Method for producing nanocarbon material and method for manufacturing wiring structure
A nano carbon material is formed on the surface of a metal catalyst by conducting an electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
The present invention relates to a method for manufacturing a nano carbon material such as carbon nanotubes and the like and a method for manufacturing a wiring structure using the nano carbon material as wires.
BACKGROUND OF THE INVENTIONNano carbon materials such as carbon nanotubes and the like have recently attracted attention. These nano carbon materials have potential to find applications as electron emission sources of electrodes, conductive films, battery electrodes and the like since they have properties different from those of conventional carbon materials such as graphite and diamond. In addition, nano carbon materials are thought suitable for wiring applications. Vapor phase synthetic and arc discharging methods are known as production (synthetic) methods for nano carbon such as the carbon nanotubes and the like mentioned above.
Simultaneously, diamond-like-carbon (DLC) and carbon film have been targets of research as novel carbon materials although they are different from the nano carbon materials mentioned above. The DLC and carbon films have previously been produced most commonly by using a vapor deposition method (CVD, PVD), but a method involving electrolytic deposition was recently proposed (Hao Wang and four others, “Deposition of diamond-like carbon films by electrolysis of a methanol solution”, US, Applied Physics Letters, Aug. 19, 1996, 69(8), pp. 1074-1076. Yoshikatsu Namba, “Attempts to grow diamond phase carbon films from an organic solution”, US, Journal of Vacuum Science Technology, September/October 1992, A10 (5), pp. 3368-3370).
SUMMARY OF THE INVENTIONHowever, no investigation has been conducted at all to address the technology to manufacture nano carbon materials such as carbon nanotubes and the like using electrochemical means. A vapor phase carbon nanotube synthesis requires a temperature of about 550° C., resulting in enormous production costs and thus limiting the fields of carbon nanotube applications. For example, the vapor phase synthetic method is difficult to apply when trying to form carbon nanotubes directly on a circuit substrate to use them for wiring since allowable temperature limit of the circuit substrate is low.
The present invention was developed to solve the problem described above, and the object of the present invention is to provide a method for manufacturing a nano carbon material and a method for manufacturing a wiring structure, which can be conducted using a simple device and at a low temperature.
The inventors conducted many studies and discovered as a result that a nano carbon material could be manufactured through electrolysis using a simple device and at a lower temperature (for example, ambient temperature) than previously used. That is, to solve the object described above, the present invention is a method for manufacturing a nano carbon material, comprising the step of: forming a nano carbon material on a surface of a metal catalyst by means of electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
In addition, the present invention is a method for manufacturing a nano carbon material, comprising the steps of: forming a metal catalyst unevenly on a surface of a semiconductor by means of electrolysis in an electrolysis solution containing metal catalyst ions, the semiconductor being used as a cathode; and forming a nano carbon material on the surface of said metal catalyst by means electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
Furthermore, the present invention is a method for manufacturing a nano carbon material, comprising the steps of: forming a metal catalyst unevenly on a surface of a semiconductor by etching the metal catalyst on the surface of the semiconductor; and forming a nano carbon material on a surface of the metal catalyst by means of electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
The present invention is a method for manufacturing a wiring structure, comprising the step of: forming a nano carbon material as a wiring between two metal catalysts by means of electrolysis in an electrolysis solution containing an organic solvent, the metal catalysts, which are formed as protrusions on both ends of a wiring forming position, each being used as a cathode and/or an anode.
BRIEF DESCRIPTION OF THE DRAWINGS
The Embodiments of a method of the present invention for manufacturing a nano carbon material is explained below.
The method of the present invention for manufacturing a nano carbon material involves the use of a semiconductor on which a metal catalyst is unevenly formed as a cathode and electrolysis conducted in an electrolytic solution containing an organic solvent to form a nano carbon material on the surface of the metal catalyst.
The nano carbon material manufactured by the present invention refers to a carbon material comprising a material constructed of pieces from about 0.1 nm to several 100 nm in size. For example, carbon nano-tubes (tubular fibrous materials with a diameter of 0.1 nm to several 10 nm are listed as examples), carbon nano-wires (solid fibrous materials with a diameter of several 100 nm are listed as examples), carbon onions (fine spherical particles with a diameter of several nm to several 100 nm containing several tens to several hundreds of graphite layers arranged in onion-like layers are listed as examples) and carbon nanowire radial aggregates (numerous carbon nanowires are bundled radially and spread like flowers) may be cited. The present invention is particularly suited for manufacturing thin, long fibrous materials such as carbon nanotubes, carbon nanowires and the like.
Silicon is readily available and preferred as the semiconductor used in the cathode, but semiconductors such as germanium and the like and high resistance metals may also be used. In addition, when silicon is used, the use of silicon with impurities doped is preferred due to its low electrical resistance.
A metal catalyst is formed unevenly on the surface of this semiconductor. Here, the uneven formation refers to the dispersed formation of island shaped and granulated, for example, on the semiconductor surface. The thinking is that the electrically conductive of the formed metal catalyst areas is higher than that of the semiconductor, and the current is concentrated on the areas where the metal catalyst is formed allowing the carbon atoms in the organic solvent present in the electrolytic solution to be deposited electrolytically around the areas where the metal catalyst is formed. Any metal catalyst having electrically conductive may be used. For example, Ni, Co, Fe, Al, Cu and Zn may be listed as examples. Ni, Co and Fe are preferred, and Ni is particularly and most preferred. Co and Fe are preferred next in this order. The formation of a metal catalyst with a thickness of several nm to several tens of nm, or preferably about 10 nm, on a semiconductor surface is preferred. Now multiple numbers of metal catalysts (for example, Ni and Fe) or alloys thereof may be formed on a semiconductor.
The thinking is that the size of the individual island-like (or granulated) metal catalyst areas formed unevenly on a semiconductor surface determines the type of the the nano carbon materials mainly formed on the surface. For example, carbon nanotubes are mainly formed when the size of individual metal catalyst areas (diameter) is 0.1 nm to several 10 nm or preferably 0.1 nm to 10 nm or more preferably from 0.1 nm to 0.5 nm. The thinking is that tubular carbon nanotubes are formed by a so-called edge effect wherein electrolytic current is concentrated on the metal catalyst edge resulting in electrolytic deposition of carbon on said edge while the metal catalyst encounters difficulties undergoing electrolytic deposition in the center. In addition, carbon nanowires are mainly manufactured when the individual metal catalyst areas (diameter) are several 100 nm or preferably from 100 nm to 200 nm. In this situation, the diameter is large enough to allow no edge effect to be manifested, and the electrolytic current flows through the entire metal catalyst surface. Then the carbon is deposited electrolytically on the entire metal catalyst surface resulting in the growth of solid carbon nanowires. In addition when a metal catalyst is present on a semiconductor surface in various sized areas (diameter), various nano carbon materials are formed according to the diameter.
As a method used to form a metal catalyst unevenly on a semiconductor surface, a method wherein an electrolysis is conducted in an electrolytic solution containing metal catalyst ions with a semiconductor used as a cathode, and the metal catalyst is unevenly electrolytically deposited on the semiconductor surface, for example, is available. In this case, the metal catalyst can be formed unevenly by lowering the metal catalyst ion concentration in the electrolysis solution and conducting electrolysis using a low electrical current density. In this case, sufficient metal ions may be dissolved in the electrolysis solution so that the film thickness is about 10 nm when the all of the metal ions dissolved in the solution are accumulated on the substrate surface (on one side). Therefore, the concentration is changed depending on the amount of electrolysis solution and is suitably adjusted along the conditions described above. Solutions obtained by dissolving a nitrate salt of the metal catalysts described above (nickel nitrate, cobalt nitrate, ferrous nitrate and the like) in an alcohol (for example, ethyl alcohol) may be used as the electrolysis solution.
As another method to form a metal catalyst unevenly on a semiconductor surface, a method in which a metal catalyst is formed on a semiconductor surface and this metal catalyst is then etched may be cited. In this case, a metal catalyst such as Ni and the like is formed to a designated thickness by, for example, spattering on a semiconductor surface, and the surface is subjected to an etching gas (for example, gaseous ammonia) to partially etch and remove Ni.
As a method to control the size (diameter) of the individual metal catalyst areas unevenly formed, the amount of metal ions in an electrolytic solution may be increased to yield large metal catalyst particles in the case of the electrolytic deposition described above. In the case of etching described above, the metal catalyst areas become smaller as the etching temperature rises and the etching time is extended. In either case, the metal catalyst particle size is ordinarily distributed over a relatively broad range, and the particle size of large particles is often several μm while that of small particles is often several nm.
The organic solvent present in an electrolysis solution is not particularly restricted, and alcohols, nitriles, benzenes and xylenes may be listed as examples. Alcohols such as methanol, ethanol and the like and aliphatic nitriles such as methane nitriles, ethane nitrites (acetonitrile) and the like are acceptable. The electrolysis solution may be an organic solvent itself or a mixture of multiple numbers of organic solvents. Furthermore, organic solvents to which water, conductivity aids and the like have been added are also acceptable.
The electrolysis solution described above is electrolyzed in the present invention. The anode is not particularly restricted, and a carbon electrode or a variety of insoluble anodes and the like, for example, may be used. In addition, the electrolysis conditions are not particularly restricted, but a direct current electrolysis using a current density of from 1 mA/cm2 to several mA/cm2 or preferably from 2 mA/cm2 to 6 mA/cm2 is preferred. The electrolysis voltage (the voltage between the anode and the cathode) changes according to the distance between electrodes and the electrical conductivity of the electrolysis solution, but 0.1 kV to several 10 kV is preferred and 0.1 kV to 5 kV is even more preferred. By raising the electrolysis voltage to this level, the carbon atoms in an organic solvent have the potential to be more readily converted into anions and deposited electrolytically. In addition, an alternating electrolysis is an option, and, in this case, the semiconductor described above may be used in one of the anode and cathode or preferably in both. Now the electrolysis temperature is not particularly restricted, and a temperature at which the electrolysis solution does not boil, for example, from room temperature to about 50° C. may be used. The electrolysis solution may be suitably cooled to remove the heat generated by the electrolysis. The electrolysis time changes according to the electrolysis conditions, but from an hour to about ten hours of electrolysis, for example, is acceptable.
The electrolysis device shown in
The nano carbon material electrolytically deposited may be mechanically peeled from the metal catalyst, for example, and recovered. In addition, nano carbon materials encapsulating the metal catalyst or nano carbon materials formed with the metal catalyst on the bottom may be obtained. Also, the nano carbon material may be used as it is electrolytically deposited on the semiconductor.
The conditions under which a nano carbon material is electrolytically deposited are shown schematically in
Next, one embodiment of method for manufacturing a wiring structure of the present invention is explained. The method for manufacturing a wiring structure of the present invention is conducted using the same procedures used to manufacture the nano carbon materials described above, but the difference from the method described above is the use of a metal catalyst formed as protrusions from both ends of a wiring formation location as the anode and the cathode. In the method for manufacturing a wiring structure of the present invention, a nano carbon material is formed as wiring on the metal catalyst between the areas acting as the anode and the cathode. This point will be explained with reference to
In
When an electrolysis is conducted using protrusions 200a and 201a as the cathode and anode, respectively (either may be the cathode but the protrusion 200a is arbitrarily designated as the cathode in this embodiment), under this condition, the nano carbon material electrolytically deposited on the protrusion 200a grows toward the protrusion 201a and the nano carbon material connects to the protrusion 201a in due course. The nano carbon material forms a wiring 300 between protrusions 200a and 201a in the manner described. [
The size (diameter) of protrusions 200a and 201a may be comparable to the size (diameter) of the metal catalyst in the nano carbon material production method described above. By controlling the diameter, the same point at which the type of nano carbon material is changed in the nano carbon material production method described above is observed. The height of protrusions 200a and 201a may be, for example, several nm to several 10 nm. Essentially, the current should be concentrated on protrusions 200a and 201a.
Next, another embodiment of the wiring structure production method is explained with reference to
When a power source is connected to individual wiring patterns 210 and 211 and an electrolysis is conducted while at least the space between the protrusions 210a and 211a is filled with the electrolysis solution described above, a nano carbon material is formed in the form of a wiring 301 between the protrusions 210a and 211a in the same manner observed in the
As described above, a wiring structure can be formed at a low temperature such as ambient temperature and the like using a nano carbon material when a method for manufacturing a wiring structure of the present invention is used. In addition, fine wiring formation that was extremely difficult to obtain previously can be easily conducted. That is, a current concentrates on a protrusion in a wiring formation location, and a nano carbon material can be selectively electrolytically deposited on the areas where wiring is desired.
EXAMPLESNext, the present invention is explained in further detail by presenting specific examples below, but the present invention is not limited to these examples.
Example 11. Metal Catalyst Formation on Semiconductor Surface.
Ni was spattered to a thickness of 30 nm on the surface of a semiconductor substrate (resistance ratio: 0.5 Ωcm, electrode area 50 mm2) consists of p type crystalline silicon and was left standing for ten minutes in a gaseous ammonia atmosphere. This treatment yielded a semiconductor substrate from which a portion of the Ni was etched and removed, leaving granular Ni. The SEM (scanning electron microscope) image of the semiconductor substrate on which Ni was unevenly formed is shown in
2. Electrolytic Deposition on Cathode Using Electrolysis.
The electrolysis device shown in the aforementioned
In this example, the uneven deposition of Ni on the semiconductor substrate described above and a nano carbon material electrolytic deposition were conducted simultaneously in the electrolysis solution described below.
First, 4.4×10−2 mg of Ni nitrate was dissolved in 2.5 ml of ethanol (purity 99.5% by volume, reagent special grade), and the solution was dissolved in 50 ml of ethanol to prepare an electrolysis solution. An electrolysis was conducted using electrolysis conditions identical to those described in Example 1 and an electrolytically deposited material was obtained on the cathode surface using the electrolysis solution and the electrolysis device described above, using the semiconductor substrate described above as the cathode and the carbon rod described above as the anode. The electrolysis time was eight hours. The thinking is that granular Ni was deposited on the semiconductor substrate in the initial stage and a nano carbon material was electrolytically deposited next on the Ni granules in this electrolysis.
COMPARATIVE EXAMPLEAn electrolysis was conducted and an electrolytically deposited material was obtained using the same procedure described in Example 1 above with the exception that Ni was not formed on the semiconductor substrate described above and ethanol was used as the electrolysis solution.
The electrolytically deposited materials obtained in the individual examples and the comparative example were identified according to the following method. First the SEM (scanning electron microscope: manufactured by Nippon Denshi JSM-5600, electron beam 15 kV) images of the cathode containing the electrolytically deposited material obtained was examined, and, in addition, TEM (transmittance type electron microscope: manufactured by Nippon Denshi, JEM-2010F, electron beam 200 kV) images of the electrolytically deposited material were examined. In addition, EDS (energy dispersive spectroscopy: an energy dispersing type X ray diffraction device, manufactured by Oxford, Link ISIS, electron beam 15 kV) measurements were taken in the same measurement zone as the SEM measurements described above. The results are shown in
First,
The results mentioned above are summarized in Table 1.
As clearly indicated by the data presented in Table 1, carbon nanotubes, carbon nanowires and carbon onions were obtained in Examples 1 and 2. In the case of the comparative example, amorphous carbon film layers were obtained, but no carbon nanotubes or carbon nanowires were obtained.
According to the method for manufacturing a nano carbon material of the present invention, a nano carbon material can be manufactured using a simple electrolytic method using a simple device and at a lower temperature (for example, ambient temperature) than previously used, and the method is particularly suited for manufacturing fibrous nano carbon materials such as carbon nanotubes, carbon nanowires and the like.
Claims
1. A method for manufacturing a nano carbon material, comprising the step of: forming a nano carbon material on a surface of a metal catalyst by means of electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
2. A method for manufacturing a nano carbon material, comprising the steps of: forming a metal catalyst unevenly on a surface of a semiconductor by means of electrolysis in an electrolysis solution containing metal catalyst ions, the semiconductor being used as a cathode; and forming a nano carbon material on the surface of said metal catalyst by means electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
3. A method for manufacturing a nano carbon material, comprising the steps of: forming a metal catalyst unevenly on a surface of a semiconductor by etching the metal catalyst on the surface of the semiconductor; and forming a nano carbon material on a surface of the metal catalyst by means of electrolysis in an electrolysis solution containing an organic solvent, the semiconductor on which the metal catalyst is unevenly formed being used as a cathode.
4. A method for manufacturing a wiring structure, comprising the step of: forming a nano carbon material as a wiring between two metal catalysts by means of electrolysis in an electrolysis solution containing an organic solvent, the metal catalysts, which are formed as protrusions on both ends of a wiring forming position, each being used as a cathode and/or an anode.
Type: Application
Filed: Dec 25, 2003
Publication Date: Jul 27, 2006
Inventor: Haruo Yokomichi (Imizu-gun)
Application Number: 10/563,018
International Classification: C25D 5/10 (20060101); C25D 9/00 (20060101);