WO2006120789A1

WO2006120789A1 - Method for manufacturing carbon nanotubes by catalyst, method for manufacturing electric field emission electron source, electric field emission electron source, and electric field emission display

Info

Publication number: WO2006120789A1
Application number: PCT/JP2006/303723
Authority: WO
Inventors: Lujun Pan; Yoshikazu Nakayama
Original assignee: Public University Corporation, Osaka Prefecture University
Priority date: 2005-05-02
Filing date: 2006-02-28
Publication date: 2006-11-16

Abstract

This invention provides a method for manufacturing carbon nanotubes, which can accurately control conditions for the growth of carbon nanotubes for electric field emission suitable for the manufacture of electric field emission electron sources or FEDs, a method for manufacturing an electric field emission electron source, an electric field emission electron source, and an electric field emission display. In the method for manufacturing carbon nanotubes in the presence of a Co/Ti catalyst or an Fe/Al catalyst, conditions for the regulation of the thickness of a catalyst film, conditions for the regulation of the thickness of catalyst film per se, conditions for whether or not a raw material gas is preheated at a stage before the contact of the raw material gas with the catalyst film, conditions for the temperature of wall of a reaction chamber, and conditions for the regulation of the catalyst contact time of the raw material gas and the flow rate of a raw material gas are used as a group of conditions for the control of the growth of carbon nanotubes to grow the carbon nanotubes at a low temperature at or below the glass softening point. In this case, the growth can be controlled with high accuracy, and this contributes to the production of high-performance FEDs and the like.

Description

Specification

Production method of carbon nanotube by catalyst, production method of field emission electron source, field emission electron source and field emission display

Technical field

The present invention relates to a carbon nanotube production method, a field emission electron source production method using carbon nanotubes, a field emission electron source, and a field emission display, and more specifically, a soft material such as a glass substrate. A method for producing carbon nanotubes using a catalyst that can hold a catalyst on a substrate having a low temperature or melting point and efficiently grow carbon nanotubes on the catalyst at a low temperature that does not soften the substrate. The present invention relates to a method for manufacturing a field emission electron source, a field emission electron source manufactured by the method, and a field emission display.

Background art

[0002] In 1991, carbon nanotubes were discovered in arc discharge deposits of carbon, and inspired by this discovery, mass production research on carbon nanotubes was started. In arc discharge, impurities such as carbon particles are generated in addition to carbon nanotubes, and it has been recognized that mass synthesis is difficult.

[0003] In 1994, Amerinckx et al. (Amelinckx, XB Zhang. We succeeded in synthesizing Bonn nanotube. Their production method is to form a metal catalyst such as Co, Fe, or Ni into a fine powder, heat the vicinity of the catalyst to 700 ° C or higher, and contact the catalyst like acetylene or benzene. It is a method of decomposing these organic molecules by circulating a simple organic gas. However, the shape of the produced carbon nanotubes was various, and carbon nanotubes such as linear, curved, planar spiral, and coil were mixed.

[0004] On the other hand, research has been conducted to improve the production efficiency of linear carbon nanotubes. 1 994 [Supapan beraphin and Dan Zhou, Applied Physics Letters, Vo 1.64 (1994) pp. 2087-2089: Non-Patent Document 2] conducted a carbon nanotube production experiment using a mixed catalyst. Their mixed catalysts are FeZNi, Ni / Mg, m T Co / Ni, C There are 5 types of oZCu. The produced carbon nanotubes were mainly single-walled carbon nanotubes, and it was found that the production efficiency did not increase so much.

[0005] Since these studies, research on mass synthesis of carbon nanotubes using catalytic CVD has been conducted. Most of these studies are methods in which a raw material gas such as acetylene is decomposed with a catalyst heated to 700 ° C or higher to produce carbon nanotubes on the catalyst. Therefore, it is assumed that the substrate holding the catalyst has a heat resistance of 700 ° C. or higher.

[0006] By the way, the use of carbon nanotubes has been studied in various ways. Among them, the field emission display (hereinafter referred to as FED) using the field emission characteristics of single-bonn nanotubes is considered promising. Field emission is a phenomenon in which when a strong electric field is applied to the solid surface, the potential barrier on the surface of the electron force confined on the solid surface is lowered, and the tunnel effect makes it easier to jump out into the vacuum. This FEED displays a picture by placing a nanotube on a glass substrate and causing electrons emitted by field emission to collide with a phosphor.

[0007] As a technology for standing carbon nanotubes on a glass substrate, a carbon nanotube production catalyst is fixed on the glass substrate, and this catalyst is used as a seed for thermal chemical vapor deposition (hereinafter referred to as thermochemical vapor deposition method). Is called a thermal CVD method.) A method of vertically growing carbon nanotubes on a catalyst is conceivable!

Non-patent literature 1: Amelinckx, X. B. Znang. D. Bernaerts, X. F. Zhang, V. Ivanov and J. B. Nagy, SCIENCE, 265 (1994) 635

Non-Patent Document 2: Supapan Seraphin and Dan Zhou, Applied Physics Letters, Vol. 64 (199 4) pp. 2087-2089

Disclosure of the invention

Problems to be solved by the invention

[0008] When carbon nanotubes are formed on a glass substrate by a thermal CVD method, it is necessary to grow the carbon nanotubes below the softening point (softening temperature) of the glass substrate. On the other hand, the soft spot of glass varies depending on the type of glass. For example, it is 690 ° C, 745 ° C, 900 ° C, etc. even for heat-resistant glass. When non-heat-resistant glass is used, the soft spot is further reduced. Examples include ° C. Therefore, when a catalyst is fixed to a glass substrate having a low soft spot and carbon nanotubes are grown at a furnace wall temperature of 700 ° C or higher, the glass softens even if the carbon nanotubes grow. There is a problem that can not be used for FED. In other words, in order to produce carbon nanotubes without softening the glass, it is necessary to set a critical temperature that does not soften the glass at 550 ° C and find a method for growing carbon nanotubes below this critical temperature. There is.

[0009] In addition, when manufacturing FED using carbon nanotubes, a field emission carbon nanotube is formed between a pair of anode electrodes and force sword electrodes formed at intervals of about several tens to several hundreds μm. It is necessary to form many standing field emission electron sources. In each field emission electron source, it is necessary to dispose the tip of the field emission nanotube at a position lower than the position of the field emission adjusting gate electrode provided between the pair of electrodes. Therefore, in order to produce high-performance field emission electron sources or FEDs using carbon nanotubes, it is necessary to grow the field emission nanotubes with precise control of growth conditions such as quality, length, and formation density. There was a problem that there was. In particular, as a quality problem, when carbon nanotubes are formed by the thermal CVD method, amorphous components are also formed, which lowers the purity of the carbon nanotubes. There is a problem in that the process of reducing the amorphous component by the tig treatment is necessary, leading to a decrease in the efficiency of the FED production process.

[0010] Therefore, an object of the present invention is to perform vertical growth with high efficiency using a catalyst for growing carbon nanotubes at a temperature of 550 ° C or lower without softening glass or the like used as a substrate. Field emission electron source, field emission force used in FED production, carbon nanotube production method, electric field that can accurately control growth conditions such as quality, length and formation density of single-bonn nanotube An emission electron source manufacturing method, a field emission electron source, and a field emission display are provided.

Means for solving the problem

[0011] The present invention has been made to solve the above-mentioned problems. The first aspect of the present invention is a CoZTi catalyst film containing at least Co element and Ti element on a substrate, or at least Fe element and A1. An FeZAl catalyst film containing elements is formed, and the catalyst film is placed in the reaction chamber to A method for producing carbon nanotubes by bringing a raw material gas into contact with heating, the conditions for adjusting the film thickness of the catalyst film, whether the raw material gas is preheated at a stage before the raw material gas contacts the catalyst film And a method for producing carbon nanotubes using a catalyst that controls the growth of carbon nanotubes by adopting at least one of the above conditions and a condition group consisting of conditions for adjusting the temperature of the reaction chamber.

[0012] In a second aspect of the present invention, in the first aspect, the condition for adjusting the time for the source gas to contact the catalyst film and the condition for adjusting the flow rate of Z or the source gas are the above conditions. It is a manufacturing method of the carbon nanotube by the catalyst added to a group.

[0013] In a third aspect of the present invention, in the first or second aspect, the catalyst film is configured by stacking metal films of the respective elements, and the film thickness of each of the metal films is adjusted. Thus, a carbon nanotube production method using a catalyst for adjusting the film thickness of the catalyst film.

[0014] A fourth aspect of the present invention is a method for producing carbon nanotubes using a catalyst that, in the third aspect, sets the thickness of each metal film to be substantially the same and adjusts the thickness. .

[0015] A fifth aspect of the present invention is the carbon nanotube by the catalyst according to the first or second aspect, wherein the preheating temperature of the raw material gas is adjusted as a furnace wall temperature in a range of 200 ° C to 1000 ° C. It is a manufacturing method.

[0016] A sixth aspect of the present invention is the carbon nanotube by the catalyst according to the first or second aspect, wherein the temperature of the reaction chamber is adjusted to a range below the glass soft point as the furnace wall temperature. It is a manufacturing method.

[0017] In a seventh aspect of the present invention, in the first or second aspect, the catalyst film comprises the catalyst according to claim 1 or 2, wherein the catalyst element contains the element as an alloy. Production method.

[0018] An eighth aspect of the present invention is a method for producing carbon nanotubes using a catalyst according to the first or second aspect, wherein the catalyst film contains each element as a metal compound.

[0019] A ninth aspect of the present invention is a method for producing carbon nanotubes using a catalyst in which the catalyst film is carbonized in the first to eighth aspects. [0020] In a tenth aspect of the present invention, a force sword electrode film is formed on a glass layer, and an insulating layer in which a through hole is formed in a required portion is disposed on the force sword electrode film, and the inside of the through hole is disposed. In a field emission electron source in which a carbon nanotube is arranged and a gate electrode film is formed on the insulating layer, a CoZ Ti catalyst containing at least Co element and Ti element on the electrode film in the through hole. Or a field emission electron source in which a FeZAl catalyst containing at least Fe element and Al element is disposed, and by using this catalyst, a carbon nanotube is formed in the through hole, and the tip of the carbon nanotube is present in the through hole. .

In an eleventh aspect of the present invention, a force sword electrode film is formed on a glass layer, and an insulating layer having a through hole formed in a required portion is disposed on the force sword electrode film, and the inside of the through hole is disposed. In a field emission electron source in which a carbon nanotube is arranged and a gate electrode film is formed on the insulating layer, a CoZ Ti catalyst containing at least Co element and Ti element on the electrode film in the through hole. A film or a FeZAl catalyst film containing at least Fe element and Al element is disposed, and the catalyst film is exposed in a reaction chamber and brought into contact with a raw material gas under heating to grow carbon nanotubes, the CoZTi catalyst film At least one of a group of conditions including a condition for adjusting the film thickness, a condition for whether the source gas is preheated before the source gas contacts the catalyst film, and a condition force for adjusting the temperature of the reaction chamber. Adopt the conditions Is a manufacturing method of a field emission electron source is present in the through hole of the tip of the carbon nanotubes after.

[0022] In a twelfth aspect of the present invention, the field emission electron source of the tenth aspect is disposed, an anode electrode is disposed opposite to the gate electrode film, and a phosphor layer is formed on the anode electrode side. A field emission display (FED) in which electrons emitted from the carbon nanotubes collide with the fluorescent material layer to emit light.

The invention's effect

[0023] The present inventors have found that carbon nanotubes are produced at a lower temperature than before by using a CoZTi or FeZAl binary catalyst for the synthesis of high-performance carbon nanotubes. In this regard, a patent application has already been filed (Application No .: Japanese Patent Application No. 2004-127395).

[0024] Furthermore, the present inventors have verified the applicability of force-bonn nanotubes formed by using a two-element catalyst of CoZTi or FeZAl to manufacture an electron source for FED. Verification As a result, it was found that by controlling the catalyst film thickness and growth conditions, it was possible to synthesize vertically aligned high-quality carbon nanotubes and at the same time to control the film thickness using the preheating effect of the reaction gas. This finding makes it possible to produce high-quality FED electron sources by generating high-quality carbon nanotubes with a specified length on the substrate without deformation of the glass substrate.

[0025] According to the first embodiment of the present invention, since the catalyst for producing carbon nano-nanotubes containing Co element and Ti element or Fe element and A1 element is used, the reactor wall temperature is 550 ° C or lower in the reaction chamber. Carbon nanotubes can be grown substantially vertically on the catalyst with high efficiency. The combined catalyst of Co element and Ti element, Fe element and A1 element was discovered for the first time by the present inventors and succeeded in synthesizing carbon nanotubes for the first time by this combination. When the substrate for the catalyst film in the present invention is a glass substrate, the substrate temperature is adjusted to 550 ° C. or lower, and the glass substrate does not soften. Therefore, the glass substrate on which the carbon nanotubes produced by this method are grown can be used as it is as an electron source for FED. Of course, when the substrate is a heat-resistant substrate, carbon nanotubes that can be adjusted to a desired temperature of 550 ° C. or higher can be grown with high efficiency.

Furthermore, according to the present embodiment, conditions for adjusting the film thickness of the catalyst film, conditions for whether or not the source gas is preheated before the source gas contacts the catalyst film, and conditions for adjusting the temperature of the reaction chamber Since the growth of carbon nanotubes is controlled by adopting at least one of the powerful conditions, the growth conditions such as the quality, length and density of carbon nanotubes can be controlled accurately, and field emission It is possible to provide a manufacturing method suitable for manufacturing an FED without an electron source.

[0026] According to the second aspect of the present invention, the length of the grown carbon nanotubes is adjusted according to the condition for adjusting the time for the source gas to contact the catalyst film and the condition for adjusting the flow rate of Z or the source gas. In addition to controlling the length (full length), it is possible to significantly reduce the amorphous component, and it is possible to provide a method for producing carbon nanotubes using a catalyst suitable for mass production of field emission electron sources or FEDs.

[0027] According to a third aspect of the present invention, in the first or second aspect, the catalyst film is C. o The film is composed of a Ti film or a Fe film and an Al film, and the film thickness of the catalyst film is adjusted by adjusting each film thickness. Therefore, in the process of forming a metal film of CoZTi or FeZAl, Carbon nanotube growth conditions can be controlled with high precision through controllable layer formation and film thickness adjustment. In addition, various PVD methods (physical vapor deposition) and CVD methods (chemical vapor deposition) such as vapor deposition, sputtering, and ion plating can be used as the method for laminating the metal film.

[0028] According to a fourth aspect of the present invention, in the third aspect, the Co film thickness and the Ti film thickness or the Fe film and the A1 film are set substantially the same, and the film thickness of each metal film is set. Therefore, the growth condition of the carbon nanotube can be controlled with high accuracy by adjusting the film thickness value that can be controlled in the metal film forming process of CoZTi or FeZAl.

[0029] According to the fifth aspect of the present invention, in the first or second aspect, since the preheating temperature of the source gas is adjusted as a furnace wall temperature, a range force of 200 ° C to 1000 ° C is also adjusted. The raw material gas whose preheating temperature is set to at least 100 ° C. or more can be supplied to the reaction chamber to efficiently grow carbon nanotubes in the catalyst, and the conditions for growing carbon nanotubes by the catalyst Can be easily controlled by the furnace wall temperature, and there can be provided a method for producing a carbon nanotube suitable for industrial production of FED without a field emission electron source.

[0030] According to the sixth aspect of the present invention, in the first or second aspect, the temperature of the reaction chamber is adjusted to a range below the glass soft spot as the furnace wall temperature. The raw material gas is supplied to the chamber so that the carbon nanotubes can be efficiently grown on the catalyst, and the growth conditions of the carbon nanotubes by the catalyst can be easily controlled by the furnace wall temperature. In addition, it is possible to provide a method for producing a carbon nanotube suitable for industrial production of FED. The glass soft spot is a temperature at which glass is softened by heating, and is preferably 550 ° C. or lower, for example. Further, the lower limit temperature can be freely set within this range as long as it is a temperature at which the carbon nanotube grows by the catalyst.

[0031] According to the seventh aspect of the present invention, a catalyst for producing carbon nano-nanotubes containing the element as an alloy is provided. Therefore, Fe and Al, Co and Ti are uniformly mixed and Single-bonn nanotubes can be uniformly grown at a high density.

[0032] According to the eighth embodiment of the present invention, since each element of the catalyst is contained as a metal compound, various compounds such as metal oxides, metal nitrides, and organometallic compounds can be used. Therefore, there is an advantage that the target catalyst can be freely prepared by a known chemical formulation.

[0033] According to the ninth embodiment of the present invention, since the catalyst surface is carbonized, particulate carbide is formed, and carbon nanotubes can be efficiently grown by this carbide catalyst. Therefore, low temperature synthesis at 550 ° C or lower can be efficiently realized.

[0034] According to the tenth aspect of the present invention, the field emission can be achieved simply by growing carbon nanotubes in the through holes by the catalyst and stopping the growth so that the tips of the carbon nanotubes exist in the through holes. An electron source can be configured. Since the tip of the carbon nanotube is located at a lower position than the gate electrode film, the electron current (current) emitted from the tip of the carbon nanotube can be adjusted by varying the gate voltage, and an effective field emission electron source can be provided. . In particular, the CoZTi catalyst and the FeZAl catalyst have the advantage that a carbon nanotube can be grown at a low temperature below the softening point of the glass layer, so that a high-performance field emission electron source without any structural deformation of the glass layer can be provided.

According to the eleventh aspect of the present invention, the field emission electron source before growing the carbon nanotubes in the tenth aspect is arranged in the reaction chamber to expose the catalyst film in the reaction chamber, and this catalyst A method of growing a carbon nanotube by bringing a film into contact with a source gas under heating, wherein the source gas is preheated at a stage before adjusting the film thickness of the catalyst film and before the source gas contacts the catalyst film. The tip of the carbon nanotube after growth can be present in the through-hole only by adopting at least one of the condition group that also has the condition force that adjusts the temperature of the reaction chamber and the condition that the temperature of the reaction chamber is adjusted. It becomes possible. Therefore, the tip of the carbon nanotube can be easily present at an arbitrary position lower than the position of the gate electrode film, and the intensity of the field-emission electron current can be freely adjusted by the gate voltage. There is an advantage that a field emission electron source can be manufactured.

[0036] According to the twelfth aspect of the present invention, the field emission electron source of the seventh aspect is disposed, the anode electrode is disposed opposite to the gate electrode film, and the fluorescent material is disposed on the anode electrode side. Simply forming the layers can provide a high-performance field emission display (FED). To the catalyst Since the total length of the grown carbon nanotubes can be freely adjusted as much as possible to form higher quality carbon nanotubes, a field emission display that can freely adjust the strength of the electron current emitted from the carbon nanotube tip by the gate voltage is provided. it can.

Brief Description of Drawings

FIG. 1 is a process diagram for explaining an example of a method for producing an FeZAl catalyst or a CoZTi catalyst according to the present invention.

FIG. 2 is a configuration diagram of a two-way catalyst carbonization apparatus according to the present invention.

FIG. 3 is a schematic configuration diagram of a carbon nanotube production apparatus according to the present invention.

[Fig. 4] SEM image of carbon nanotubes grown at 550 ° C with CoZTi catalyst without carbonization.

FIG. 5 is an AFM image of a CoZTi catalyst carbonized at 500 ° C.

[Figure 6] S of carbon nanotubes grown with CoZTi catalyst carbonized at 500 ° C

EM image.

[Fig. 7] FE-SEM and AFM images of FeZAl catalyst carbonized at 450 ° C.

[Fig. 8] FE-SEM and AFM images of FeZAl catalyst carbonized at 500 ° C.

[Fig. 9] Particle distribution diagram of FeZAl catalyst that has been carbonized at 450 ° C and 500 ° C.

[Fig. 10] SEM image of carbon nanotubes grown at 550 ° C with carbonized FeZAl catalyst.

[Fig. 11] SEM image of carbon nanotubes grown at 550 ° C with FeZAl catalyst without carbonization.

FIG. 12 is a Raman spectroscopic view of the produced carbon nanotube.

FIG. 13 is an SEM image of carbon nanotubes grown when the CoZTi catalyst film thickness is set to 0.5 nm / 0.5 nm.

FIG. 14 is an SEM image of a carbon nanotube grown when the CoZTi catalyst film thickness is set to InmZlnm.

FIG. 15 is an SEM image of a carbon nanotube grown when the CoZTi catalyst film thickness is 2 nmZ2 nm. FIG. 16 is an SEM image of a carbon nanotube grown when the CoZTi catalyst film thickness is 4 nmZ4 nm.

[Fig. 17] SEM image of carbon nanotubes grown by pre-heat treatment, when the CoZTi catalyst film thickness is InmZlOnm and the reactor wall temperature in reaction chamber B is 550 ° C.

FIG. 18 is an SEM image of carbon nanotubes grown by preheating, when the CoZTi catalyst film thickness is 4 nmZ10 nm, and the furnace wall temperature in reaction chamber B is 550 ° C.

FIG. 19 is an SEM image of carbon nanotubes grown without pre-heat treatment, with a CoZTi catalyst film thickness of 0.5 nm / 0.5 nm and a furnace wall temperature in reaction chamber B of 450 ° C. .

FIG. 20 is an SEM image of carbon nanotubes grown when pre-heat treatment was not performed and the CoZTi catalyst film thickness was 0.5 nm / 0.5 nm and the furnace wall temperature in reaction chamber B was 500 ° C. .

[Fig.21] SEM image of carbon nanotubes grown without pre-heat treatment, CoZTi catalyst film thickness 0.5nm / 0.5nm, and reactor chamber B wall temperature at 550 ° C .

FIG. 22 is an SEM image of carbon nanotubes grown by pre-heat treatment, when the CoZTi catalyst film thickness is 0.5 nm / 0.5 nm and the furnace wall temperature in reaction chamber B is 450 ° C.

FIG. 23 is an SEM image of carbon nanotubes grown by pre-heat treatment, when the CoZTi catalyst film thickness is 0.5 nm / 0.5 nm and the furnace wall temperature in reaction chamber B is 500 ° C.

FIG. 24 is a characteristic diagram showing the growth characteristics of carbon nanotubes in the carbon nanotube production method using the CoZTi catalyst according to the present invention.

FIG. 25 is a schematic cross-sectional view for explaining a field emission electron source and FED manufacturing process by a carbon nanotube manufacturing method using a CoZTi catalyst according to the present invention.

Explanation of symbols

2 Glass substrate

4 Mask

5 Open surface

6 Catalyst body

8 Catalyst

8a 1st catalyst

8b Second catalyst 10 Gas transport pipe

12 Carbonized heater

14 Carbonization chamber

20 Gas transport pipe

22 Preheater heater

22a First preheater

22b Second preheater

26 Reaction heater

30 valves

32 Exhaust pipe

34 oil

50 glass substrate

51 Glass substrate

52 Force sword electrode membrane

53 Anode electrode

53a Phosphor layer

54 Insulation layer

55 Gate electrode

56 carbon nanotubes

57 Through hole

58 Field emission electron source

59 FED

h First catalyst thickness

H Second catalyst thickness

BEST MODE FOR CARRYING OUT THE INVENTION

[0039] Hereinafter, a carbon nanotube production method according to the present invention, a FED production method using the carbon nanotube production method, and an embodiment of the FED produced thereby will be described in detail with reference to the drawings.

FIG. 1 illustrates an example of a method for producing an FeZAl catalyst or a CoZTi catalyst according to the present invention. It is process drawing. In (1A), a mask 4 is placed on the upper surface of the glass substrate 2 and A1 or Ti is evaporated. As a result, an A1 or Ti metal film is formed on the open surface 5. In (1B), Fe or Co is vapor-deposited thereon, and a second metal film is formed on the metal film. In this embodiment, in FeZAl, the lower metal film is A1, and the upper metal film is Fe. In CoZTi, the lower metal film is Ti and the upper metal film is Co. This upside down may be reversed

[0041] In (1C), the catalyst body 6 in which the catalyst 8 is formed as a double film on the glass substrate 2 is completed. In this example, the catalyst membrane width was designed to be 2 mm and the depth was 10 mm. In (1D), a cross section of the main part of the catalyst body 6 is shown. A first catalyst 8a (A1 or Ti) and a second catalyst (Fe or Co) are laminated on the upper surface of the glass substrate 2. The first catalyst thickness h and the second catalyst thickness H are preferably adjusted to a range of 0.1 to 15 nm, more preferably 0.3 to 7 nm.

FIG. 2 is a configuration diagram of a two-way catalyst carbonization apparatus used in the present embodiment. The gas transport pipe 10 is made of a heat-resistant quartz tube, and a carbonized heater 12 is disposed on the outer periphery thereof, and a carbonized chamber 14 is formed on the inner side. A catalyst body 6 is arranged in the carbonization chamber 14, and the catalyst 8 is configured to be exposed to the raw material gas.

[0043] The carrier gas is a gas that feeds the raw material gas, and examples of the carrier gas include He, Ar, and N.

2 Inert gas is used. The source gas is a carbon supply gas for growing carbon nanotubes, and is suitable because hydrocarbon gas does not contain unnecessary elements. C H, CH, C

2 2 4

Anolecan such as H, alkyne, and anoleken are used. Carrier gas and raw material gas

twenty four

Is not limited to the above, and all gases having a function of growing carbon nanotubes can be used. The carbonization temperature is preferably 550 ° C or less, but can be set freely to a temperature at which carbonization occurs effectively. In this embodiment, the carbonization temperature is adjusted to 450 ° C, 500 ° C, and 550 ° C, the He flow rate is adjusted to 230 sccm, the CH flow rate is adjusted to 30 sccm, and the carbonization time is adjusted to 30 minutes.

twenty two

It was.

FIG. 3 is a schematic configuration diagram of a carbon nanotube production apparatus according to the present invention. A carbon nanotube synthesis test was conducted using the carbonized CoZTi catalyst or FeZAl catalyst. The gas transport pipe 20 is divided into a preheating chamber A and a reaction chamber B in the former stage. The preheating chamber A is heated by the first preheating heater 22a and the second preheating heater 22b. This implementation Although the preheating chamber A is divided into two in the form, it may be configured in one stage, so that the first preheating heater 22a and the second preheating heater 22b can be combined by the preheating heater 22.

[0045] The reaction chamber B is heated by the reaction heater 26, and the catalyst body 6 is disposed in the reaction chamber B. The furnace wall temperatures in preheating chamber A and reaction chamber B are measured by three temperature sensors 28. Via the valve 30, a source gas (C H) and a carrier gas (He) are supplied in the direction of arrow a. C H flow

The amount of 2 2 2 2 was set to 60 sccm, and the flow rate of He was set to 200 sccm.

[0046] The furnace wall temperature in the preheating chamber A was adjusted to 700 ° C, and the furnace wall temperature in the reaction chamber B was adjusted to 550 ° C. In the preheating chamber A, the raw material gas is heated to increase the gas activity. The furnace wall temperature is 700 ° C. 1S When the temperature exceeds 100 ° C, the reactivity with the catalyst increases and the efficiency of decomposition of the raw material gas increases, so the gas temperature of the raw material gas itself reaches 100 ° C or higher. In order to form such an environment, it is recommended to set the furnace wall temperature between 200 ° C and 1000 ° C according to the thermal conductivity of the furnace wall. The reaction chamber B is set to a low temperature of 550 ° C., and is configured so as to realize low-temperature synthesis of carbon nanotubes without softening the glass substrate 2. The supply time of source gas was set to 10 minutes. The exhaust gas is published from the exhaust pipe 32 into the oil 34 and discharged in the direction of arrow b.

FIG. 4 is an SEM image of carbon nanotubes grown at 550 ° C. using a CoZTi catalyst without carbonization. The first catalyst thickness h (Ti) was set to 4 nm, and the second catalyst thickness H (Co) was also set to 4 nm. Carbon nanotubes are produced using the equipment shown in Fig. 3, and the gas is preheated at 700 ° C. With the CoZTi catalyst, carbon nanotubes could be vertically grown at high density without carbonization.

[0048] FIG. 5 is an AFM image of a CoZTi catalyst carbonized at 500 ° C. It was confirmed that the CoZTi catalyst was made into particles by carbonization. Next, a carbon nanotube synthesis test was performed using the carbonized CoZTi catalyst with the apparatus shown in FIG.

[0049] Fig. 6 is an SEM image of carbon nanotubes grown with a CoZTi catalyst carbonized at 500 ° C. The growth conditions are the same as described in FIG. It was found that amorphous carbon was deposited on the front end surface of the carbon nanotube. However, it has been demonstrated that carbon nanotubes can grow vertically at a high density to produce brush-like carbon nanotubes. [0050] In order to oxidize the amorphous carbon, the catalyst substrate was thermally oxidized at 600 ° C for 1 minute in the atmosphere. As a result, it was found that amorphous carbon was removed and high-purity, single-bonn nanotubes could be produced.

[0051] Figure 7 shows the FE-SEM and AFM images of the FeZAl catalyst carbonized at 450 ° C. The FE-SEM image shown in (7A) is a field emission scanning electron microscope image, and the AFM image is an atomic force microscope image. The surface of the catalyst is made fine by carbonization, and the FE-SEM image power in the left figure is understood. (7B) is an AFM image, and a cross-sectional view of the straight line is shown on the lower side. In the embodiment of the FeZAl catalyst, both the first catalyst thickness h and the second catalyst thickness H are designed to be 4 nm.

[0052] Figure 8 shows the FE-SEM and AFM images of the FeZAl catalyst carbonized at 500 ° C. It can be clearly understood that the catalyst surface is finely divided by the carbonization treatment. (8A) is an FE-S EM image, (8B) is an AFM image, and a cross-sectional view of the straight line is shown on the lower side. Compared with Fig. 7, it can be seen that the diameter and height of the particles are increasing because the carbonization temperature is 50 ° C higher.

[0053] Fig. 9 is a particle distribution diagram of the FeZAl catalyst that has been carbonized at 450 ° C and 500 ° C. The horizontal axis indicates the particle size (Size), and the vertical axis indicates the number of particles (Number). (9A) is a particle distribution map at 450 ° C, with 12 nm being the approximate median value. (9B) is a particle distribution map at 500 ° C, with 18nm being the approximate median value. It can be understood that as the carbonization temperature increases, the particle height increases and the force tends to be uniform in particle size.

FIG. 10 is an SEM image of carbon nanotubes grown at 550 ° C. using a carbonized FeZAl catalyst. (10A) shows a vertically grown carbon nanotube immediately after synthesis. It can be seen that amorphous carbon is deposited on the surface and part of the tip of the carbon nanotube. The perpendicularity grows with high force and high density, and it was demonstrated that the present invention can produce brush-like carbon nanotubes.

[0055] (10B) is an SEM image of carbon nanotubes of (10A) thermally oxidized at 600 ° C in the atmosphere. When the catalyst of carbon nanotube growth (10A) was heated in the atmosphere at 600 ° C for 1 minute, the amorphous component was oxidized and removed, and high purity carbon nanotubes could be realized. Therefore, it has been found that amorphous components can be removed by hot acid. It was.

FIG. 11 is an SEM image of carbon nanotubes grown at 550 ° C. using an FeZAl catalyst not subjected to carbonization. Manufactured by the equipment shown in Fig. 3, the gas is preheated at 700 ° C. However, carbon nanotubes have grown in all directions and have a low vertical growth potential. For FeZAl catalysts, it has been demonstrated that vertical growth is significantly improved by carbonization.

[0057] The above facts also contributed to the following. The FeZAl catalyst can produce brush-like carbon nanotubes when carbonized, and can produce carbon nanotubes that are not brush-like when not carbonized. With a CoZTi catalyst, brush-like carbon nanotubes can be produced with or without carbonization. In addition, when an amorphous force is deposited, amorphous carbon can be removed by thermal oxidation.

FIG. 12 is a Raman spectroscopic diagram of the produced carbon nanotube. The horizontal axis is Raman shift, and the vertical axis is intensity in arbitrary units. The solid line is a Raman spectrograph of carbon nanotubes preheated at 550 ° C with carbonized FeZAl catalyst, and the long dashed line is the carbon nanotubes preheated at 550 ° C with non-carbonized CoZTi catalyst. The Raman spectrograph and the short dashed line are the Raman spectrographs of carbon nanotubes grown at 700 ° C with Fe catalyst for comparison.

[0059] The ratio (GZD ratio) of Gband (about 1600cm-), which shows the crystallinity of graphite, to Dband (about 1350cm-1), which is the peak of amorphous carbon, is 1.15 for the solid line and 1.37 for the long dashed line. The short dashed line was 1.26. The carbon nanotubes (solid line and long broken line) according to the catalyst of the present invention are not so different from the carbon nanotubes (short broken line) with the normal Fe catalyst, and it is proved that the method of the present invention is effective for the production method of brush-like carbon nanotubes. It was.

Next, the present inventors use the carbon nanotube production apparatus of FIG. 3 for the ease of control over the growth conditions relating to the length and the like of the produced carbon nanotubes in the carbon nanotube production method using the CoZTi catalyst. And verified.

[0061] First, in order to verify the dependency of the film thickness H (h) when forming a CoZTi catalyst film, four types (0.5 nm of each film thickness (HZh) of the CoZTi catalyst film in the catalyst medium 6 are used. /0.5nm, lnm Zlnm, 2nmZ2nm, 4nmZ4nm). The production conditions of the carbon nanotube production equipment are as follows: CH flow rate of source gas is 30sccm, He flow rate of carrier gas is 230sccm

twenty two

The furnace wall temperature in reaction chamber B was adjusted to 550 ° C, and the preheat treatment in preheating chamber A was performed at a furnace wall temperature of 700 ° C. Figures 13 to 16 show the results of synthesizing a single-bonn nanotube by supplying a source gas in reaction chamber B for 5 minutes under these experimental conditions. Figures 13 to 16 show SEM of synthetic carbon nanotubes corresponding to the setting conditions of CoZTi catalyst film thickness (HZh) force 0.5nm / 0.5nm, lnm / lnm, 2nm mZ2nm, 4nmZ4nm, respectively. It is a statue. Under the setting conditions in Fig. 13, the average length of the total length (height) of the synthetic carbon nanotube is about 12 / zm. Similarly, in the case of Fig. 14, Fig. 15, and Fig. 16, about 7 / zm and about 4 respectively. m, about 3 m. From these results, the length of the carbon nanotube is increased to several micron force to several tens of microns by reducing the film thickness H, h of the catalyst CoZTi from 4 nm to 2 nm, lnm, and 0.5 nm. The strength and vertical orientation are improved by reducing the strength and the amorphous component. Therefore, in the carbon nanotube production method using CoZTi catalyst, as shown in (24A) of Fig. 24, the average total length L of the synthetic carbon nanotubes is dependent on the film thickness H (h). It was found that the conditions for adjusting the thickness of the catalyst film can be a control factor for controlling the growth of carbon nanotubes. In this experiment, the Co film thickness H and the Ti film thickness h were set to be the same, but they may be substantially the same level.

In addition, the dependence when the film thickness of each film of the CoZTi catalyst film was changed was also verified. The growth conditions were the same as the setting conditions described above, and the thickness h of the Ti catalyst was set to lOnm, and the thickness H of the Co catalyst was changed to two types (lnm and 4nm). The same applies to the preheating of the raw material gas with the furnace wall temperature in the preheating chamber A set to 700 ° C. The experimental condition results are shown in FIG. 17 and FIG. Fig. 17 is an SEM image of carbon nanotubes grown when the Co film thickness is In m, and Fig. 18 is an SEM image of carbon nanotubes grown when the film thickness is 4 nm. In the case of Fig. 17, the average measurement length of the total length (height) of the synthetic carbon nanotube is about 2 _m , whereas in the case of Fig. 18, it is about. Therefore, in the carbon nanotube production method using a CoZTi catalyst, as shown in FIG. 24 (24C), the total length L of the synthetic carbon nanotube is recognized to be dependent on the Co catalyst film thickness H. The condition for adjusting the film thickness is carbon It has also become a component that can be a control factor for controlling the growth of carbon nanotubes.

[0063] Next, the influence on the growth of carbon nanotubes by the presence or absence of source gas preheating was verified. In this experiment, the thickness (HZh) of the CoZTi catalyst film in the catalyst body 6 was set to a constant value of 0.5 nm / 0.5 nm, and the case where the preheat treatment in the preheating chamber A was not performed was performed. In preheating, the furnace wall temperature in preheating chamber A was set to 700 ° C. The production conditions of the carbon nanotube production equipment are as follows.

twenty two

The gas He flow rate was 230 sccm, and the furnace wall temperature in reaction chamber B was adjusted to 450 ° C, 500 ° C, and 550 ° C.

[0064] The results of carbon nanotube synthesis for 5 minutes in the reaction chamber B under these experimental conditions are shown in FIGS. 19 to 23 and FIG. Figures 19 to 21 show the case where the preheat treatment in the preheating chamber A is not performed, and the furnace wall temperatures in the reaction chamber B are 450 ° C (Fig. 19), 500 ° C (Fig. 20), and 550 °, respectively. This is an SEM image of a synthetic carbon nanotube corresponding to the setting condition of C (Fig. 21). Figures 22, 23, and 13 show the case where preheat treatment was performed in preheating chamber A, and the furnace wall temperatures in reaction chamber B were 450 ° C (Fig. 22), 500 ° C (Fig. 23), and 550, respectively. This is an SEM image of a synthetic carbon nanotube corresponding to the setting condition of ° C (Fig. 13). Under the setting conditions in Fig. 19, the total measured length (height) of synthetic carbon nanotubes is about 0.8 m. Similarly, in Fig. 20 and Fig. 21, about 2.6 m and about 5. 5 μm. In Fig. 22, Fig. 23 and Fig. 13, they are about 1.2 m, 4.2 m and 12 m, respectively. These results are shown in (24B) of FIG. In the figure, white circles indicate no preheating (corresponding to FIGS. 19 to 21), and black circles indicate preheating (corresponding to FIGS. 22, 23, and 13).

Therefore, in the carbon nanotube production method using a CoZTi catalyst, as shown in FIG. 24 (24B), as the furnace wall temperature T in the reaction chamber B increases to 450 ° C., 500 ° C., and 550 ° C. However, the total length L of the synthetic carbon nanotubes with or without preheating increases, but clearly with or without preheating, the total length L of the synthetic carbon nanotubes grows longer than without the preheating. Dependence on the presence or absence of preheating is recognized, so that the condition of whether or not the source gas is preheated before it contacts the CoZTi catalyst membrane can be a control factor that controls the growth of carbon nanotubes. Tsuta. In particular, with preheating, carbon nanotubes grow longer, improving orientation and quality. It was recognized that It was also confirmed that the furnace wall temperature T in the reaction chamber B, in other words, the temperature inside the reaction chamber, can be a control factor for controlling the growth of carbon nanotubes when using the CoZTi catalyst.

[0066] In addition, an experiment showing that the unillustrated defects on the FeZAl catalyst film can be a control factor for controlling the growth of the carbon nanotubes even though the film thickness of the catalyst film, the presence or absence of preheating, and the temperature of the reaction chamber. The result is obtained. Furthermore, according to experiments in which the supply flow rate of the source gas is changed or the supply time is changed in units of seconds, by reducing the flow rate of the source gas and shortening the supply time of the source gas, It was confirmed that high-quality carbon nanotubes with few amorphous components were synthesized. In particular, the reduction of the raw material gas flow greatly contributes to the reduction of the formation of amorphous components. Therefore, the conditions for adjusting the time for the source gas to contact the Co ZTi catalyst film or the FeZAl catalyst film in seconds and the conditions for adjusting the flow rate of the source gas are control factor groups (condition groups) that control the growth of carbon nanotubes. It was confirmed that it could be one of

From the above verification, in the carbon nanotube production method using the catalyst according to the present invention, the conditions for adjusting the film thickness of the catalyst film, the conditions for adjusting the film thickness of the catalyst film itself, Adjust the conditions for whether or not the source gas is preheated before contacting the membrane, the furnace wall temperature T in the reaction chamber B, in other words, the temperature conditions in the reaction chamber, and the time for the source gas to contact the catalyst membrane The conditions for adjusting the flow rate of the raw material gas can be used as a group of control conditions for controlling the growth of the carbon nanotubes, and at least one of these conditions is employed to increase the growth of the carbon nanotubes. This is a method for producing carbon nanotubes that is easy to control and can be accurately controlled, and that is suitable for production of FEDs and the like.

[0068] A method of manufacturing a field emission electron source for FED by the above-described method of manufacturing a carbon nanotube will be described with reference to FIG.

First, a cathode electrode film 52 such as aluminum is formed on the surface layer of the glass substrate 50 by a film forming apparatus (not shown). After an insulating film and a gate electrode film are formed on the force sword electrode film 52, a through hole 57 is formed in a required portion with respect to the insulating film and the gate electrode film to form an insulating layer 54 and a gate electrode 55. Next, a CoZTi catalyst film was applied in the through-hole 57, and the carbon of FIG. Carbon nanotubes are grown in the reaction chamber B of the carbon nanotube production equipment, using the CoZTi catalyst film as a seed. Thereby, the vertically aligned carbon nanotubes 56 are formed in the through holes 57. As described above, in the present invention, by using a low-temperature catalyst of CoZTi, the synthesis of high-quality carbon nanotubes on the substrate and the length thereof can be controlled to several microns without deformation of the glass substrate. In addition, the vertical carbon nanotube 56 having a predetermined height can be erected at a position where the tip end of the field emission carbon nanotube 56 is lower than the gate electrode 55. As described above, the field emission electron source 58 comprising the force sword electrode film 52, the insulating layer 54, the gate electrode 55, and the carbon nanotube 56 for field emission in the through hole 57 is manufactured on the glass substrate 50. Can do.

[0069] Further, when manufacturing an FED using the field emission electron source 58, first, an anode glass 53 and an anode glass sheet in which a fluorescent material layer 53a is formed on the surface of the anode electrode 53 are formed on a glass substrate 51. Then, the fluorescent material layer 53a and the anode electrode 53 are arranged with an interval e of several tens of microns so as to face the force sword electrode film 52 and the gate electrode 55. As a result, the FED 59 that emits visible light g by the electrons f emitted from the gate electrode 55 and the carbon nanotube 56 colliding with the fluorescent material layer 53a can be obtained. By using the manufacturing method of the single-bonn nanotube according to the present invention, it is possible to control the growth length of carbon nanotubes 56 by the number / zm order that is not accompanied by quality degradation. Source 58 can be formed. Then, a high-performance FED capable of performing high-density light emission using the field emission electron source 58 can be manufactured.

Industrial applicability

[0070] According to the first embodiment of the present invention, since the catalyst for producing carbon nano-nanotubes containing Co element and Ti element or Fe element and A1 element is used, the reactor wall temperature is 550 ° C or lower in the reaction chamber. Carbon nanotubes can be grown substantially vertically on the catalyst with high efficiency. The combined catalyst of Co element and Ti element, Fe element and A1 element was discovered for the first time by the present inventors and succeeded in synthesizing carbon nanotubes for the first time by this combination. When the substrate for the catalyst film in the present invention is a glass substrate, the substrate temperature is adjusted to 550 ° C. or lower, and the glass substrate does not soften. Therefore, the glass substrate on which the carbon nanotubes produced by this method are grown remains as it is. It can be used as an electron source for FED. Of course, when the substrate is a heat-resistant substrate, carbon nanotubes that can be adjusted to a desired temperature of 550 ° C. or higher can be grown with high efficiency. Alternatively, according to the present embodiment, the conditions for adjusting the thickness of the catalyst film, the conditions for whether or not the source gas is preheated before the source gas contacts the catalyst film, and the temperature of the reaction chamber are adjusted. Since the growth of carbon nanotubes is controlled by adopting at least one of the conditional force groups, the growth conditions such as the quality, length and density of carbon nanotubes can be controlled accurately, and field emission It is possible to provide a manufacturing method suitable for manufacturing an FED without an electron source.

[0071] According to the second aspect of the present invention, the length of the carbon nanotube after growth is adjusted according to the condition for adjusting the time for the source gas to contact the catalyst film and the condition for adjusting the flow rate of Z or the source gas. In addition to controlling the length (full length), it is possible to significantly reduce the amorphous component, and it is possible to provide a method for producing carbon nanotubes using a catalyst suitable for mass production of field emission electron sources or FEDs.

[0072] According to a third aspect of the present invention, in the first or second aspect, the catalyst film is formed by stacking a Co film and a Ti film or an Fe film and an A1 film, By adjusting the thickness of the catalyst film, the thickness of the catalyst film is adjusted. Therefore, in the metal film formation process of CoZTi or FeZAl, the growth conditions of the carbon nanotubes can be controlled with high accuracy by controlling the layer formation and adjusting the film thickness. I can do it. In addition, various PVD methods (physical vapor deposition methods) and CVD methods (chemical vapor deposition methods) such as a vapor deposition method, a sputtering method, and an ion plating method can be used as the metal film lamination method.

[0073] According to the fourth embodiment of the present invention, in the third embodiment, the Co film thickness and the Ti film thickness or the Fe film and the A1 film are set substantially the same, and the film thickness of each metal film is set. Therefore, the growth condition of the carbon nanotube can be controlled with high accuracy by adjusting the film thickness value that can be controlled in the metal film forming process of CoZTi or FeZAl.

[0074] According to the fifth aspect of the present invention, in the first or second aspect, the preheating temperature of the raw material gas is adjusted as a furnace wall temperature in the range of 200 ° C to 1000 ° C. The raw material gas having a preheating temperature set to a gas temperature of at least 100 ° C. or more can be supplied to the reaction chamber, and carbon nanotubes can be efficiently grown on the catalyst. The growth conditions of carbon nanotubes by a catalyst can be easily controlled by the furnace wall temperature, and there can be provided a carbon nanotube production method suitable for industrial production of FED without a field emission electron source.

[0075] According to the sixth aspect of the present invention, in the first or second aspect, the temperature of the reaction chamber is adjusted to a range below the glass soft spot as the furnace wall temperature. The raw material gas is supplied to the chamber so that the carbon nanotubes can be efficiently grown on the catalyst, and the growth conditions of the carbon nanotubes by the catalyst can be easily controlled by the furnace wall temperature. In addition, it is possible to provide a method for producing a carbon nanotube suitable for industrial production of FED. The glass soft spot is a temperature at which glass is softened by heating, and is preferably 550 ° C. or lower, for example. Further, the lower limit temperature can be freely set within this range as long as it is a temperature at which the carbon nanotube grows by the catalyst.

[0076] According to the seventh aspect of the present invention, there is provided a catalyst for producing carbon nano-nanotubes containing the element as an alloy. Therefore, Fe and Al, or Co and Ti are uniformly mixed and Bonn nanotubes can be uniformly and densely grown.

[0077] According to an eighth aspect of the present invention, there is provided a carbon nanotube manufacturing catalyst containing each of the elements as a metal compound. As the metal compound, various compounds such as metal oxides, metal nitrides, and organometallic compounds can be used. Therefore, there is an advantage that the target catalyst can be freely prepared by a known chemical formulation.

[0078] According to a ninth aspect of the present invention, in the first to eighth aspects, the catalyst for carbon nanotube production is obtained by carbonizing the catalyst. When the catalyst surface is carbonized, particulate carbides are formed, and carbon nanotubes can be efficiently grown by the carbide catalyst. Therefore, low temperature synthesis below 550 ° C can be realized efficiently.

[0079] According to the tenth aspect of the present invention, field emission can be achieved simply by growing carbon nanotubes in the through-holes using the catalyst and stopping the growth so that the tips of the carbon nanotubes exist in the through-holes. An electron source can be configured. Since the tip of the carbon nanotube is located at a lower position than the gate electrode film, the electron current (current) emitted from the tip of the carbon nanotube can be adjusted by changing the gate voltage, and an effective field emission electron source. Can provide. In particular, the CoZTi catalyst and the FeZAl catalyst have the advantage that a carbon nanotube can be grown at a low temperature below the softening point of the glass layer, so that a high-performance field emission electron source without any structural deformation of the glass layer can be provided.

[0080] According to the eleventh aspect of the present invention, the field emission electron source before growing the carbon nanotubes in the tenth aspect is arranged in the reaction chamber to expose the catalyst film in the reaction chamber, and this catalyst A method of growing a carbon nanotube by bringing a film into contact with a source gas under heating, wherein the source gas is preheated at a stage before adjusting the film thickness of the catalyst film and before the source gas contacts the catalyst film. The tip of the carbon nanotube after growth can be present in the through-hole only by adopting at least one of the condition group that also has the condition force that adjusts the temperature of the reaction chamber and the condition that the temperature of the reaction chamber is adjusted. It becomes possible. Therefore, the tip of the carbon nanotube can be easily present at an arbitrary position lower than the position of the gate electrode film, and the intensity of the field-emission electron current can be freely adjusted by the gate voltage. There is an advantage that a field emission electron source can be manufactured.

[0081] According to the twelfth aspect of the present invention, the field emission electron source of the seventh aspect is disposed, the anode electrode is disposed opposite to the gate electrode film, and the fluorescent material is disposed on the anode electrode side. Simply forming the layers can provide a high-performance field emission display (FED). The total length of the grown carbon nanotubes can be adjusted as much as possible by forming high-quality carbon nanotubes with the above-mentioned catalyst. Can provide a display.

Claims

The scope of the claims

[1] A CoZTi catalyst film containing at least Co element and Ti element or a FeZAl catalyst film containing at least Fe element and A1 element is formed on a substrate, and the catalyst film is disposed in a reaction chamber to provide a raw material gas. In which carbon nanotubes are produced by contacting them under heating, the conditions for adjusting the film thickness of the catalyst film, and the conditions for whether or not the source gas is preheated before the source gas contacts the catalyst film And a method for producing carbon nanotubes using a catalyst, wherein the growth of carbon nanotubes is controlled by adopting at least one of a group consisting of conditions for adjusting the temperature of the reaction chamber.

[2] The carbon nanotube by the catalyst according to claim 1, wherein the condition for adjusting the time for the source gas to contact the catalyst film and the condition for adjusting the flow rate of Z or the source gas are added to the condition group. Manufacturing method.

[3] The catalyst film according to claim 1 or 2, wherein the catalyst film is configured by laminating metal films of the respective elements, and the film thickness of the catalyst film is adjusted by adjusting the film thickness of each metal film. A method for producing carbon nanotubes using a catalyst.

4. The method for producing carbon nanotubes using a catalyst according to claim 3, wherein the film thickness of each element is set to be substantially the same, and the film thickness is adjusted.

[5] The method for producing carbon nanotubes using the catalyst according to [1] or [2], wherein a range force of 200 ° C. to 1000 ° C. is adjusted as the furnace wall temperature at which the preheating temperature of the source gas is adjusted.

6. The method for producing carbon nanotubes using a catalyst according to claim 1 or 2, wherein the temperature of the reaction chamber is adjusted to a range below the glass softening point as a furnace wall temperature.

7. The method for producing carbon nanotubes using a catalyst according to claim 1, wherein the catalyst film contains the elements as an alloy.

8. The method for producing carbon nanotubes using a catalyst according to claim 1 or 2, wherein the catalyst film contains each element as a metal compound.

[9] The method for producing a single-bonn nanotube by the catalyst according to any one of [1] to [8], wherein the catalyst film is carbonized.

[10] A force sword electrode film is formed on the glass layer, an insulating layer having a through hole formed in a required portion is disposed on the force sword electrode film, and a carbon nanotube for field emission is disposed in the through hole. , In a field emission electron source in which a gate electrode film is formed on the insulating layer, a CoZTi catalyst containing at least Co element and Ti element or an FeZAl catalyst containing at least Fe element and A1 element on the electrode film in the through hole. And a carbon nanotube is formed in the through-hole by the catalyst, and a tip of the carbon nanotube is present in the through-hole.

[11] A force sword electrode film is formed on the glass layer, an insulating layer having a through hole formed in a required portion is disposed on the force sword electrode film, and a carbon nanotube for field emission is disposed in the through hole. In a field emission electron source in which a gate electrode film is formed on the insulating layer, a CoZTi catalyst film containing at least Co element and Ti element or FeZAl containing at least Fe element and A1 element on the electrode film in the through hole. A method of growing a carbon nanotube by placing a catalyst film, exposing the catalyst film in a reaction chamber and bringing it into contact with a raw material gas under heating, the conditions for adjusting the film thickness of the CoZTi catalyst film, At least one of a group of conditions including whether or not the raw material gas is preheated in the stage before contacting the catalyst film and the condition for adjusting the temperature of the reaction chamber is adopted, so that the carbon nanocrystals after the growth are used. Chu Producing how the field emission electron source, characterized in that the presence of a tip of the probe in said hole.

[12] The field emission electron source according to claim 10 is disposed, an anode electrode is disposed opposite to the gate electrode film, a fluorescent material layer is formed on the anode electrode side, and the carbon nanotube emits light. A field emission display, wherein emitted electrons collide with the phosphor layer and emit light.