JP5099331B2 - Nanocarbon material composite, method for producing the same, and electron-emitting device using the same - Google Patents

Description

  The present invention relates to a nanocarbon material composite expected to be applied as a strength reinforcing material, an electron-emitting device material, a battery electrode material, an electromagnetic wave absorbing material, a catalyst material, or an optical material, and a manufacturing method suitable for the production About.

Nano-carbon materials have a nanometer (nm) -sized fine structure composed of carbon sp ² hybrid orbitals, and therefore have characteristics that surpass conventional materials and are not found in conventional materials. It is expected to be applied as a next-generation functional material such as a strength reinforcing material, an electron-emitting device material, a battery electrode material, an electromagnetic wave absorbing material, a catalyst material, or an optical material.

  Known methods for synthesizing nanocarbon materials such as carbon nanotubes include arc discharge, laser ablation, plasma chemical vapor deposition, and thermal chemical vapor deposition. Among these methods, arc discharge method, laser ablation method and plasma chemical vapor deposition method are non-equilibrium reactions, so it is easy to generate amorphous components, and generally the yield of carbon nanotubes to be generated is low. It is also known that the thickness and type of the produced carbon nanotubes are not uniform.

  On the other hand, Patent Documents 1 and 2 disclose a thermal chemical vapor deposition method for producing carbon nanotubes by thermally decomposing hydrocarbon gas using a catalyst. The thermal chemical vapor deposition method is known to have a relatively high yield because it uses a chemical equilibrium reaction. In this method, carbon fibers grown using catalyst particles such as ultrafine iron and nickel as the core are used. can get. The obtained carbon fiber has a carbon net layer grown concentrically and hollowly. Moreover, with these methods, it is difficult to control the particle size and chemical state of the metal used as a catalyst, and it is impossible to synthesize by controlling the shape and thickness of the nanocarbon material. A required material having a desired structure cannot be obtained separately, and it is inevitable that the yield decreases as a result.

  In addition, in the conventional nanocarbon material, when processing the synthesized nanocarbon material into a use form, for example, when processing into the shape of a battery electrode, carbon impurities other than the nanocarbon material such as graphite particles and amorphous carbon are used. It is necessary to purify the nanocarbon material from the reaction product containing, and to collect the required amount of carbon nanotubes by scraping off the carbon nanotubes grown on the substrate. Therefore, a member using a nanocarbon material having a desired structure in a large amount could not be manufactured.

  Furthermore, conventional nanocarbon materials have individual crystallinity, and materials having a fibrous form are obtained. For example, the aggregate in terms of grams is a disorderly assembly and has a low density. It is a powdery or clustered solid. In order to apply such a nanocarbon material as a practical material, even if it is made into a paste or mixed with other materials such as a resin, it is a disordered and low-density assembly, so uniform mixing is not easy .

  Patent Document 3 discloses a method for producing carbon nanotubes in an alcohol solution using a metal catalyst selected from iron, cobalt, and nickel. In this method, similarly to the thermal chemical vapor deposition method, the obtained carbon fiber has a carbon network layer grown concentrically and in a hollow shape, for example, a spiral surface shape having a large surface area or an edge. No nanocarbon material having the desired structure is obtained.

  On the other hand, a cathode ray tube is widely used as an electronic display device. However, the cathode ray tube consumes a large amount of energy to emit thermal electrons from the cathode of an electron gun, and requires a large volume in structure. There was a problem. For this reason, there has been a demand for a flat display that can use cold electrons instead of thermal electrons, reduce energy consumption as a whole, and reduce the size of the device itself. Realization of high-speed response and high resolution for the display is also strongly demanded.

As a structure of a flat display using such cold electrons, a structure in which minute electron-emitting devices are arranged in an array in a flat plate cell of high vacuum is promising. For this purpose, a field emission type electron emission device utilizing a field emission phenomenon has attracted attention as an electron emission device used. In this field emission type electron-emitting device, when the strength of the electric field applied to the substance is increased, the width of the energy barrier on the surface of the substance is gradually reduced according to the strength, and the electric field strength is 10 ⁷ V / cm or more. This makes use of the phenomenon that electrons in a substance can break through its energy barrier by the tunnel effect, and thus electrons are emitted from the substance. In this case, since the electric field follows Poisson's equation, if a member that emits electrons, that is, a portion where the electric field concentrates on the emitter, cold electrons can be emitted efficiently with a relatively low extraction voltage (non- (See Patent Documents 1 and 2).

  In recent years, nanocarbon materials have attracted attention as emitter materials for the above emitters. The most typical carbon nanotube among nanocarbon materials is a hollow cylinder made by rolling a graphene sheet in which carbon atoms are regularly arranged. The outer diameter is on the order of nm, and the length is usually 0.5 to several. It is a fine substance with a very high aspect ratio of 10 μm. For this reason, an electric field tends to concentrate on the tip portion, and high electron emission ability is expected. In addition, carbon nanotubes are characterized by high chemical and physical stability, so that adsorption and reaction of residual gas in an operating vacuum are difficult to occur, and are not easily damaged by heat generated by ion bombardment or electron emission. It has characteristics.

  When carbon nanotubes are used as emitters, they are often made into a paste and applied onto a substrate by a printing method. For example, Patent Document 4 discloses an emitter formation method by screen printing. First, the cathode electrode is formed in stripes on the substrate at a predetermined pitch, and the paste containing the carbon nanotubes is formed on the cathode electrode in the form of a square or a circle in the same pitch as the cathode electrode by screen printing. To do. Next, an insulating layer is screen-printed between the resin layers containing carbon nanotubes, and then baked in an air atmosphere. Thereby, the resin component of the resin layer containing the carbon nanotube is decomposed, and the carbon nanotube is exposed to form an electron emission portion. Finally, a grid electrode is formed on the insulating layer to produce an emitter.

  In general, the paste used for manufacturing the emitter as described above is added to a carbon nanotube by adding a solvent, a dispersant, a glass frit as an adhesive, a filler, etc., and mixing them so that their distribution state is uniform. To disperse. After mixing, the mixture is filtered and mixed in a vehicle composed of a solvent and a resin to form a paste. This paste is mixed well to enhance the dispersion state and then filtered to complete the carbon nanotube paste. The carbon nanotube paste obtained by the above process is printed on a substrate, and the vehicle is oxidatively decomposed by drying and baking to obtain a carbon nanotube film.

JP 2002-255519 A JP 2002-285334 A JP 2003-12312 A JP 2003-272517 A C. A. Spindt: J. Appl. Phys., 39, 3504 (1968) K. Betsui: Tech. Dig. IVMC., (1991) p26

  As described above, the conventional nanocarbon material has a problem that a member using the nanocarbon material having a desired structure cannot be manufactured.

  In silicon emitters that apply conical emitters or semiconductor integrated circuit manufacturing technology, the emitter material of metal, silicon, or a compound thereof forms an oxide on the surface, so it has a low electron emission capability and is an electron emission part. Concentration of the electric field on the emitter was indispensable. Therefore, in order to emit electrons from the surface of these emitter materials, it is necessary to make the radius of curvature of the electron emission portion as small as possible. It was indispensable to use a conical shape with a radius of curvature at the tip of several nm or less.

  In order to use it as a surface electron source for a display or the like, it is necessary to produce a large number of conical emitters obtained by performing the ultrafine processing as described above and arrange them on the array. However, since ultra-precision machining is required, structural defects are likely to occur, and it is not easy to uniformly produce a large area, yield is reduced, defect inspection is indispensable, and manufacturing costs are increased.

  In addition, in order to use a conventional nanocarbon material as an emitter material, the nanocarbon material must be purified from reaction products containing carbon impurities other than nanocarbon materials such as graphite particles and amorphous carbon. In addition, since it is necessary to collect the required amount of carbon nanotubes by scraping off the carbon nanotubes grown on the substrate, a nanocarbon material having a desired structure was used in large quantities at a low cost. The member cannot be manufactured.

  In addition, conventional nanocarbon materials have individual crystallinity and have a fibrous form, but for example, the aggregates in gram units are disordered assemblages and low-density powders. Or it is a cluster-like solid. When such a nanocarbon material is used as an emitter material, it is difficult to control the nanocarbon material to have a desired structure and to produce it uniformly. An emitter with high uniformity cannot be obtained.

In view of the above problems, the first object of the present invention is to provide a nanocarbon material composite having a structure suitable for various applications.
The second object of the present invention is to provide a method for producing a nanocarbon material composite capable of controlling the shape and thickness of the nanocarbon material.

In order to achieve the first object, the nanocarbon material composite of the present invention has a base made of a low resistance semiconductor and a metal thin film made of palladium or platinum palladium formed on the base. It is characterized by having a nano-carbon material having a helical structure with a diameter of 20 nm or more .
Here, the spiral structure refers to a structure in which the fibers of the nanocarbon material are spirally or twisted (hereinafter also referred to as “nanocoils”). By integrating a nanocarbon material having a helical structure on the substrate, it becomes easy to handle the nanocarbon material as an aggregate, and when it is pasted or mixed with other substances, it becomes non-uniform or scattered Process suitability can be improved. In addition, by using a nanocarbon material having a helical structure, the surface area per unit volume is increased compared to the carbon nanotube, which is the most common nanocarbon material, and there is no hollow structure and the structure is dense. Therefore, when applied as a practical material, the efficiency and reliability of various elements can be improved.

To achieve the above second object, a manufacturing method of the nano carbon material composite of the present invention includes a first step of forming on a substrate made of a metal thin film made of palladium or platinum palladium from the low resistance semiconductor thin metal holding the film carrying substrate in a liquid hydrocarbon, by passing a current to the metal thin film bearing substrate viewed contains a second step of heating in a liquid hydrocarbon, and a diameter on the substrate through the metal thin film over 20nm It is characterized by forming a helical nanocarbon material .
In the above structure, the metal thin film is preferably an oxide of palladium or an oxide of platinum palladium. The thickness of the metal thin film is preferably 2 to 10 nm.
The heating temperature of the substrate is preferably 600 ° C. to less than 900 ° C.
The liquid hydrocarbon is preferably a hydrocarbon having 6 to 10 carbon atoms, and preferably octane.
In the second step, the metal thin film carrying substrate is preferably held with the metal thin film carrying surface facing downward or perpendicular.
As described above, Patent Document 3 discloses a method for producing carbon nanotubes in an alcohol solution using a metal catalyst selected from iron, cobalt, or nickel. The phase components are different. This difference affects the formation of helical nanocarbon on the substrate. That is, in a combination of a metal other than palladium or an alloy thereof and a liquid phase other than liquid carbon, spiral nanocarbon is not formed on the substrate, but only a linear hollow structure nanocarbon tube is formed.

The nanocarbon material composite of the present invention is easy to handle as an aggregate because the substrate and the helical nanocarbon material are integrated, causing non-uniformity and scattering when pasted or mixed with other materials It is excellent in practical process suitability.
Moreover, since it has a helical structure, it has high mechanical strength and a large surface area. Therefore, when the nanocarbon material composite of the present invention is used as an electrode material of a structural material, an electron emission material, an electric double layer capacitor / battery, a fuel cell, or a general secondary battery, it has good practical physical properties. In addition, the process suitability is shown, and the manufacturing cost can be reduced.

  In the case of carbon nanotubes, there is no electron emission from the wall surface, but the nanocarbon material composite has an edge in the nanocarbon fiber, so the number of electron emission points increases, and the electron emission device has a variation different from that of carbon nanotubes. As a wide range of use.

  According to the method for producing a nanocarbon material composite of the present invention, as described above, not only can the helical nanocarbon material be integrally formed on the substrate, but also the temperature at which the metal-supported substrate is heated in the liquid hydrocarbon. By controlling the thickness, it is possible to control the thickness of the nanocarbon material. For this reason, the nanocarbon material composite which has the nanocarbon material of the helical structure without the variation of high electron emission ability between lots can be manufactured easily.

Hereinafter, embodiments of the present invention will be described in detail.
First, the nanocarbon material composite of the present invention will be described.
FIG. 1 is a schematic cross-sectional view showing the configuration of the nanocarbon material composite of the present invention. The nanocarbon material composite 1 of the present invention comprises a base 2 and a nanocarbon material 3 having a helical structure grown on the base 2. Although FIG. 1 shows a case where the nanocarbon material 3 having a helical structure is present directly on the substrate 2, there may be a case where the nanocarbon material 3 having a helical structure is present on the substrate 2 through a metal. is there.

  As the substrate 2, in addition to single crystal silicon, a semiconductor substrate such as germanium, gallium arsenide, phosphorus gallium arsenide, gallium nitride, silicon carbide, or the like, glass, ceramics, quartz, or the like can be used. The thickness of the substrate 2 is not particularly limited, but a normal thickness of 100 to 1500 μm is desirable.

Next, a method for producing the nanocarbon material composite of the present invention will be described.
FIG. 2 shows an example of an apparatus for producing a nanocarbon material composite of the present invention. This apparatus includes a water cooling means 12 for cooling the liquid tank 11 outside the liquid tank 11, an electrode 13 for holding the base 2 and for passing a current through the base 2, and an organic that evaporates from the liquid tank 11. A lid 17 that holds a condensing means 15 comprising a water-cooled pipe 14 that cools and condenses liquid vapor and returns it to the liquid tank 11, and a valve 16 that introduces the condensing means 15 and an inert gas for removing air in the apparatus. And the liquid hydrocarbon 10 is hermetically held by the liquid tank 11 and the lid 17.

  According to this apparatus, the temperature of the organic liquid can be maintained below the boiling point, and the substrate temperature can be maintained at a temperature at which the thickness of the nanocarbon fiber is formed. In addition, since the organic liquid phase is condensed, the raw organic liquid is not wasted, and there is no risk of explosion or flame due to mixing of the organic gas phase and air.

Next, the method for producing the nanocarbon material composite of the present invention will be described in detail. First, the substrate is cleaned, and a thin film of metal selected from palladium or an alloy thereof is deposited on the substrate.
As described above, the substrate may be made of a semiconductor substrate such as germanium, gallium arsenide, phosphorus gallium arsenide, gallium nitride, or silicon carbide, glass, ceramics, quartz, or the like in addition to single crystal silicon. The thickness of the substrate 2 is not particularly limited, but a normal thickness of 300 to 1500 μm is desirable.
Here, palladium or an alloy thereof is palladium or platinum palladium, and includes oxides thereof. Of these, palladium is particularly preferable. With metals other than palladium or its alloys and oxides thereof, such as Fe and Co, helical nanocarbon fibers are not formed on the substrate 2, but nanotubes are formed.
The means for depositing these metals on a substrate is a sputtering method or adding a predetermined amount of metal salt, then evaporating excess water, drying and firing in an air stream at 400 to 500 ° C. Decomposition and oxidation may be performed to convert the metal salt to an oxide. When a thin film of palladium or an alloy thereof is deposited by sputtering, it is preferable to perform a treatment in which the substrate is exposed to hydrogen plasma. By this treatment, the oxide film and impurities on the surface of the metal thin film can be removed. Although the thickness of the metal thin film to deposit is not specifically limited, What is necessary is just to select suitably in the range of 2-10 nm which is normal thickness.

Subsequently, the surface on which the metal thin film of the substrate 2 is deposited is disposed on the electrode 13 of the manufacturing apparatus so as to be parallel and downward with respect to the apparatus bottom surface, and the liquid hydrocarbon 10 is filled in the apparatus. In the case where the substrate 2 is installed horizontally, if the metal thin film is disposed upward, the nanowires of spiral nanocarbon are not formed on the substrate 2. The installation direction is not limited to the horizontal direction, and may be a direction perpendicular to the bottom surface of the apparatus. In the case of installing in the vertical direction, the direction of the metal thin film is not limited.
The liquid phase filled in the apparatus is liquid hydrocarbon, and methanol or ethanol, which is an alcohol solvent, does not form helical nanocarbon fibers on the substrate 2. The hydrocarbon preferably has 6 to 10 carbon atoms. More preferred is octane. With hydrocarbons in other ranges, the operability is poor due to the boiling point and viscosity.

  From the viewpoint of safety, it is preferable to introduce an inert gas into the apparatus through the valve 16 and replace the residual air in the apparatus with an inert gas or nitrogen gas. Then, a current is passed through the electrode 13 to heat the substrate 2. Heating is performed at a temperature of the substrate 2 in the range of 550 ° C to 950 ° C. At temperatures outside this range, no helical nanocarbon fibers are formed on the substrate 2. When the substrate temperature is in the range of 500 ° C. to less than 800 ° C., fibers having a diameter of less than 20 nm are formed, and helical nanocarbon fibers having a diameter of 20 nm or more are formed at 800 ° C. to less than 900 ° C. Thus, by controlling the temperature of the substrate 2, the thickness of the helical nanocarbon fiber can be controlled.

  During production, hydrocarbon bubbles are generated from the surface of the substrate 2, and the substrate surface is covered with the bubbles. At this time, it is necessary to keep the temperature of the liquid hydrocarbon below the boiling point, and the water cooling means 12 is used for cooling. Further, the hydrocarbon in the gas phase is returned to the liquid by the condensing means 15 and returned to the liquid tank 11. The length of the helical nanocarbon fiber can be formed by maintaining the substrate 2 at a constant temperature for a certain period of time according to the desired length of the helical nanocarbon fiber.

  As shown in FIG. 3, the formation of the helical nanocarbon fiber is considered to form a helical shape by laminating the nanocarbon fibers in the horizontal direction with respect to the substrate 2 while sliding the edges little by little. . For this reason, the helical nanocarbon fiber has an open edge at both ends thereof. Unlike carbon nanotubes, this increases the number of electron emission locations, and can have a variation of electron emission ability different from that of carbon nanotubes. In the manufacturing process, the thickness of the fiber can be made uniform by controlling the temperature of the substrate 2, so that an electron-emitting device having excellent electron emission stability can be obtained.

Hereinafter, the present invention will be described in more detail based on examples.
Palladium was deposited on a Si (100) substrate (n-type, low resistance) using magnetron sputtering. The palladium thin film formed on the substrate was 4 nm in terms of the weight of the substrate converted into a film thickness. The obtained palladium-supported substrate was placed on the electrode of the manufacturing apparatus shown in FIG. 2 with the palladium thin film forming surface 4 facing downward, and the apparatus was filled with liquid octane.
Next, the palladium-supported substrate was heated at 600 ° C., 700 ° C., 800 ° C., 850 ° C. and 900 ° C. for 10 minutes, respectively, to form a nanocarbon material on the substrate.
The surface structure of the obtained nanocarbon material composite was observed with a field emission scanning electron microscope (FE-SEM). The results are shown in FIGS.

FIG. 4 is a field emission scanning electron microscope image of the surface structure of the nanocarbon material composite when the metal support is heated to 600 ° C. It can be seen that the nanocarbon fibers are formed but are not spiral, and the spiral nanocarbon material is not formed on the substrate.
FIG. 5 is a field emission scanning electron microscope image of the surface structure of the nanocarbon material composite when the metal carrier is heated to 700 ° C. As in FIG. 4, nanocarbon fibers are formed, but are not spiraled, and it can be seen that no spiral nanocarbon material is formed on the substrate.
FIG. 6 is a field emission scanning electron microscope image of the surface structure of the nanocarbon material composite when the metal support is heated to 800 ° C. Helical 50 nm to 100 nm thick nanocarbon fibers are formed.
FIG. 7 is a field emission scanning electron microscope image of the surface structure of the nanocarbon material composite when the metal carrier is heated to 850 ° C. Helical 50 nm to 100 nm thick nanocarbon fibers are formed.
FIG. 8 is a field emission scanning electron microscope image of the surface structure of the nanocarbon material composite when the metal carrier is heated to 900 ° C. Carbon fibers are formed in a film shape, not in a fibrous or helical nanocarbon fiber.

As shown in FIGS. 4 to 8, when the formed nanocarbon fiber has a palladium film thickness of 4 nm formed on the substrate, the heating temperature of the substrate is in the range of 500 ° C. to less than 800 ° C. Non-spiral fibers having a diameter of less than 20 nm were obtained, and spiral nanocarbon fibers having a diameter of 800 nm to less than 900 ° C. and a diameter of 20 nm or more were formed.
In addition, when the substrate was placed horizontally and the palladium thin film forming surface was facing upward, the spiral nanocarbon fiber was not formed under any temperature condition.
This shows that the thickness of the fiber can be controlled and made uniform by controlling the heating temperature.

As in Example 1, palladium was deposited on a Si (100) substrate (n-type, low resistance) using magnetron sputtering. The palladium thin film formed on the substrate was adjusted to two thicknesses of 2 nm and 10 nm, with the weight of the substrate converted into a film thickness.
The obtained palladium-supported substrate was placed on the electrode of the manufacturing apparatus shown in FIG. 2 with the palladium thin film forming surface 4 facing downward, and the apparatus was filled with liquid octane.
Next, the palladium-supported substrate was heated at 600 ° C., 700 ° C., 800 ° C., 850 ° C., and 900 ° C. for 10 minutes, respectively, to form a helical nanocarbon material on the substrate to obtain a nanocarbon material composite. Table 1 shows the shape of the carbon fibers formed on the substrate. The data on the film thickness of 4 nm is described by adding the data of Example 1.
In Table 1, “nanocarbon fiber” means a nanocarbon material that does not form a helical shape, and “nanocoil” means a helical nanocarbon material having a diameter of 20 nm or more.

When the palladium thin film is 2 nm, the helical nanocarbon material is not formed when the heating temperature of the substrate is 700 ° C. or lower or 900 ° C. or higher. A helical nanocarbon material having a diameter of 20 nm or more is formed at a temperature higher than 700 ° C. and lower than 900 ° C.
When the palladium thin film is 10 nm, a helical nanocarbon material having a heating temperature of 600 ° C. or more and less than 900 ° C. and a diameter of 20 nm or more is formed, and when the heating temperature of the substrate is 900 ° C. or more, non-helical nanocarbon fibers are formed. It had been.
From these, it can be seen that the formation of the helical nanocarbon material is affected by the thickness of the metal thin film on the substrate and the heating temperature of the substrate.
When the heating temperature of the substrate is 900 ° C. or higher, a non-helical carbon material is formed. However, when the film thickness is 10 nm or less, it is understood that a heating temperature of less than 900 ° C. is preferable.
In addition, regarding the thickness of the palladium thin film, as the thickness increases, a helical nanocarbon material tends to be easily formed.

(Comparative Example 1)
As a comparative example of Example 1, the liquid phase solvent was changed to ethanol and methanol, and the same conditions as in Example 1 were performed. Even under the conditions of 600 ° C., 700 ° C., 800 ° C., 850 ° C. and 900 ° C. A helical carbon material having a diameter of 20 nm or more was not formed on the substrate.

  The nanocarbon material composite of the present invention can be used as, for example, a field emission type electron-emitting device (field emitter) that emits electrons by a strong electric field. More specifically, as an electron generation source or electron gun for an optical printer, an electron microscope, an electron beam exposure apparatus, or the like, or as an ultra-compact illumination source for an illumination lamp, and further, a surface of an arrayed field emitter array constituting a flat display Needless to say, the present invention can be used as an electron-emitting device useful as an electron source, but is not limited thereto.

It is a schematic cross section which shows the structure of the nano carbon material composite_body | complex of this invention. It is a figure which shows an example of the manufacturing apparatus of the nano carbon material composite_body | complex of this invention. It is sectional drawing which shows typically the state of a helical nanocarbon fiber. It is a figure which shows the scanning electron microscope image of the nanocarbon material formed when it heated at 600 degreeC. It is a figure which shows the scanning electron microscope image of the nanocarbon material formed when it heated at 700 degreeC. It is a figure which shows the scanning electron microscope image of the nanocarbon material formed when it heated at 800 degreeC. It is a figure which shows the scanning electron microscope image of the nanocarbon material formed when it heated at 850 degreeC. It is a figure which shows the scanning electron microscope image of the nano carbon material formed when it heated at 900 degreeC.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nanocarbon material composite body 2 Base | substrate 3 Nanocarbon material 4 Metal thin film formation surface 10 Liquid hydrocarbon 11 Liquid tank 12 Water cooling means 13 Electrode 14 Water cooling pipe 15 Condensing means 16 Valve 17 Lid

Claims (9)

A first step of forming on a substrate made of a metal thin film made of palladium or platinum palladium from the low resistance semiconductor,
A second step of heating in the thin metal film carrying substrate held in the liquid hydrocarbon, the metal thin film bearing substrates by applying a current in the liquid hydrocarbon,
Only including,
A method for producing a nanocarbon material composite, wherein a helical nanocarbon material having a diameter of 20 nm or more is formed on the substrate via the metal thin film . The metal thin film is an oxide or oxides of platinum palladium palladium, manufacturing method of the nano-carbon material composite according to claim 1. The method for producing a nanocarbon material composite according to claim 1, wherein the thickness of the metal thin film is 2 to 10 nm. The method for producing a nanocarbon material composite according to claim 1, wherein the heating temperature of the substrate is 600 ° C. to less than 900 ° C.   The method for producing a nanocarbon material composite according to claim 1, wherein the liquid hydrocarbon is a hydrocarbon having 6 to 10 carbon atoms.   The method for producing a nanocarbon material composite according to claim 1, wherein the liquid hydrocarbon is octane. Wherein in the second step, the metal thin film carrying substrate, a manufacturing method of the thin metal film carrying surface facing downward or vertical direction, characterized in that it is installed, the nano carbon material composite according to claim 1, wherein. Characterized by comprising a substrate made of a low-resistance semiconductor, a nano-carbon materials formed palladium or platinum of palladium consists via a metal thin film formed on the base body diameter greater than 20nm helical structure on said substrate A nanocarbon material composite. A substrate made of a low-resistance semiconductor, nano-carbon material through a metal thin film made of palladium or platinum palladium formed on said substrate formed on said substrate diameter has a nanocarbon material or more helical structure 20nm An electron-emitting device made of a composite.