JP4403618B2 - Method for producing carbon nanotube - Google Patents

Method for producing carbon nanotube Download PDF

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Publication number
JP4403618B2
JP4403618B2 JP36226599A JP36226599A JP4403618B2 JP 4403618 B2 JP4403618 B2 JP 4403618B2 JP 36226599 A JP36226599 A JP 36226599A JP 36226599 A JP36226599 A JP 36226599A JP 4403618 B2 JP4403618 B2 JP 4403618B2
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Prior art keywords
substrate
protein
carbon nanotubes
method
inorganic material
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Expired - Fee Related
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JP36226599A
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Japanese (ja)
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JP2001181842A (en
Inventor
一郎 山下
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パナソニック株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing carbon nanotubes, and more particularly, to a method for producing carbon nanotubes arranged on a substrate surface with high density and high accuracy.
[0002]
[Prior art]
Since the carbon nanotube has a high aspect ratio and a small radius of curvature at the tip, it is suitable as a constituent material (cold cathode material) of an electron emission source in a field emission electron emitter (cold cathode device).
[0003]
For example, it has been reported that a high emission current density of 400 μA / cm 2 can be obtained from a carbon nanotube in which a large number of carbon nanotubes are bundled with a low turn-on voltage of 64V.
[0004]
Thus far, several proposals and reports have been made on synthesis techniques and application techniques of carbon nanotubes which are attracting attention as a high-current electron beam emission source driven at a low voltage.
[0005]
For example, in order to apply a field emission type emitter using carbon nanotubes as a cold cathode member to a flat panel display, it is desirable to align the carbon nanotubes as much as possible, preferably perpendicular to the electrode surface, preferably to the phosphor. Thus, it is desirable to arrange them in a two-dimensional array. There are the following reports and proposals regarding this array technology.
[0006]
Walt de Heer et al. Science 268 (1995), page 845, by flowing a suspension of carbon nanotubes through a ceramic filter to arrange the carbon nanotubes on the surface of the filter and transferring it onto a plastic sheet. A technique for forming an in-plane oriented carbon nanotube layer is disclosed.
[0007]
Japanese Patent Application Laid-Open No. 10-149760 discloses a technique of using carbon nanotubes as an electron emitter material in a field emission cold cathode device. In forming a plurality of electron emitters on a support substrate, for example, an arc Each electron emitter is configured by disposing carbon nanotubes formed by sublimating the carbon of the anode electrode by discharge and depositing it on the cathode so that the fallen trees overlap with each other by coating and dispersing. The technology is disclosed.
[0008]
Japanese Patent Laid-Open No. 10-12124 discloses a technique for growing carbon nanotubes used as electron emitters by the action of a metal catalyst deposited in pores regularly arranged in an anodic oxide film.
[0009]
Furthermore, “Pan-Pacific Imaging Conference / Japan Hardcopy '98” (held from July 15 to 17, 1998) published by the Society of Imaging Society of Japan (Electronic Photography of Japan) is a field-type emitter. A technique is disclosed in which carbon nanotubes to be arranged are aligned in the direction of an applied electric field by electrophoresis, and are moved and fixed to a holding member made of polysilane or the like formed on a substrate.
[0010]
[Problems to be solved by the invention]
However, all of the above reports and proposals are technologies for preparing carbon nanotubes separately and arranging and fixing them on the substrate, and the productivity is not necessarily good. Therefore, it is not always easy to arrange and fix with high accuracy and high precision (for example, in a desired position such as a two-dimensional array arrangement corresponding to a phosphor), and as an electron beam emission source There are many problems with the vertical arrangement on the ideal substrate surface.
[0011]
The present invention is a method for producing carbon nanotubes directly synthesized on a substrate, and the synthesis facilitates the arrangement and fixation of carbon nanotubes with high density and high precision and the ideal vertical arrangement on the substrate surface. An object of the present invention is to provide a method for producing a carbon nanotube that can be realized.
[0012]
[Means for Solving the Problems]
In order to achieve the above object, in the method for producing a carbon nanotube of the present invention, inorganic material atoms made of iron oxide, nickel oxide, or cobalt oxide are held in the inner cavity, and the periphery thereof is covered with protein. After the molecules are arranged two-dimensionally in the form of dots on the substrate, the inorganic material atoms are reduced, and further, the proteins are removed to synthesize the reduced inorganic material atoms remaining on the substrate as seeds. It is characterized by becoming.
[0013]
Protein molecules of the above, (a) virus (e.g., adenovirus, rotavirus, poliovirus, HK97, CCMV etc.), (b) off ferritin and ferritin family, such as apoferritin, (c) DpsA protein or MrgA protein (See Protein Data Bank) . Inorganic material atoms upper Symbol iron oxide, nickel oxide, Ru any one Tanedea cobalt oxide. The above synthesis method may be a CVD method.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, first, molecules having inorganic material atoms held in the lumen and covered with proteins (hereinafter sometimes referred to as “protein molecules”) are formed on the substrate at a high density and at a desired position. Deploy and arrange (that is, arrange and fix two-dimensionally) with accuracy (in the present invention, “high accuracy” means “high accuracy at a desired position”).
[0015]
For example, as schematically shown in FIG. 1, the protein molecule is a metal protein complex in which a core 1 of inorganic material atoms is held in a lumen portion and is surrounded by a protein shell 2, Ferritin extracted from organs such as spleen and liver of animals such as cattle, and apoferritin in which various inorganic material atoms are encapsulated in the lumen can be preferably used.
[0016]
In the case of ferritin, the inorganic material atom of the core 1 is usually iron oxide (Fe 2 O 3 ), the diameter of the core 1 is about 6 nm, the total number of iron oxide is about 3000, and the shell 2 has a molecular weight of 20,000. The outer diameter of the entire 24-mer is about 12 nm.
[0017]
In the case of Dps protein, although not shown, the diameter of the core 1 is about 4 nm, the shell 2 is a tetrahedral dodecahedron, and the outer diameter of the entire 12-mer is about 9 nm.
[0018]
In the present invention, an inorganic material atoms of the core 1 is not limited to iron oxide, nickel, or an oxide of cobalt.
[0019]
This two-dimensional arrangement / fixation of protein molecules is performed, for example, by the method described in JP-A-11-45990.
[0020]
Specifically, as shown in FIG. 2, a buffer solution (solution) in which protein molecules 4 are dispersed (equivalent mixed solution of a phosphate buffer solution having a concentration of 40 mM and pH 5.3 and a sodium chloride aqueous solution having a concentration of 40 mM, etc.) 3) A polypeptide film 5 is stretched on the surface of 3 to adjust the pH of the buffer 3 (FIG. 2A). Since the polypeptide film 5 is positively charged while the protein molecule 4 is negatively charged, the protein molecule 4 adheres to the polypeptide film 5 as time passes, and 2 of the protein molecule 4 A dimensional crystal is formed (FIG. 2B).
[0021]
The substrate 6 is placed (floated) on the polypeptide film 5 and the polypeptide film 5 is attached to the substrate 6 (FIG. 2C). If this substrate 6 is taken out, the substrate 6 to which the two-dimensional crystal of the protein molecule 4 is attached can be obtained through the polypeptide film 5 (FIG. 2D).
[0022]
Alternatively, as shown in FIG. 3, a substrate 6 is placed in a solution 3 in which protein molecules 4 are dispersed (pure water, pure water to which an electrolyte substance such as sodium chloride is added) 3, and the substrate 6 is perpendicular to the liquid surface. When the film is gradually pulled up, wetting films 7 are formed on both surfaces of the substrate 6. Since the protein molecules 4 are two-dimensionally dispersed in the wetting film 7, if the film 7 is dried, the substrate 6 on which the two-dimensional crystals of the protein molecules 4 are adhered to both surfaces can be obtained.
[0023]
Further, as shown in FIG. 4, a platinum blade 9 is set up vertically on a substrate 6 placed on a table 8, and a solution in which protein molecules similar to those in FIG. 2 are dispersed between the substrate 6 and the blade 9. 3 is subjected to surface tension, the blade 9 is fixed, and the base 8, that is, the substrate 6 is gradually moved in the direction of the arrow at a constant speed, a thin film 7 of the solution 3 is formed on the substrate 6. Since the protein molecules 4 are two-dimensionally dispersed in the thin film 7, when the film 7 is dried, the substrate 6 having the two-dimensional crystals of the protein molecules 4 attached to one surface can be obtained.
[0024]
Furthermore, as shown in FIG. 5 (A), the substrate 6 is placed perpendicular to the solution 3 (not shown) in the container 10 into which the solution 3 in which the protein molecules 4 are dispersed is injected as in FIG. However, the solution 3 is gradually extracted from above the container 10 with a syringe (not shown) or the like at a constant speed (not shown, but a hole is made below the container 10 and the hole 3 5 may be gradually extracted at a constant speed by the action of gravity or the like), and wet films 7 are formed on both surfaces of the substrate 6 as shown in FIG. Since the protein molecules 4 are two-dimensionally dispersed in the wet film 7 as in the case of the wet film 7 in FIG. 2, when the film 7 is dried, the two-dimensional crystals of the protein molecules 4 are formed on both surfaces. The adhered substrate 6 can be obtained.
[0025]
In the methods shown in FIGS. 2 to 5, the two-dimensional crystal of the protein molecule 4 may be formed on the entire surface of the substrate 6, or may be formed in an appropriate pattern only on a specific portion. Are prepared on the surface of the substrate 6 in advance with a region where the protein molecule 4 is likely to adhere and a region where the protein molecule 4 is difficult to adhere (for example, a hydrophobic region and a hydrophilic region by a processing method described later) After attaching 4 in a two-dimensional manner, a method of removing the molecule 4 in an appropriate pattern is adopted.
[0026]
Moreover, even if the method is based on the transcription method developed by Yoshimura et al. (See Adv. Biophys. Vol. 34, p99-107 (1987)) as shown in FIGS. 4 two-dimensional crystal film can be obtained.
[0027]
First, in FIG. 6A, when a protein molecule (apoferritin containing iron oxide) 4 is injected into a specific solution (2% sucrose solution) 3 using a syringe 11 or the like, protein molecule 4 Floats on the sucrose solution 3 as shown in FIG.
[0028]
The protein molecules 4 that first reach the gas-liquid interface form an amorphous film 12 'as shown in FIG. 6C, and the protein molecules 4 that reach later adhere to the film 12', As shown in FIG. 6D, a two-dimensional crystal 12 ″ is formed under the film 12 ′.
[0029]
When the substrate 6 is placed on the film 12 composed of the amorphous film 12 'and the two-dimensional crystal 12 "as shown in FIG. 6D, the protein molecule film 12 is transferred to the substrate 6 side. Is done.
[0030]
This film 12 can be easily transferred to the substrate 6 side by treating the substrate 6 to be hydrophobic.
[0031]
The hydrophobic treatment of the substrate 6 is, for example, a treatment with hexamethyldisilazane (HMDS) ((CH 3 ) 3 SiNHSi (CH 3 ) 3 ) or the like for a silicon substrate, or a single molecule of fluorocarbon for a glass substrate. It can be performed by covering with a film.
[0032]
Also in this transfer method, the protein two-dimensional crystal film 12 may be formed on the entire surface of the substrate 6, and if the conditions are selected, the film 12 is transferred only to the hydrophobic region and to the hydrophilic region. Therefore, it is possible to form the film 12 in an appropriate pattern by previously forming a hydrophobic region and a hydrophilic region on the substrate 6 in an appropriate pattern.
[0033]
In the present invention, after the protein molecules are developed and arranged on the substrate in a two-dimensional crystal state as described above, the inorganic material atoms that have been removed from the protein and retained in the lumen of the protein molecules are formed on the substrate. Appear in two dimensions.
[0034]
This protein portion is generally removed by heat treatment.
[0035]
For example, when held in an inert gas such as nitrogen at 400 to 500 ° C. for an appropriate time (for example, 1 hour), the protein portion and the polypeptide film in the case of FIG. Remains in two-dimensional, high-density dots.
[0036]
This may be further maintained at 500 to 900 ° C. in a reducing gas atmosphere such as hydrogen for an appropriate time to reduce the inorganic material atoms.
[0037]
The carbon nanotube of the present invention is an inorganic material atom developed and arranged on a substrate as described above (in the present invention, “inorganic material atom” means its oxide and other compounds) Is used as a seed and synthesized directly on the substrate.
[0038]
This synthesis method may be any method as long as carbon nanotubes can be synthesized, but the CVD method is preferably applicable.
[0039]
That is, a substrate on which inorganic material atoms are deployed and placed is placed in a closed system, and an organic compound serving as a raw material for carbon nanotubes is introduced into the closed system, and the substrate temperature is set to 500 to 900 ° C. Thereby, the organic compound is decomposed to generate carbon particles, and the carbon particles synthesize and grow carbon nanotubes using inorganic material atoms as seeds.
[0040]
The CVD method in the present invention can also be performed under reduced pressure (for example, less than 1 Pa to about 10 −6 Pa).
[0041]
Further, the carbon source is not particularly limited as long as it is an organic compound, but the aromatic ketone compound shown in Chemical Formula 1, orthomethyl diazole ketone, phthalocyanine, other aromatic compounds, various aliphatic compounds, etc. It can be preferably used.
[0042]
[Chemical 1]
[0043]
This CVD method is performed using, for example, an apparatus as shown in FIG.
[0044]
In FIG. 7, the substrate 6 is set on the heater 21 in the sealed chamber 20, the inside of the chamber 20 is evacuated by the vacuum pump 22, and an inert gas such as nitrogen or argon is discharged from the pipe 23 with the nozzle 24. The substrate 6 is heated by the heater 21 while introducing more).
[0045]
After the temperature of the substrate 6 is stabilized, the switching valve 25 is operated and the vapor of the organic compound as described above is supplied from the carbon source supply device 26 into the sealed chamber 20 along with a carrier gas such as nitrogen or argon. Then, it is guided onto the substrate 6 by the nozzle 24.
[0046]
The vapor of the organic compound is decomposed in the vicinity of the substrate 6 to generate carbon particles, and carbon nanotubes are synthesized and grown using the inorganic material atoms on the substrate 6 as seeds.
[0047]
After synthesizing and growing carbon nanotubes by using inorganic material atoms as seeds by the above CVD method, an inert gas atmosphere such as nitrogen or argon is taken out of the same sealed chamber or taken out from the chamber with an appropriate heating means. The carbon nanotubes may be annealed at 400-900 ° C. for about 1 hour. This annealing makes it possible to improve the adhesion with the seed inorganic material atoms and to improve the electrical conductivity.
[0048]
FIG. 8 schematically shows the state of synthesis and growth of the carbon nanotubes according to the present invention described above in order.
[0049]
First, as shown in FIG. 8A, protein molecules 4 (two-dimensional crystals) are developed and arranged on a substrate 6 with high density and high accuracy.
[0050]
Next, the substrate 6 is heat-treated to burn off the protein portion 2 of the protein molecule 4, and as shown in FIG. 8B, the inorganic material atoms 1 held in the lumen of the molecule 4 are The substrate 6 is left in a two-dimensional dot shape with high density and high accuracy.
[0051]
When the substrate 6 in this state is placed in a closed system and carbon vapor is allowed to fly into the system by the CVD method, the carbon nanotubes 13 are synthesized and grown using the inorganic material atoms 1 on the substrate 6 as seeds. The growth direction may be upward as shown in FIG. 8C or downward as shown in FIG. 8D.
[0052]
This is annealed by an appropriate heating means to obtain the carbon nanotube of the present invention.
[0053]
FIG. 8 shows a mode in which the protein molecules 4 and the inorganic material atoms 1 are attached to one side of the substrate 6 and the carbon nanotubes 13 are synthesized and grown. However, these 4, 1 are attached to both sides of the substrate 6. However, the carbon nanotubes 13 may be synthesized and grown.
[0054]
Thus, in the present invention, the inorganic material atoms (6 nm) developed and arranged on the surface of the substrate 6 are two-dimensionally arranged in a high density in the form of dots at a predetermined interval (approximately 12 nm interval). The carbon nanotubes 13 synthesized and grown using atoms as seeds are synthesized and grown in close proximity to each other, so that the carbon nanotubes 13 grow in the vertical direction due to the presence of the carbon nanotubes 13, 13. The characteristics to be improved.
[0055]
On the other hand, in the above-described conventional method for fixing and arranging carbon nanotubes, adjacent carbon nanotubes are close to each other because the arrangement of metals as seeds for arranging and fixing separately prepared carbon nanotubes is rough. Therefore, there is no effect due to the existence of the carbon nanotubes that grow two-dimensionally at high density as in the present invention, and the possibility that the carbon nanotubes are fixed and arranged by bending or the like becomes extremely high. This makes it difficult to control the vertical arrangement.
[0056]
In addition, the tendency of the growth characteristic in the vertical direction in the present invention described above becomes remarkable when the Dps protein is used as the protein molecule 4. That is, in the Dps protein, the size of the inorganic material atoms is 4 nm and the interval is 9 nm, and the tendency to align vertically becomes even stronger.
[0057]
As described above, the carbon nanotubes in the present invention are arranged extremely well with respect to the substrate surface, and can be preferably applied as a low-current-driven large current electron beam emission source. For example, a field emission type of a flat panel display It can be suitably used as a cold cathode member in the emitter.
[0058]
In the case where carbon nanotubes are synthesized and grown on both sides of the substrate, both sides can be used as the electron beam emission source, or only one side can be used.
[0059]
【Example】
Example 1
Using apoferritin holding iron oxide 1 in the lumen as the protein molecule 4, using two silicon substrates as the substrate 6, each of the two substrates 6 in the form shown in FIG. Apoferritin (two-dimensional crystal) 4 was developed and arranged with high density and high precision, and two substrates 6 (however, apoferritin 4 was attached to both sides) as shown in FIG. 8A were obtained. .
[0060]
As the apoferritin solution 3, a solution containing apoferritin collected from horse spleen at a concentration of 100 ng / ml in physiological saline is used, and the silicon substrate 6 is hydrophilic with activated ozone by ultraviolet rays at 110 ° C., respectively. What was sexually treated was used.
[0061]
In addition, the two substrates 6 are set in a single container 10 at a predetermined interval, and a syringe (not shown) is used to extract the apoferritin solution 3 from the container 10 (liquid level lowering speed). Solution 3 was extracted at 0.1 mm / min.
[0062]
The two substrates 6 obtained as described above were heat-treated by holding them at 450 ° C. for 1 hour in a nitrogen gas atmosphere, and the protein portion 2 was burned away, so that the iron oxide as shown in FIG. Two substrates 6 were obtained, in which 1 was two-dimensionally formed in a high-density dot shape and deployed (on both sides).
[0063]
One of the two substrates 6 was further reduced by holding it in a hydrogen gas atmosphere at 700 ° C. for 1 hour to reduce the iron oxide spread on both sides of the substrate 6 to obtain iron.
[0064]
Using the CVD apparatus shown in FIG. 7, the two substrates 6 were set on the heater 21 in the sealed chamber 20 in the apparatus at intervals.
[0065]
Next, the inside of the chamber 20 is evacuated by the vacuum pump 22, and argon gas is introduced into the chamber 20 from the pipe 23 through the nozzle 24, and the two substrates 6 are each 600 while holding the inside of the chamber 20 at 1 Pa. Heated to ° C.
[0066]
Thereafter, the switching valve 25 was switched, and the vapor of orthomethyldiazole ketone as a carbon particle source was supplied from the supply device 26 to the argon gas and introduced into the chamber 20 through the nozzle 24.
[0067]
In the chamber 20, the orthomethyldiazole ketone is decomposed to generate carbon particles, and the reduced iron is used as a seed to form carbon on each (both sides) of the two substrates 6 as shown in FIG. Nanotubes 13 were synthesized and grown.
[0068]
Subsequently, the synthesized and grown carbon nanotubes 13 were annealed by holding at 600 ° C. for 1 hour in the same sealed chamber 20 to obtain the carbon nanotubes in the present invention.
[0069]
Carbon nanotube 1 3 is synthesized and grown as described above, for each of the two substrates 6 annealed and subjected to electron emission tests.
[0070]
The test conditions and method were as follows: a carbon nanotube cathode and a platinum-coated chip on the counter electrode were used, and an electric field of 10 V / μm (= 10 6 to 10 7 V / m) was applied.
[0071]
As a result of the test, a current density on the order of several mA / cm 2 could be obtained with the two substrates.
[0072]
【The invention's effect】
As described above, the carbon nanotubes of the present invention can be directly synthesized and grown on a substrate, and are extremely easy to arrange and fix with high density and high accuracy and ideal vertical arrangement on the substrate surface. is there.
[0073]
Along with this, it is possible to produce a high-quality carbon nanotube as a low-voltage driven large-current electron beam emission source with high production efficiency.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing the structure of a protein molecule. FIG. 2 is an explanatory diagram showing an example of a two-dimensional arrangement / fixation method of protein molecules in the order of steps.
(A) shows a step of applying a polypeptide film on the surface of a dispersion of protein molecules and adjusting the pH of the solution. (B) is a step of forming a two-dimensional protein molecule by attaching the protein molecule to the polypeptide membrane. (C) shows a step of placing a substrate on a polypeptide film and attaching the film to the substrate (D) shows a substrate on which a two-dimensional crystal of protein molecules is attached via the polypeptide film. FIG. 3 is an explanatory view showing another example of a two-dimensional arrangement / fixation method of protein molecules. FIG. 4 is another example of a two-dimensional arrangement / fixation method of protein molecules. FIG. 5 is an explanatory view showing still another example of a two-dimensional arrangement / fixation method of protein molecules,
FIG. 6A is a diagram showing the method. FIG. 6B is a diagram schematically showing the wetting film obtained by the method. FIG. 6 shows another example of a two-dimensional protein molecule alignment / fixation method. FIG. 7 is a diagram for explaining an apparatus used when performing the CVD method according to the present invention. FIG. 8 shows an example of the carbon nanotube synthesis / growth method according to the present invention in order. It is an explanatory diagram,
(A) schematically shows a state where protein molecules are developed and arranged on a substrate (B) is a diagram (C) schematically showing a state where the protein portion of the protein molecules is burned off to form inorganic material atomic particles. Diagram showing the rigidity and growth of carbon nanotubes using inorganic material atoms as seeds [Description of symbols]
1 Inorganic material atomic core 2 Protein shell 3 Buffer solution (protein) in which protein molecules 4 are dispersed
4 Protein molecule 5 Polypeptide film 6 Substrate 7 Wet film 8 Stand 9 Platinum blade 10 Container 13 Carbon nanotube

Claims (6)

  1. A molecule having a lumen and covering the periphery with a protein, the molecule having an inorganic material atom made of iron oxide, nickel oxide, or cobalt oxide held in the lumen on the substrate The carbon nanotubes are synthesized by using the reduced inorganic material atoms remaining on the substrate as seeds by reducing the inorganic material atoms and further removing the protein after two-dimensionally arranging them in a dot shape Manufacturing method.
  2.   The method for producing carbon nanotubes according to claim 1, wherein the protein molecule is a virus.
  3.   The method for producing carbon nanotubes according to claim 1, wherein the protein molecule is a ferritin family.
  4.   The method for producing carbon nanotubes according to claim 3, wherein the ferritin family is ferritin or apoferritin.
  5.   The method for producing carbon nanotubes according to claim 1, wherein the protein molecule is DpsA protein or MrgA protein.
  6. Method for producing a carbon nanotube according to any one of claims 1 to 5, wherein the synthesis method is a CVD method.
JP36226599A 1999-12-21 1999-12-21 Method for producing carbon nanotube Expired - Fee Related JP4403618B2 (en)

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EP1550633B1 (en) 2002-09-20 2011-02-09 Panasonic Corporation Method for preparing nano-particles
WO2004051726A1 (en) 2002-11-29 2004-06-17 Nec Corporation Semiconductor device and its manufacturing method
CN1720346B (en) * 2003-01-13 2011-12-21 南泰若股份有限公司 The method of manufacturing a carbon nanotube film, layer, web, strip, and articles of elements
JP3697257B2 (en) 2003-03-25 2005-09-21 キヤノン株式会社 Carbon fiber, electron-emitting device, electron source, image forming apparatus, light valve, and secondary battery manufacturing method
US6921670B2 (en) * 2003-06-24 2005-07-26 Hewlett-Packard Development Company, Lp. Nanostructure fabrication using microbial mandrel
US20050151126A1 (en) * 2003-12-31 2005-07-14 Intel Corporation Methods of producing carbon nanotubes using peptide or nucleic acid micropatterning
JP4636466B2 (en) * 2004-02-26 2011-02-23 ヴィジョンアーツ株式会社 Method of immobilizing molecules on a substrate
JP2005295747A (en) * 2004-04-02 2005-10-20 Namiki Precision Jewel Co Ltd Electric contact mechanism for small-sized motor
JP4801334B2 (en) * 2004-07-29 2011-10-26 株式会社アルバック Method for producing carbon nanofiber
JP4765584B2 (en) * 2004-12-01 2011-09-07 日新電機株式会社 Carbon nanotube formation method and apparatus
WO2006068250A1 (en) * 2004-12-24 2006-06-29 Japan Science And Technology Agency Nanographite structure/metal nanoparticle composite
JP4857591B2 (en) * 2005-04-22 2012-01-18 東レ株式会社 Method for producing four-walled carbon nanotube, composition containing four-walled carbon nanotube, electron-emitting material, and transparent conductive film
JP2007039297A (en) * 2005-08-05 2007-02-15 Nippon Telegr & Teleph Corp <Ntt> Method for forming carbon nanotube
KR101501609B1 (en) 2009-03-16 2015-03-11 삼성전자주식회사 Method of coating catalyst metal layer using nucleic acid and method of forming nano carbon
JP2011148673A (en) * 2009-12-25 2011-08-04 Chiba Univ Method for producing carbon nanotube and method for producing electrode for fuel cell
JP5983610B2 (en) 2011-08-08 2016-09-06 味の素株式会社 Porous structure and method for producing the same
KR101452219B1 (en) * 2013-01-23 2014-10-22 포항공과대학교 산학협력단 Methods for manufacturing of carbon nanotubes by using polymerized protein

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