrode. [0214] (Sixth Embodiment) [0215] [0215]FIG. 16 is a schematic sectional view showing the sixth embodiment of the carbon nanotube device of the invention. The carbon nanotube device is manufactured by attaching the terminals 126A and 126B to the carbon nanotube of the first embodiment and distributing light emitting molecules (the molecules emitting when a voltage is applied) 122 in the network of the carbon nanotube structure 68. [0216] With respect to the carbon nanotube device of embodiment, the terminals 126A and 126B are attached to the construction of the carbon nanotube structure of the first embodiment and the light emitting molecules 122 are immersed in the carbon nanotube structure 68 by soaking the structure into a solution containing the following constituents, in which light emitting molecules are dispersed. [0217] ?bConstituents of solution?n [0218] bCarbon tetrachloride: 100 ml [0219] bToluene: 20 ml [0220] bTris: (8-hydroxyquinolinora-aluminum complex (A1Q3)): 1 g [0221] With respect to the resulting carbon nanotube device, electric resistance of the carbon nanotube structure 68 is increased and when a voltage higher than the threshold voltage (5.5 V) is applied to the carbon nanotube structure 68, light is observed under an inverted fluorescence microscope. This suggests that the light emitting molecules 122 are inserted at the gaps among the carbon nanotubes 68 and the voltage applied to the carbon nanotube structure 68 is transmitted through the carbon nanotubes 64 disposed at the portions of the carbon nanotube structure 68 to the light emitting molecules 122. Thus, according to the carbon nanotube structure of the invention, the molecular element can be used for the carbon nanotube wiring. [0222] (Seventh Embodiment) [0223] [0223]FIG. 17 is a schematic, enlarged perspective view showing the seventh embodiment of the carbon nanotube device of the invention. The carbon device of the invention is manufactured by forming a carbon nanotube structure layer 138A, a first functional organic thin film layer 136A, a carbon nanotube structure layer 138B, a second functional organic thin film layer 136A, a carbon nanotube structure layer 138C, a third functional organic thin film 136C, and the carbon nanotube structure layer 138D on the planar board 132 at the ends of which the input terminals 134A to 134D and the output terminals 134A′ to 134D′ are attached in that order. [0224] Each of the layers will be described below in detail. [0225] Silica glass is used for the planar board 132. [0226] With respect to the carbon nanotube structure layers 138A to 138D, the liquid, which is diluted by factors 3.5, 3, 2.5, and 2, is prepared by adding water to the high density liquid W (the density of the carbon nanotubes: 2 g/little) used as a concentrate solution and each of the 138A, 138B, 138C, and 138D layers is formed by spin coating using the various density of liquid prepared before in that order. [0227] The first and second functional thin films 136A and 136B are formed by spin-coating to 0.2 μm of thickness using a solution, which is prepared by dissolving 1 mg of PMMA polymer in 10 ml of acetonitrile. Note that the planar board is heated to 120� C. after spin coating aiming at removal of acetonitrile, which is a residual medium, from the film layers and higher adhesiveness of the film layers to the carbon nanotube structure. [0228] Note that when the current characteristics are compared between the device with only the first functional organic thin film layer (136A) and the device with the second layer (136B) added, an increase in the current values is observed in several pairs of input and output terminals. This suggests that the parts among the network is magnetically connected with each other through PMMA, as an organic functional layer and that a high-order network, which is partially broken, partially connected, and transmitted signals across multi-layers, can be formed instead of the network, which is simply connected as a whole. [0229] By adding another functional organic thin film layer to the device, the third layer (the third functional organic thin film layer 136C) is formed as follows. Two grams of azobenzene is dissolved into 100 ml of monochlorobenzene and a thin film is formed by spin-coating. The thickness of the resulting thin film is about 100 nm or thinner. By further spin-coating, another 200 nm of film in total (the third layer (136C)) is formed. [0230] By emitting a laser beam onto the carbon nanotube device of the embodiment, which is resulted from the addition of the third layer, from above (in the direction normal to the plane of the device) cis-trans substitution of azobenzene molecules is induced. The result shows that the current values for certain pairs of input and output channels are increased or decreased depending on the laser being on or off. When a laser is applied at another site, no difference in the current values for certain pairs of input and output channels is found. On the other hand, it is found that the current values for another pair of input and output channels are increased or decreased depending on a laser being on or off. This means that the device, which can control the current for any pair of input and output channels connected to the network when a stimulus is applied externally, is achieved. [0231] According to the invention, the carbon nanotube structures, in which the networks, where electric and/or magnetic connections are established between the carbon nanotubes each other, have been formed into the desired area and volume, can be achieved and the method of manufacturing the carbon nanotube structures are easily manufactured with less carbon nanotubes can be provided. Further, according to the invention, the carbon nanotube devices using such useful carbon nanotube structures can be provided. [0232] The entire disclosure of Japanese Patent Application No. 2001-150904 filed on May 21, 2001 including specification, claims, drawings and abstract is incorporated herein by reference in its entirety. 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B82B1/00, B81C99/00Cooperative ClassificationY10T428/2918, Y10S977/742, Y10S977/938, C01B31/0253, B82Y30/00, D01F9/12, B82Y15/00, B82Y40/00European ClassificationB82Y30/00, B82Y15/00, C01B31/02B4D, B82Y40/00, D01F9/12Legal EventsDateCodeEventDescriptionDec 14, 2001ASAssignmentOwner name: FUJI XEROX CO., LTD., JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HORIUCHI, KAZUNAGA;SHIMIZU, MASAAKI;YOSHIZAWA, HISAE;REEL/FRAME:012392/0666;SIGNING DATES FROM 20011115 TO 20011119Dec 24, 2008FPAYFee paymentYear of fee payment: 4Dec 27, 2012FPAYFee paymentYear of fee payment: 8RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services