JP5228986B2 - Nanocarbon material composite substrate manufacturing method - Google Patents

Description

  The present invention relates to a nanocarbon material composite substrate, an electron-emitting device using the nanocarbon material composite substrate, and a nanocarbon material composite substrate manufacturing method suitable for manufacturing the nanocarbon material composite substrate.

Nano-carbon materials have nanometer (nm) -sized fine shapes composed of sp ² hybrid orbitals of carbon atoms, and therefore have characteristics that surpass conventional materials or that do not exist in conventional materials. Therefore, application as next-generation functional materials such as strength reinforcing materials, electron-emitting device materials, battery electrode materials, electromagnetic wave absorbing materials, catalyst materials, and optical materials is expected.

In the nanocarbon material as described above, it may be preferable to form the nanocarbon material at a higher density and use a larger surface area.
For example, in the electrode material, the higher the purity of the nanocarbon material and the larger the surface area, the higher the efficiency of power storage or power generation.
For example, when used as a field emission type electron-emitting device material, the nanocarbon material has a high purity and a concavo-convex structure with a high aspect ratio, thereby improving the electric field concentration efficiency and reducing the electrons at a lower voltage. Release is possible.

  Further, as a method for synthesizing a nanocarbon material as described above, an arc discharge method, a laser ablation method, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and the like are known. Among these methods, the arc discharge method, laser ablation method, and plasma chemical vapor deposition method are non-equilibrium reactions, so that it is easy to generate an amorphous component, and generally the yield of carbon nanotubes to be generated is low. Moreover, it is known that the thickness and type of the produced carbon nanotubes are not uniform.

For example, Patent Literature 1 and Patent Literature 2 disclose a thermal chemical vapor deposition method for producing carbon nanotubes by thermally decomposing a 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, and carbon fibers grown using catalyst particles such as ultrafine iron or nickel as a nucleus can be obtained. The obtained carbon fiber has a carbon net layer grown concentrically and hollowly. However, with these methods, it is difficult to control the particle size and chemical state of the metal used as a catalyst, and it is not possible to synthesize by controlling the shape and thickness of the nanocarbon material. Since a material having a desired desired structure cannot be obtained separately, it is inevitable that the yield is lowered as a result.

Patent Document 3 discloses a solid-liquid interface catalytic decomposition method as a method for synthesizing a nanocarbon material.
The solid-liquid interfacial decomposition method is based on a unique interfacial decomposition reaction that occurs when a solid substrate and an organic liquid come into contact with a rapid temperature difference, and can synthesize high-purity carbon nanotubes that do not require purification. This is a synthesis method with a very high yield.

On the other hand, as an electronic display device, a high-vacuum flat plate cell in which minute electron-emitting devices, particularly field emission type electron-emitting devices are arranged in an array is promising. In the field emission type electron-emitting device, when the strength of an electric field applied to a substance is increased, the width of the energy barrier on the surface of the substance is gradually narrowed according to the strength, and when the electric field strength becomes 10 ⁷ V / cm or more, The electron can break through the energy barrier by the tunnel effect, and the phenomenon that electrons are emitted from the material is utilized. 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 efficiently emitted with a relatively low extraction voltage.

  In recent years, nanocarbon materials have attracted attention as emitter materials for the above-described electron-emitting devices. 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, and has an outer diameter of the order of nm and a length of usually 0.5 to several tens of μm. It is a minute substance with a very high aspect ratio. Therefore, 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.

For example, Patent Document 4 discloses an emitter formation method in which carbon nanotubes are used as an emitter, which is formed into a paste and applied onto a substrate by a printing method.
First, the cathode electrodes are formed in a stripe pattern on the substrate at a predetermined pitch, and a paste containing carbon nanotubes is formed on the cathode electrode by screen printing in the form of an isolated rectangle or circle at the same pitch as the cathode electrode. Then, an insulating layer is screen-printed between the resin layers containing carbon nanotubes and fired 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 obtained by adding a solvent, a dispersant, a glass frit as an adhesive, a filler, and the like to carbon nanotubes, and mixing them so that the distribution state is uniform. Disperse. Filtration is performed after mixing, and the mixture is mixed into a vehicle composed of a solvent and a resin to form a paste. The paste is mixed well to increase the dispersion state and then filtered to prepare a 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 firing to obtain carbon nanotubes. By such a method, carbon nanotubes can be formed on the cathode electrode.

  However, when the emitter is formed by the printing method, it is necessary to paste the carbon nanotubes, and mixing with various binders is indispensable. Therefore, deterioration of characteristics due to the stay of the binder is inevitable. In addition, in an emitter formed by a printing method, it is difficult to align the directions of the carbon nanotubes in the paste, and it is difficult to use pure carbon nanotubes themselves as a site where the electric field concentrates.

JP 2002-255519 A JP 2002-285334 A JP 2003-12312 A JP 2003-272517 A

  An object of the present invention is to provide a nanocarbon material composite substrate manufacturing method capable of manufacturing a nanocarbon material composite substrate formed by patterning nanocarbon materials on a substrate.

The present invention includes a step of supporting a cobalt or cobalt oxide catalyst on the surface of a silicon substrate with a thickness of 2 to 10 nm , and heat-treating the substrate on which the catalyst is supported at 600 to 1000 ° C. in air. And a step of forming a three-dimensional structure pattern including a plurality of convex portions and concave portions on the side of the substrate on which the catalyst is supported by etching or a cutting blade to remove a part of the substrate together with the catalyst. And the step of leaving the catalyst only on the upper surface of the convex part, and the substrate is immersed in an organic liquid and heated to 550 to 1000 ° C., and the substrate on which the catalyst is supported by a solid-liquid interface catalytic decomposition method And a step of growing a nanocarbon material on the surface of the nanocarbon material composite substrate manufacturing method.

  In the method for producing a nanocarbon material composite substrate of the present invention, a catalyst is supported on a substrate, the catalyst is heat-treated, a three-dimensional structure pattern is formed on the substrate, and a solid-liquid interface catalytic decomposition method is formed on the surface of the substrate on which the catalyst is supported. To grow nanocarbon materials. Since the three-dimensional structure pattern is formed on the substrate after supporting the catalyst, the catalyst can be selectively left only on the upper surface of the convex portion, and the nanocarbon material can be selectively formed only on the upper surface of the convex portion. I can do it. Accordingly, it is possible to manufacture a nanocarbon material composite substrate in which nanocarbon materials are formed in a pattern array on the substrate.

It is a schematic process drawing which shows the nanocarbon material composite substrate manufacturing method of this invention. It is the schematic which shows an example of the manufacturing apparatus used for the nanocarbon material composite substrate manufacturing method of this invention. It is the schematic which shows an example of the nanocarbon material composite substrate of this invention. It is the schematic which shows an example of the nanocarbon material composite substrate of this invention. It is the schematic which shows an example of the electron-emitting element of this invention. It is a scanning electron micrograph image photograph of the nanocarbon material composite substrate of the present invention manufactured in an example.

  Hereinafter, the manufacturing method of the nanocarbon material composite substrate of the present invention will be specifically described with reference to FIGS.

  The nanocarbon material composite substrate manufacturing method of the present invention comprises a step of supporting a catalyst on the surface of a substrate, a step of performing a heat treatment on the substrate on which the catalyst is supported, and a side of the substrate on which the catalyst is supported, A step of forming a three-dimensional structure pattern consisting of convex portions and concave portions, leaving the catalyst only on the upper surface of the convex portions, and heating the substrate by immersing it in an organic liquid, by a solid-liquid interface catalytic decomposition method, And growing a nanocarbon material on the surface of the substrate on which the catalyst is supported.

First, as shown in FIG. 1A, the catalyst 4 is deposited and supported on the surface of the substrate 1.
As the catalyst 4, transition metals such as cobalt, iron, nickel, and palladium, oxides thereof, or compounds thereof can be used.
As a method for depositing these catalysts 4 on the surface of the substrate 1, a known thin film forming method may be used as appropriate, for example, a sputtering method or the like can be used.
Moreover, after applying a predetermined amount of metal salt aqueous solution, evaporating excess water and drying, it is fired in an air stream at 400 to 500 ° C. to cause decomposition and oxidation of the metal salt to convert the metal salt into an oxide. You may convert.
Although the thickness of the catalyst 4 to deposit is not specifically limited, The range of 2-10 nm is preferable. Further, the substrate may be washed before loading the catalyst.

Next, the substrate 1 carrying the catalyst 4 is subjected to heat treatment. The heat treatment may be appropriately performed by a known method according to the selected catalyst. For example, the heat treatment may be appropriately selected from an oxidizing atmosphere, a reducing atmosphere, and an inert atmosphere.
When the above-described transition metal is used as the catalyst, the temperature is preferably 600 ° C. to 1000 ° C., and the time is preferably 10 minutes or more. By this treatment, the catalyst particles can be miniaturized and fixed to the substrate, and there is an effect of preventing the catalyst particles from peeling off from the substrate in the three-dimensional structure pattern forming step described later.

Next, as shown in FIG. 1B, the substrate 1 on which the catalyst 4 is carried is processed, and a three-dimensional structure pattern including the concave portions 3 and the convex portions 2 is formed on the substrate 1.
As a method for forming a three-dimensional structure pattern, a known fine processing technique may be used as appropriate. Specific examples include (1) a method of forming a mask by lithography and performing etching, and (2) a machining method using a cutting blade.

(1) A method of performing etching by forming a mask by lithography.
If light or electron beam lithography is used, an etching mask having a fine and arbitrary pattern shape can be formed, and a micron order three-dimensional structure pattern of 1 μm or more can be processed by etching.
Further, fine processing at a semiconductor level is possible, and by applying a technique such as trench etching, a three-dimensional structure pattern having a high aspect ratio can be processed with an extremely fine pattern or pitch.
At this time, dry etching, wet etching, or the like can be used as an etching method.

(2) A machining method using a cutting blade.
Since the machining method using a cutting blade can form a linear groove along the direction by moving the cutting blade in one direction, a linear recess is continuously formed. I can do it. Further, by forming a plurality of linear recesses in parallel and forming a plurality of line recesses in parallel again so as to intersect with the linear recesses, convex portions arranged in an array can be formed. I can do it. At this time, the shape of the convex portion can be controlled by the intersection angle between the concave portions and the cross-sectional inclination angle of the cutting blade. Further, when machining using a cutting blade is used, a three-dimensional structure pattern having a high aspect ratio that reaches the millimeter order can be formed.

  In particular, when machining such as a cutting blade is used, it is preferable that “the substrate is a silicon substrate, the organic liquid contains methanol, and the catalyst contains cobalt or cobalt oxide”. When processing by machining, the catalyst supported by the thin film on the substrate surface is stressed in the direction in which the thin film peels during processing, and the catalyst may be peeled off. In the present invention, since the heat treatment after the catalyst is carried, when cobalt or cobalt oxide is carried on the silicon substrate, the catalyst particles are miniaturized and fixed to the substrate by the heat treatment. For this reason, even if it forms a three-dimensional structure pattern by machining, it can suppress that a catalyst peels.

Next, as shown in FIG. 1 (c), the substrate 1 carrying the catalyst 4 is immersed in an organic liquid and heated, and the nanocarbon material 5 is applied to the surface of the substrate by a solid-liquid interface catalytic decomposition method. The nanocarbon material composite substrate 10 is manufactured by growing.
At this time, since the catalyst 4 exists only on the surface of the convex portion 2, the nanocarbon material 5 also grows selectively only on the convex portion 2.
In the solid-liquid interfacial catalytic decomposition method, the substrate and the organic liquid come into contact with each other with a rapid temperature difference, so that a specific interfacial decomposition reaction occurs and carbon nanotubes are synthesized on the catalyst fine particles.

FIG. 2 shows an example of a manufacturing apparatus for carrying out the solid-liquid interface catalytic decomposition method.
An organic liquid 12 is accommodated in the liquid tank 11. A water cooling means (not shown) is provided around the liquid tank 11. The upper part of the liquid tank 11 is sealed with a lid 13. A pair of electrodes 14 is attached to the lid 13 so as to be immersed in the organic liquid 12. The substrate 1 is held under the pair of electrodes 14 and immersed in the organic liquid 12, and in this state, current is passed through the substrate 1 to heat it. A condenser 16 having a water cooling pipe 15 that cools and condenses the organic liquid vapor evaporated from the liquid tank 11 and returns it to the liquid tank 11 is provided above the lid 13. A filter 17 is provided on the top of the condenser 16. The lid 13 is provided with a valve 18 for introducing an inert gas in order to remove air from the liquid tank 11 and the condenser 16.

  The substrate 1 carrying the catalyst 4 on the surface is attached to the lower part of the pair of electrodes 13, and the organic liquid 12 is put into the liquid tank 11. As the organic liquid 12, alcohols such as methanol, ethanol, and octanol, or hydrocarbons such as benzene can be used. It is preferable to introduce an inert gas into the liquid tank 11 through the valve 18 to replace the residual air in the liquid tank 11. In this way, there is no risk of explosion or flame due to mixing of air and organic gas. A current is passed through the pair of electrodes 13 to heat the substrate 1. The heating temperature of the substrate 1 is preferably set in the range of 550 to 1000 ° C. Bubbles of the organic liquid 12 are generated on the surface of the substrate 1, and the surface of the substrate 1 is covered with the bubbles. At this time, in order to keep the temperature of the organic liquid 12 below the boiling point, it is cooled using water cooling means around the liquid tank 11. The organic liquid in the gas phase is condensed by the condenser 16 and returned to the liquid tank 11. For this reason, the organic liquid is not wasted. By controlling the temperature and heating time of the substrate 1, a nanocarbon material having a desired form can be obtained.

  If silicon is used as the material of the substrate 1, a stable oxidation state is formed with cobalt as a catalyst, so that the form of the nanocarbon material can be controlled more stably. When cobalt or an oxide thereof is used as a catalyst and methanol is used as an organic liquid, a nanocarbon material perpendicularly oriented with respect to the surface of the substrate 1 can be grown.

  As described above, since the substrate is heated to 550 to 1000 ° C. in the solid-liquid interface catalytic decomposition method, those skilled in the art will avoid applying a substrate having fine irregularities on the surface. This is because when the substrate having fine irregularities on the surface is heated at a high temperature, it is feared that the substrate is cracked. However, according to the study by the present inventors, even when a substrate having fine irregularities on the surface is applied to the solid-liquid interface contact decomposition method, the substrate does not crack and has a three-dimensional structure pattern. Further, the present inventors have found that a highly pure and highly crystalline nanocarbon material can be easily formed at a low cost by controlling the shape uniformly.

  In addition, when the present inventors carry a catalyst and perform substrate processing immediately, the catalyst is very thin, such as several nanometers, or is scattered in clusters. However, when the catalyst is loaded and then heat-treated, the catalyst and the substrate cause a chemical reaction and are sufficiently fixed to the substrate. I found.

  In the nanocarbon material composite substrate manufacturing method of the present invention, the catalyst is supported only on the upper surface of the convex portion of the three-dimensional structure pattern by forming the three-dimensional structure pattern after supporting the catalyst. Only a nanocarbon material composite substrate on which a nanocarbon material is selectively grown can be produced.

  Hereinafter, the nanocarbon material composite substrate of the present invention will be described with reference to FIG.

  The nanocarbon material composite substrate of the present invention includes a substrate, a three-dimensional structure pattern formed of convex portions and concave portions formed on the substrate, a catalyst supported on an upper surface of the convex portion, and a substrate on which the catalyst is supported. And a nanocarbon material formed on the surface.

  An example of the nanocarbon material composite substrate of the present invention will be described with reference to schematic cross-sectional views shown in FIGS. 3 (a) and 3 (b). In the nanocarbon material composite substrate 10 shown in FIG. 3A, the convex portion 2 is formed on the surface of the substrate 1, and the nanocarbon material 5 is selectively grown only on the upper surface of the convex portion 2. In FIG. 3A, the nanocarbon material 5 is randomly oriented. In the nanocarbon material composite substrate 10 shown in FIG. 3B, the nanocarbon material 5 is grown so as to be oriented perpendicularly to the upper surface of the convex portion 2.

  As the substrate 1, a semiconductor substrate such as single crystal silicon, germanium, gallium arsenide, phosphorus gallium arsenide, gallium nitride, or silicon carbide, glass, ceramics, quartz, or the like can be used. Although the thickness of the board | substrate 1 is not specifically limited, 100-1500 micrometers is preferable.

  In the present specification, the three-dimensional structure of the three-dimensional structure pattern specifically means that the height of the convex portion 2 (distance between the bottom surface of the concave portion and the top surface of the convex portion) is 1 μm or more, more preferably 10 μm. In addition, it means a three-dimensional structure pattern of 50 μm or more, 100 μm or more, or 1000 μm or more.

  Moreover, a surface area becomes large, so that the aspect ratio of the convex part 2 is high. It is preferable to appropriately design the aspect ratio of the convex portion 2 according to the application.

Moreover, as a shape of the convex part 2, you may design suitably by a use. When used as an electron-emitting device, the distribution of the electric field around the convex portion 2 varies depending on the shape of the convex portion 2, so that the edge portion where the upper surface and the side surface of the convex portion 2 are connected by a line so that the electric field is easily concentrated. It is preferable to provide.
In FIG. 4, an example of the shape of the convex part 2 is shown concretely. 4 (a) is a cylinder, FIG. 4 (b) is a truncated cone, FIG. 4 (c) is a quadrangular prism, and FIG. 4 (d) is a quadrangular frustum. In FIG. 4C and FIG. 4D, a quadrangular prism and a quadrangular pyramid are illustrated. However, in the present invention, the shape of the convex portion 2 is not limited to this, and other polygonal prisms and polygonal truncated pyramids may be used. good.

The nanocarbon material 5 is a crystalline carbon nanotube having a nano-sized diameter, a carbon nanohorn, a carbon nanofilament, a carbon nanowall, or a carbon nanocoil.
When the nanocarbon material 5 is oriented only perpendicularly to the surface of the substrate 1 only on the upper surface of the convex portion 2 as shown in FIG. 3B, the electric field concentrates when used as the emitter of the electron-emitting device. The nanocarbon material is selectively present only at the edge portion. Therefore, the electric field is suitably concentrated on the portion where the nanocarbon material is present, and electron emission can be obtained with a low electric field strength.

  According to the nanocarbon material composite substrate of the present invention, particularly when applied to a field emission type electron-emitting device, since it has a concavo-convex shape, the electric field is easily concentrated, electron emission is facilitated, and low voltage driving is possible. Become. In addition, if 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, a battery, a fuel cell or a general secondary battery, it can be selectively applied only to a specific part. Since a nanocarbon material can be disposed, good practical characteristics can be obtained.

Hereinafter, the electron-emitting device of the present invention will be specifically described with reference to the drawing shown in FIG.
The electron-emitting device of the present invention uses the nanocarbon material composite substrate described above as an emitter.

  FIG. 5A shows a cross-sectional view of the electron-emitting device of the present invention. The electron-emitting device 50 uses the nanocarbon material composite substrate 10 as an electron-emitting portion (emitter). In the nanocarbon material composite substrate 10, the convex portion 2 is formed on the surface of the substrate 1, and the nanocarbon material 5 is selectively grown on the upper surface of the convex portion 2. An extraction gate electrode 51 is provided above the nanocarbon material composite substrate 10.

  In the nanocarbon material composite substrate of the present invention, the nanocarbon material is selectively grown only on the upper surface of the convex portion. For this reason, when used as an emitter of an electron-emitting device, the nanocarbon material selectively exists at the edge portion where the electric field concentrates. Therefore, the electric field is suitably concentrated on the portion where the nanocarbon material is present, and electron emission can be obtained with a low electric field strength.

<Example 1>
Hereinafter, an Example is concretely described about the manufacturing method of the nanocarbon material composite substrate of this invention.

First, a catalyst was supported on the substrate surface.
At this time, the substrate was a low-resistance n-type single crystal silicon (100) substrate.
Further, the catalyst was supported by carrying out a sputtering film formation of cobalt with a thickness of 6 nm and performing a heat treatment at 900 ° C. for 10 minutes in the air.

Next, a plurality of linear grooves are formed in parallel on the substrate on which the catalyst is supported by mechanical cutting, and the linear grooves are again parallel so as to intersect the linear grooves at right angles. A plurality of the three-dimensional structure patterns having a quadrangular prism were formed.
At this time, the width of the upper surface of the convex portion of the three-dimensional structure pattern was 25 μm, and the processing depth, which is the distance between the bottom surface of the concave portion and the upper surface of the convex portion, was 100 μm.

  Next, the substrate is immersed in methanol and energized through the electrode. The substrate is initially heated at 600 ° C. for 3 minutes and then at 900 ° C. for 6 minutes, and the solid-liquid interface catalytic decomposition reaction in the vicinity of the substrate. And carbon nanotubes were produced using carbon atoms in methanol as raw materials.

  As described above, it was possible to obtain a nanocarbon material composite substrate in which carbon nanotubes on the substrate were arranged in a pattern only on the upper surface of the convex portion of the three-dimensional structure pattern. At this time, the carbon nanotubes grew in a vertical orientation with respect to the substrate surface. Moreover, the length of the grown carbon nanotube was about 2 to 3 μm.

FIG. 6 shows a scanning electron micrograph of the nanocarbon material composite substrate produced in this example and having carbon nanotubes formed thereon. In FIG. 6, FIG. 6A is an overall view of the convex portion, and FIG. 6B is an enlarged top view of the convex portion.
From FIG. 6, it was observed that carbon nanotubes were grown on the upper surface of the convex portion with high density selectively and vertically.

<Example 2>
Using the nanocarbon material composite substrate produced in Example 1, field electron emission characteristics as an electron-emitting device were evaluated.

  The nanocarbon material composite substrate manufactured in Example 1 is used as the emitter of a field emission type electron-emitting device, a 1 mm gap is provided from the emitter, a gate electrode (opening diameter 2 mm) is installed, and about 10 mm from the front gate electrode. And an anode with a phosphor was placed facing each other, and measurement was performed by applying 5 kV to the anode in a vacuum.

  As a result of the measurement, it was confirmed that the phosphor emitted light at a gate voltage of 1.0 kV, and that electron emission was obtained with a low electric field strength. At this time, a good circular light emission pattern corresponding to the opening of the gate electrode could be obtained.

<Example 3>
In the same manner as in Example 2, field electron emission characteristics as an electron-emitting device were evaluated using a nanocarbon material composite substrate. However, a nanocarbon material composite substrate was used in which the catalyst was supported after formation of the three-dimensional structure pattern and carbon nanotubes were grown on the entire surface of the substrate on which the three-dimensional structure pattern was formed.

  As a result of the measurement, the emission of the phosphor was confirmed at a gate voltage of 1.4 kV, and it was confirmed that electron emission was obtained with a low electric field strength. At this time, a non-circular broken light emission pattern could be obtained.

The nanocarbon material composite substrate of the present invention is expected to be used as a substrate for electron-emitting device materials, strength reinforcing materials, battery electrode materials, electromagnetic wave absorbing materials, catalyst materials, optical materials, and the like.
In particular, it is expected to be used as a field emission type electron-emitting device that emits electrons by a strong electric field. Specifically, for example, an electron generation source such as an optical printer, an electron microscope, an electron beam exposure apparatus, an electron gun, an illumination It is useful as an electron-emitting device for applications such as an ultra-small illumination source of a lamp and a surface electron source of an arrayed field emitter array constituting a flat display.
In addition, the use of the nanocarbon material composite substrate of the present invention is not limited to the above use.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Convex part 3 ... Concave 4 ... Catalyst 5 ... Nanocarbon material 10 ... Nanocarbon material composite substrate 11 ... Liquid tank 12 ... Organic liquid 13 ... Lid 14 ... Electrode 15 ... Water cooling pipe 16 ... Condenser 17 ... Filter 18 ... valve 50 ... electron-emitting device 51 ... gate electrode

Claims (4)

A step of supporting a cobalt or cobalt oxide catalyst with a thickness of 2 to 10 nm on the surface of a silicon substrate;
Subjecting the substrate carrying the catalyst to a heat treatment at 600 to 1000 ° C. in air;
A three-dimensional structure pattern composed of a plurality of convex portions and concave portions is formed on the side of the substrate on which the catalyst is supported, a part of the substrate is removed together with the catalyst by a cutting blade, and the concave portions are formed. Leaving the catalyst only on the upper surface of
The substrate is immersed in an organic liquid and heated to 550 to 1000 ° C., and a nanocarbon material is grown on the surface of the substrate on which the catalyst is supported by a solid-liquid interface catalytic decomposition method;
A method for producing a nanocarbon material composite substrate, comprising:   2. The method for producing a nanocarbon material composite substrate according to claim 1, wherein a distance between a bottom surface of the concave portion and an upper surface of the convex portion is 10 μm or more.   2. The nanocarbon material composite substrate manufacturing method according to claim 1, wherein the nanocarbon material is grown substantially perpendicular to the surface of the substrate.   The said organic liquid contains methanol, The nanocarbon material composite substrate manufacturing method in any one of Claim 1 to 3 characterized by the above-mentioned.