JP2002361599A - Carbon nanotube structure and its manufacturing method, cold cathod field electron emitting element and its manufacturing method, and cold cathod field electron emission displaying device and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cold cathode field electron emitting element with which a carbon nanotube can certainly be fixed onto the underlay and no problem originating from the material used to make fixation is likely to be generated. SOLUTION: The cold cathode field electron emitting element is composed of a cathode electrode 11 formed on a support 10 and an electron emission part 15 provided on the cathode electrode, wherein the electron emission part 15 is structured so that carbon nanotube 20 is fixed onto the cathode electrode 11 using diamond-form amorphous carbon 21 as a binder material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carbon nanotube structure and a method of manufacturing the same, a cold cathode field emission device and a method of manufacturing the same, and a cold cathode field emission display and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, a carbon crystal having a tube structure called a carbon nanotube and wound with a carbon graphite sheet has been discovered. This carbon nanotube has a diameter of about 0.7 nm to 30 nm and has a structure in which a single-layer carbon graphite sheet is wound and a structure in which two or more layers of carbon graphite sheets are wound. Multi-walled carbon nanotubes are known. Such a nano-sized crystal having a tube structure is regarded as a unique substance unlike any other. Furthermore, carbon nanotubes have properties that can be both semiconductors and conductors depending on how the carbon graphite sheet is wound, and their unique properties are expected to be applied to electronic and electrical devices.

[0003] When an electric field having a strength exceeding a certain threshold is applied to a metal or semiconductor placed in a vacuum, electrons pass through an energy barrier near the surface of the metal or semiconductor due to the quantum tunnel effect. Electrons are emitted to Electron emission based on such a principle is called cold cathode field emission, or simply field emission (field emission). 2. Description of the Related Art In recent years, a flat-type cold-cathode field-emission display device that applies the principle of field emission to image display, a so-called field emission display (FED), has advantages such as high brightness and low power consumption. Therefore, it is expected as an image display device which replaces a conventional cathode ray tube (CRT).

[0004] Such a cold cathode field emission device or cold cathode field emission display is one of the fields where the application of carbon nanotubes is most expected. That is,
Carbon nanotubes have a lower threshold electric field and higher electron emission efficiency than refractory metals, and are used as an element in the cold cathode field emission device of the cold cathode field emission display device. Excellent material. The active matrix of a transistor is also one of the fields where the application of carbon nanotubes is expected.
That is, by applying the carbon nanotube to an active matrix, which is a passage of electrons in the transistor, a transistor with smaller size and lower power consumption can be obtained.

[0005] At present, carbon nanotubes are classified into a thin film produced by a chemical vapor deposition (CVD) method and a powder produced by an arc method or a laser ablation method. In particular, a large-scale synthesis method of powdered carbon nanotubes has been established, and its application is particularly expected.

[0006]

However, it can be said that an appropriate technique has been established for fixing powdery carbon nanotubes on a base (for example, on a cathode electrode constituting a cold cathode field emission device). hard. Conventionally, organic binder materials such as epoxy resins and inorganic binder materials such as water glass have been used to fix the powdered carbon nanotubes on the base. However, when the base material is heat-treated after fixing the carbon nanotubes on the base material,
There is a problem that it is decomposed and its fixing force is significantly reduced. In addition, the inorganic binder material has a problem that a gas is generated in a baking process or the like, which causes deterioration of characteristics of the carbon nanotube.

When these binder materials are used, a substance adsorbed on the surface of the carbon nanotube becomes a problem. That is, when an organic binder material or an inorganic binder material is used, the constituent components of these binder materials are adsorbed on the surface of the carbon nanotube.
By the way, the electrons in the carbon nanotube tend to move in the axial direction (z-axis direction) of the tube structure, and in particular, move in the outermost region of the carbon nanotube. When different types of adsorbed substances are present on the surface of the carbon nanotube, the crystallinity of the portion of the carbon nanotube, which is the path of electrons, changes, or the bonding state of atoms in such a portion changes, resulting in electrical characteristics. Changes occur. As a result, undesirable phenomena such as generation of noise, decrease in electron mobility, and change in electric resistance value occur. That is, noise is generated when the carbon nanotube is applied to the transistor, and the field emission current becomes unstable when the carbon nanotube is applied to the cold cathode field emission device. Such a problem occurs not only in the powdery carbon nanotubes but also in the thin film carbon nanotubes manufactured by the CVD method.

Accordingly, it is an object of the present invention to provide a carbon nanotube structure in which a carbon nanotube is securely fixed on a substrate, and in which a problem due to a material used for fixing is unlikely to occur, a method of manufacturing the same, and a method of manufacturing the carbon nanotube. It is an object of the present invention to provide a cold cathode field emission device using a nanotube structure and a method of manufacturing the same, a cold cathode field emission display incorporating the cold cathode field emission device, and a method of manufacturing the same.

[0009]

In order to achieve the above object, a carbon nanotube structure of the present invention has a structure in which carbon nanotubes are fixed on a substrate using diamond-like amorphous carbon as a binder material. It is characterized by.

In order to achieve the above object, a method for producing a carbon nanotube structure according to the present invention comprises: (a) disposing a carbon nanotube on a substrate; and (b) providing a carbon nanotube on the substrate and the carbon nanotube. Diamond-like amorphous carbon is deposited as a binder material,
And fixing the carbon nanotubes on the substrate.

According to the carbon nanotube structure of the present invention or the method of manufacturing the same, an electron emission portion of a cold cathode field emission device, an electron beam source in an electron gun incorporated in a cathode ray tube, a passage of electrons in a fluorescent display tube, and a transistor. Thus, a transistor in which carbon nanotubes are applied to an active matrix can be obtained.

The first object of the present invention for achieving the above object is as follows.
The cold cathode field emission device according to the aspect of the present invention is a cold cathode field emission device comprising (A) a cathode electrode provided on a support, and (B) an electron emission portion provided on the cathode electrode. The electron emission portion is characterized in that carbon nanotubes are fixed on the cathode electrode using diamond-like amorphous carbon as a binder material.

The first object of the present invention for achieving the above object is as follows.
In the cold cathode field emission display according to the aspect, the cathode panel provided with a plurality of cold cathode field emission elements, and the anode panel including the phosphor layer and the anode electrode are joined at their peripheral portions. A so-called two-electrode cold cathode field emission display device, comprising: (A) a cathode electrode provided on a support; and (B) a cathode electrode provided on the cathode electrode. Wherein the carbon nanotubes are fixed on the cathode electrode using diamond-like amorphous carbon as a binder material.

The second object of the present invention to achieve the above object.
The cold cathode field emission device according to the aspect of the present invention is characterized in that (A) a cathode electrode provided on a support, (B) an electron emission portion provided on the cathode electrode, and (C) an electron emission portion above the electron emission portion. The electron emission portion is provided with a gate electrode having an opening, and the electron emission portion is characterized in that carbon nanotubes are fixed on the cathode electrode using diamond-like amorphous carbon as a binder material.

The second object of the present invention for achieving the above object.
In the cold cathode field emission display according to the aspect, the cathode panel provided with a plurality of cold cathode field emission elements, and the anode panel including the phosphor layer and the anode electrode are joined at their peripheral portions. A so-called three-electrode cold cathode field emission display device, comprising: (A) a cathode electrode provided on a support; and (B) a cathode electrode provided on the cathode electrode. An electron emitting portion,
(C) a gate electrode provided above the electron-emitting portion and having an opening, wherein the electron-emitting portion has a carbon nanotube fixed on the cathode electrode using diamond-like amorphous carbon as a binder material. It is characterized by comprising.

In the cold cathode field emission device according to the second aspect of the present invention or the cold cathode field emission device in the cold cathode field emission display device, an insulating layer is formed on the support and the cathode electrode. A gate electrode is formed on the insulating layer, a second opening communicating with the opening provided in the gate electrode is formed in the insulating layer, and an electron emitting portion is formed at the bottom of the second opening. May be exposed. Note that such a configuration is referred to as a cold cathode field emission device having the first structure for convenience.

Alternatively, in the cold cathode field emission device or the cold cathode field emission device in the cold cathode field emission display according to the second aspect of the present invention, a strip-shaped or cross-girder-shaped insulating material is used. A gate electrode supporting portion is formed on a support, and a gate electrode made of a strip-shaped material having a plurality of openings formed thereon is in contact with a top surface of the gate electrode supporting portion and above an electron emitting portion. It can also be a structure that is stretched so that is located. Incidentally, such a configuration is referred to as a cold cathode field emission device having the second structure for convenience.

The first object of the present invention for achieving the above object is as follows.
The method of manufacturing a cold cathode field emission device according to the aspect of
A method of manufacturing a cold cathode field emission device comprising (A) a cathode electrode provided on a support, and (B) an electron emission portion provided on the cathode electrode, wherein the electron emission portion is:
(A) arranging carbon nanotubes on a desired region of the cathode electrode; and (b) depositing diamond-like amorphous carbon as a binder material on the cathode electrode and the carbon nanotubes. Fixing the carbon nanotube on a desired area.

The first object of the present invention for achieving the above object is as follows.
The method for manufacturing a cold cathode field emission display according to the aspect of the present invention comprises: a cathode panel provided with a plurality of cold cathode field emission devices; and an anode panel including a phosphor layer and an anode electrode. A cold cathode field emission display device of a so-called two-electrode type, comprising: (A) a cathode electrode provided on a support; and (B) a cold cathode field emission device. An electron emitting portion provided on the cathode electrode, wherein the electron emitting portion is formed by: (a) disposing the carbon nanotube on a desired region of the cathode electrode; and (b) forming the carbon nanotube on the cathode electrode and the carbon nanotube. Depositing diamond-like amorphous carbon as a binder material and fixing carbon nanotubes on the desired region of the cathode electrode. And wherein the Rukoto.

In the method for manufacturing a cold cathode field emission device according to the first aspect of the present invention or the method for manufacturing a cold cathode field emission display according to the first aspect, a method for forming an electron emission portion is provided. More specifically, (a) a step of forming a mask layer made of a mask material on a support and a cathode electrode; and (ii) a portion of the mask layer on a region of the cathode electrode where carbon nanotubes are to be formed. (C) arranging carbon nanotubes on the mask layer and the exposed cathode electrode; and (d) depositing diamond-like amorphous carbon on the carbon nanotubes and the exposed cathode electrode. Removing the mask layer and the carbon nanotubes and diamond-like amorphous carbon thereon. When referring to the method of manufacturing is) can be exemplified.

The second object of the present invention for achieving the above object is as follows.
The method of manufacturing a cold cathode field emission device according to the aspect of
(A) a cathode electrode provided on a support, (B) an electron-emitting portion provided on the cathode electrode, and (C) a gate electrode provided above the electron-emitting portion and having an opening. A method of manufacturing a cold cathode field emission device comprising: (a) disposing a carbon nanotube on a desired region of a cathode electrode; and (b) forming an electron emission portion on the cathode electrode and the carbon nanotube. And depositing diamond-like amorphous carbon as a binder material, so that carbon is deposited on the desired region of the cathode electrode.
The method is characterized by being formed by a step of fixing nanotubes.

The second object of the present invention for achieving the above object is as follows.
The method for manufacturing a cold cathode field emission display according to the aspect of the present invention comprises: a cathode panel provided with a plurality of cold cathode field emission devices; and an anode panel including a phosphor layer and an anode electrode. A method of manufacturing a so-called three-electrode type cold cathode field emission display device, wherein the cold cathode field emission device comprises: (A) a cathode electrode provided on a support; An electron emission portion provided on the cathode electrode; and (C) a gate electrode provided above the electron emission portion and having an opening, wherein the electron emission portion is formed on (a) a desired region of the cathode electrode. (B) depositing diamond-like amorphous carbon as a binder material on the cathode electrode and the carbon nanotube,
Fixing the carbon nanotube on the desired region of the cathode electrode.

In the method for manufacturing a cold cathode field emission device according to the second aspect of the present invention or the method for manufacturing a cold cathode field emission display according to the second aspect, a method for forming an electron emission portion is provided. More specifically, (a) an insulating layer is formed on a support and a cathode electrode, a gate electrode having an opening is formed on the insulating layer, and then an opening provided in the gate electrode is formed. Forming a communicating second opening in the insulating layer and exposing the cathode electrode at the bottom of the second opening; and (b) a mask layer having a hole in the center of the second opening. On the cathode electrode, on the side of the second opening,
(C) arranging carbon nanotubes on the mask layer and the exposed cathode electrode; (d) mask layer, carbon nanotubes and exposed Depositing diamond-like amorphous carbon on the formed cathode electrode, and then removing the mask layer and the carbon nanotubes and diamond-like amorphous carbon thereon (hereinafter, may be referred to as a 2A manufacturing method). ).

Alternatively, (a) forming a mask layer made of a mask material on the support and the cathode electrode;
(B) removing a portion of the mask layer on the region of the cathode electrode where carbon nanotubes are to be formed;
Disposing carbon nanotubes on the mask layer and the exposed cathode electrode; and (d) depositing diamond-like amorphous carbon on the mask layer, the carbon nanotubes and the exposed cathode electrode, (E) forming an insulating layer on the entire surface, forming a gate electrode having an opening on the insulating layer, and then removing the opening provided on the gate electrode. Forming a communicating second opening in the insulating layer and exposing the electron-emitting portion at the bottom of the second opening (hereinafter, may be referred to as a 2B manufacturing method). Can be.

The cold cathode field emission device having the first structure can be obtained by the manufacturing methods 2A and 2B.

Alternatively, in the method for manufacturing a cold cathode field emission device according to the second aspect of the present invention or the method for manufacturing a cold cathode field emission display according to the second aspect, Forming a strip-shaped or cross-shaped gate electrode support made of a material on a support, and forming a cathode electrode and an electron emission portion on the support; and (b) a strip having a plurality of openings formed therein. Stretching the band-shaped material such that the gate electrode made of the material is in contact with the top surface of the gate electrode support portion and the opening is located above the electron emission portion (hereinafter referred to as 2C). In some cases). Thus, a cold cathode field emission device having the second structure can be obtained. Note that the cathode electrode and the electron-emitting portion may be basically formed based on the first manufacturing method.

In the manufacturing method 2C, when the gate electrode supporting portion is a region between adjacent stripe-shaped cathode electrodes, or when a plurality of cathode electrodes constitute a group of cathode electrodes, the adjacent cathode electrodes are formed. What is necessary is just to form in the area | region between electrode groups. As a material forming the gate electrode supporting portion, a conventionally known insulating material can be used. For example, a material in which a metal oxide such as alumina is mixed with widely used low melting glass, or an insulating material such as SiO ₂ is used. Materials can be used. Examples of the method for forming the gate electrode supporting portion include a combination of a CVD method and an etching method, a screen printing method, a sandblast method, a dry film method, and a photosensitive method. The dry film method involves laminating a photosensitive film on a support, removing the photosensitive film where the gate electrode support is to be formed by exposure and development, and forming a gate electrode support in the opening created by the removal. Is a method of burying and firing an insulating material for use.
The photosensitive film is burned and removed by baking, and the insulating material for forming the gate electrode support buried in the opening remains to serve as the gate electrode support. The photosensitive method is a method in which an insulating material for forming a gate electrode supporting portion having photosensitivity is formed on a support, and the insulating material is patterned by exposure and development, followed by baking.

The carbon nanotube structure of the present invention or the method of manufacturing the same, the cold cathode field emission device according to the first or second embodiment or the method of manufacturing the same, and the cold cathode field emission device according to the first or second embodiment In a cathode field emission display or a method of manufacturing the same (hereinafter sometimes collectively simply referred to as the present invention), diamond-like amorphous carbon has a wavelength of 514.5 n.
In a Raman spectrum using a laser beam of m, a half-width of 30 cm in a wave number range of 1400 to 1630 cm ^-1 , preferably in a range of 1460 to 1630 cm ^-1.
-1 or more, preferably it is desirable to have a half-value width 50 cm ^-1 or more peaks. When the peak exists on the higher wave number side than 1480 cm ⁻¹ , the wave numbers 1330 to 1400 c
There may be another peak at m ^-1 .

The diamond-like amorphous carbon of the present invention has many sp ³ , which is the same bond as general diamond (specifically, for example, 20 to 90%
Cluster carbon as well as amorphous carbon). As for the cluster carbon, for example, “Generation and deposition of fullerene-andna
notube-rich carbon thin films ", M. Chhowalla, et a
See l., Phil. Mag. Letts, 75 (1997), pp 329-335.

As the method of forming the diamond-like amorphous carbon in the present invention, not only the CVD method but also the cathodic carbon method (for example, the method described in the document "Properties o
f filtered-ion-beam-deposited diamondlike carbon a
sa function of ion energy ", PJ Fallon, et al.,
Phys. Rev. B 48 (1993), pp. 4777-4782), a laser ablation method, a sputtering method, and various other physical vapor deposition methods (PVD methods).
The diamond-like amorphous carbon may contain hydrogen or may be doped with nitrogen, boron, phosphorus, or the like.

The thickness of the diamond-like amorphous carbon is 0.5 nm to 500 nm, preferably 0.5 nm
m to 10 nm is desirable.

The carbon nanotubes in the present invention may be macroscopically in the form of a powder or a thin film, and may be produced by a known arc method, laser ablation method, or CVD method. Can be mentioned. As a method for arranging carbon nanotubes on a substrate or a desired region of a cathode electrode, carbon nanotubes are used.
A method of dispersing nanotubes in an organic solvent, applying the organic solvent on a substrate or a desired region of a cathode electrode, and removing the organic solvent, various spray methods such as a nano spray method and an atomic spray method. can do. The carbon nanotube in the present invention,
For example, it has a tube structure in which a carbon graphite sheet is wound, and has a diameter of about 0.7 nm to 30 nm and a length of about 0.1 μm to 100 μm. Also,
It may be a single-walled carbon nanotube having a structure in which a single-layer carbon graphite sheet is wound, or 2
It may be a multi-walled carbon nanotube having a structure in which a carbon graphite sheet having more than two layers is wound.
It should be noted that the carbon nanotubes in the present specification also include carbon nanofibers. The carbon atom having an sp ² bond usually forms a six-membered ring from six carbon atoms, and a collection of these six-membered rings forms a carbon graphite sheet. What has a tube structure in which the carbon graphite sheet is wound is a carbon nanotube. On the other hand, carbon nanofibers are formed by unwrapping a carbon graphite sheet and overlapping carbon graphite fragments to form a fiber.

Substrate or cold cathode field emission device
Tungsten as a material constituting the cathode electrode in
Ten (W), niobium (Nb), tantalum (Ta), moly
Buden (Mo), chrome (Cr), aluminum (A
l), metals such as copper (Cu); alloys containing these metal elements
Gold or a compound (for example, nitride such as TiN, WSi
_Two, MoSi_Two, TiSi_Two, TaSi_TwoEtc.
Semiconductor) such as silicon (Si); or ITO
(Indium tin oxide). Caso
As a method of forming a cathode electrode, for example, an electron beam evaporation method or
Evaporation method such as hot filament evaporation method, sputtering
Method, CVD method, ion plating method and etching method
, Screen printing method, plating method, lift-off
And the like. Screen printing method and plating
According to the method, directly form a striped cathode electrode
It is possible to

The materials constituting the gate electrode in the cold cathode field emission device having the first structure include tungsten (W), niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum (Mo), and chromium. (Cr), aluminum (Al), copper (Cu), gold (Au), silver (A
g), nickel (Ni), cobalt (Co), zirconium (Zr), iron (Fe), platinum (Pt) and zinc (Z
n) at least one metal selected from the group consisting of: alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , MoSi ₂ , TiSi
₂ , silicide such as TaSi ₂ ); or silicon (S
semiconductors such as i); and conductive metal oxides such as ITO (indium tin oxide), indium oxide, and zinc oxide. To manufacture a gate electrode, a CVD method,
Sputtering, vapor deposition, ion plating,
A thin film made of the above-mentioned constituent material is formed on the insulating layer by a known thin film forming technique such as an electrolytic plating method, an electroless plating method, a screen printing method, a laser ablation method, and a sol-gel method. When a thin film is formed on the entire surface of the insulating layer, the thin film is patterned using a known patterning technique to form a gate electrode in a stripe shape. After the formation of the stripe-shaped gate electrode, an opening may be formed in the gate electrode, or an opening may be formed in the gate electrode at the same time as the formation of the stripe-shaped gate electrode. If a resist pattern is formed in advance on the insulating layer before the formation of the gate electrode conductive material layer, the gate electrode can be formed by a lift-off method. Furthermore, if vapor deposition is performed using a mask having an opening corresponding to the shape of the gate electrode or screen printing is performed using a screen having such an opening, patterning after film formation becomes unnecessary. In addition, a gate electrode can be provided by preparing a band-shaped material having an opening from the above-described materials as appropriate and fixing the band-shaped material on a gate electrode supporting portion. The cold cathode field emission device having the structure described above can be obtained.

In the cold cathode field emission display according to the present invention, the anode panel includes a substrate, a phosphor layer, and an anode electrode. Depending on the structure of the anode panel, the surface to be irradiated with electrons is composed of a phosphor layer, or
It consists of an anode electrode.

The constituent material of the anode electrode may be appropriately selected depending on the structure of the cold cathode field emission display. That is, when the cold cathode field emission display is a transmission type (an anode panel corresponds to a display surface) and an anode electrode and a phosphor layer are laminated on the substrate in this order, the substrate is Originally, the anode electrode itself must be transparent, and a transparent conductive material such as ITO (indium tin oxide) is used. On the other hand, when the cold cathode field emission display is of a reflection type (the cathode panel corresponds to the display surface),
And, when the phosphor layer and the anode electrode are laminated on the substrate in this order even in the transmission type, in addition to ITO,
The materials described above in relation to the cathode electrode and the gate electrode can be appropriately selected and used.

As the phosphor constituting the phosphor layer, a phosphor for high-speed electron excitation or a phosphor for low-speed electron excitation can be used. When the cold cathode field emission display is a monochromatic display, the phosphor layer may not be particularly patterned. When the cold cathode field emission display is a color display, phosphor layers corresponding to the three primary colors of red (R), green (G), and blue (B) patterned in stripes or dots are alternately arranged. It is preferable to arrange them in
The gap between the patterned phosphor layers may be filled with a black matrix for the purpose of improving the contrast of the display screen.

As an example of the configuration of the anode electrode and the phosphor layer,
(1) An anode electrode is formed on a substrate, and a phosphor layer is formed on the anode electrode. (2) A phosphor layer is formed on the substrate, and an anode electrode is formed on the phosphor layer. Configuration. In the configuration of (1), a so-called metal back film that is electrically connected to the anode electrode may be formed on the phosphor layer. In the configuration of (2), a metal back film may be formed on the anode electrode.

It is preferable that the projected image of the striped gate electrode and the projected image of the striped cathode electrode extend in a direction orthogonal to each other, from the viewpoint of simplifying the structure of the cold cathode field emission display. Note that an electron emitting portion (1) is provided in an overlapping area where the projected images of the striped cathode electrode and the striped gate electrode overlap (an electron emitting area, which corresponds to one pixel area or one subpixel area). Or, a plurality of cold cathode field emission devices are provided, and such an overlapping region is usually provided in an effective region (a region functioning as an actual display portion) of the cathode panel.
They are arranged in a dimensional matrix.

In the cold cathode field emission device according to the second aspect of the present invention or the cold cathode field emission device in the cold cathode field emission display device, the opening or the second
The planar shape of the opening (shape when the opening is cut by a virtual plane parallel to the support surface) is circular, elliptical, rectangular,
Any shape such as a polygon, a rounded rectangle, and a rounded polygon can be used. The opening can be formed by, for example, isotropic etching, a combination of anisotropic etching and isotropic etching, or
Depending on the method for forming the gate electrode, the opening can be formed directly. One opening is provided in the gate electrode, and one opening communicates with one opening provided in the gate electrode.
Two second openings may be provided in the insulating layer, one electron emission portion may be provided in the second opening provided in the insulating layer, or a plurality of openings may be provided in the gate electrode, One second opening communicating with a plurality of openings provided in the insulating layer is provided in the insulating layer, and one or a plurality of electron emitting portions are provided in the one second opening provided in the insulating layer. Good.

As the constituent material of the insulating layer, SiO ₂ , Si
N, SiON, SOG (spin-on-glass), low melting point glass, and glass paste can be used alone or in appropriate combination. CVD is used for forming the insulating layer.
Known processes such as a method, a coating method, a sputtering method, and a screen printing method can be used. The formation of the second opening is
For example, it can be performed by isotropic etching, or a combination of anisotropic etching and isotropic etching.

A resistor layer may be provided between the cathode electrode and the electron emission section. By providing the resistor layer, the operation of the cold cathode field emission device can be stabilized and the electron emission characteristics can be made uniform. As a material forming the resistor layer, a carbon-based material such as silicon carbide (SiC), a semiconductor material such as SiN or amorphous silicon,
Examples thereof include high melting point metal oxides such as ruthenium oxide (RuO ₂ ), tantalum oxide, and tantalum nitride. As a method of forming the resistor layer, a sputtering method, a CVD method,
And a screen printing method. The resistance value may be approximately 1 × 10 ⁵ to 1 × 10 ⁷ Ω, preferably several MΩ.

The support constituting the cathode panel or the substrate constituting the anode panel only needs to have at least the surface made of an insulating member. A glass substrate, a glass substrate having an insulating film formed on the surface, a quartz substrate, A quartz substrate having an insulating film formed on its surface and a semiconductor substrate having an insulating film formed on its surface can be given.

When the cathode panel and the anode panel are joined at the peripheral edge, the joining may be performed using an adhesive layer, or a combination of a frame made of an insulating rigid material such as glass or ceramics and the adhesive layer. You may go.
When the frame and the adhesive layer are used together, by appropriately selecting the height of the frame, the facing distance between the cathode panel and the anode panel is set longer than when using only the adhesive layer. It is possible to In addition, as a constituent material of the adhesive layer, frit glass is generally used, but a so-called low melting point metal material having a melting point of about 120 to 400 ° C. may be used. Examples of such low melting point metal materials include In (indium: melting point: 157 ° C.); indium-gold based low melting point alloy; Sn ₈₀ Ag ₂₀ (melting point: 220 to 370 ° C.);
n ₉₅ Cu ₅ (melting point 227 to 370 ° C) such as tin (Sn)
High-temperature solder: Pb _97.5 Ag _2.5 (melting point 304 ° C),
Pb _94.5 Ag _5.5 (melting point 304-365 ° C), Pb
Lead (Pb) such as _97.5 Ag _1.5 Sn _1.0 (melting point 309 ° C)
-Based high-temperature solder; zinc (Zn) -based high-temperature solder such as Zn ₉₅ Al ₅ (melting point 380 ° C.); Sn ₅ Pb ₉₅ (melting point 300 to
314 ° C.), Sn ₂ Pb ₉₈ (melting point 316-322 ° C.), etc .; tin-lead based solder; Au ₈₈ Ga ₁₂ (melting point 38
1 ° C) brazing filler metal (All subscripts above represent atomic%)
Can be exemplified.

When the cathode panel, the anode panel and the frame are joined together, the three may be joined simultaneously,
Alternatively, one of the cathode panel and the anode panel may be joined to the frame in the first stage, and the other of the cathode panel and the anode panel may be joined to the frame in the second stage. If the three-member simultaneous bonding and the bonding in the second stage are performed in a high vacuum atmosphere, the space surrounded by the cathode panel, the anode panel, the frame, and the adhesive layer is evacuated simultaneously with the bonding. Alternatively, after the joining of the three members, the space surrounded by the cathode panel, the anode panel, the frame, and the adhesive layer may be evacuated to a vacuum. When evacuation is performed after the bonding, the pressure of the atmosphere at the time of the bonding may be either normal pressure or reduced pressure. The gas constituting the atmosphere may be air, nitrogen gas, or group 0 of the periodic table. May be an inert gas containing a gas belonging to (for example, Ar gas).

When evacuation is performed after joining, the evacuation can be performed through a chip tube previously connected to the cathode panel and / or the anode panel. The tip tube is typically configured using a glass tube, and has a cathode panel and / or
Alternatively, it is bonded to the periphery of the penetrating portion provided in the ineffective area (the area that does not function as an actual display portion) of the anode panel using frit glass or the above-mentioned low melting point metal material, and the space reaches a predetermined vacuum degree After that, it is sealed off by heat fusion. Note that if the entire cold cathode field emission display is once heated and then cooled before the sealing is performed, the residual gas can be released into the space, and the residual gas can be removed to the outside by exhaust. This is preferable because

In the present invention, since diamond-like amorphous carbon is used as the binder material, the carbon nanotubes can be securely fixed on the substrate or the cathode electrode. In addition, unlike the related art, problems caused by the use of an inorganic binder material such as an organic binder material or water glass are less likely to occur.

[0048]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings based on embodiments of the invention (hereinafter abbreviated as embodiments).

(Embodiment 1) Embodiment 1 is directed to a carbon nanotube structure and a method of manufacturing the same according to the present invention, and a cold cathode field emission device according to the first embodiment (hereinafter abbreviated as field emission device). The present invention also relates to a so-called two-electrode type cold cathode field emission display (hereinafter abbreviated as a display) according to the first aspect and a method of manufacturing the same.

FIG. 1 is a schematic partial cross-sectional view of the display device of the first embodiment, FIG. 2 is a schematic perspective view of one electron-emitting portion, and FIG. A partial cross-sectional view is shown in FIG.

The carbon nanotube structure according to the first embodiment is provided on a substrate (specifically, on the cathode electrode 11 in the first embodiment) on a diamond-like amorphous carbon 21 (DLC 21 in the drawing) as a binder material. The carbon nanotube 20 is fixed by using the following.

The field emission device according to the first embodiment includes a cathode electrode 11 provided on a support 10 and an electron emission portion 15 provided on the cathode electrode 11. The electron emitting section 15 is formed by fixing carbon nanotubes 20 on the cathode electrode 11 using diamond-like amorphous carbon 21 as a binder material. Further, the display device according to the first embodiment includes:
A cathode panel CP provided with a plurality of field emission devices, and an anode panel including a phosphor layer 31 (red light emitting phosphor layer 31R, green light emitting phosphor layer 31G, blue light emitting phosphor layer 31B) and an anode electrode 33. APs are joined at their periphery and have a plurality of pixels. In the cathode panel CP of the display device according to the first embodiment, a large number of electron emission regions formed of a plurality of the above-described field emission devices are formed in a two-dimensional matrix in the effective region.

A through-hole (not shown) for evacuation is provided in an invalid area of the cathode panel CP, and a chip tube (not shown) which is sealed off after evacuation is connected to this through-hole. Have been. The frame body 34 is made of ceramics or glass, and has a height of, for example, 1.0 mm. In some cases, only the adhesive layer may be used instead of the frame 34.

The anode panel AP is, specifically, a substrate 30, a phosphor layer 31 formed on the substrate 30 and formed according to a predetermined pattern (for example, a stripe shape or a dot shape), and the entire surface of the effective area. And an anode electrode 33 made of, for example, an aluminum thin film. A black matrix 32 is formed on the substrate 30 between the phosphor layers 31. Note that the black matrix 32 can be omitted. Further, when a monochrome display device is assumed, the phosphor layer 31 does not necessarily need to be provided according to a predetermined pattern. Furthermore,
An anode electrode made of a transparent conductive film such as ITO
Between the anode and the phosphor layer 31 or the anode electrode 3 made of a transparent conductive film provided on the substrate 30.
3, a phosphor layer 31 and a black matrix 32 formed on the anode electrode 33, and light formed of aluminum formed on the phosphor layer 31 and the black matrix 32 and electrically connected to the anode electrode 33. It can also be composed of a reflective conductive film.

One pixel is arranged on the cathode panel side in a rectangular cathode electrode 11, an electron emitting portion 15 formed thereon, and an effective area of the anode panel AP so as to face the electron emitting portion 15. And a phosphor layer 31. In the effective area, such pixels are arranged, for example, in the order of several hundred thousand to several million.

Further, spacers 35 are arranged between the cathode panel CP and the anode panel AP at equal intervals in the effective area as auxiliary means for maintaining a constant distance between the panels. The shape of the spacer 35 is
The shape is not limited to a columnar shape, and may be, for example, a spherical shape or a stripe-shaped partition wall (rib). Also, the spacer 35
Need not necessarily be arranged at the four corners of the overlapping region of all the cathode electrodes, and may be arranged more sparsely or irregularly.

In this display device, in units of one pixel,
The voltage applied to the cathode electrode 11 is controlled. The planar shape of the cathode electrode 11 is, as schematically shown in FIG.
Each cathode electrode 11 is substantially rectangular, and is connected to a cathode electrode control circuit 40A via a wiring 11A and a switching element (not shown) formed of, for example, a transistor. Further, the anode electrode 33 is connected to an acceleration power supply 42. When a voltage equal to or higher than the threshold voltage is applied to each cathode electrode 11, electrons are emitted from the electron emitting portion 15 based on the electric field formed by the anode electrode 33 and quantum tunnel effect, and the electrons are emitted from the anode electrode 33.
And collides with the phosphor layer 31. The brightness is controlled by a voltage applied to the cathode electrode 11.

Hereinafter, a method for manufacturing the carbon nanotube structure, the field emission device, and the display device according to the first embodiment will be described with reference to FIGS.

[Step-100] First, a conductive material layer for forming a cathode electrode is formed on a support 10 made of, for example, a glass substrate, and then based on a well-known lithography technique and a reactive ion etching method (RIE method). By patterning the conductive material layer, a rectangular cathode electrode 11 is formed on the support 10 (see FIG. 3A). At the same time, the wiring 11 connected to the cathode electrode 11
A (see FIG. 2) is formed on the support 10. The conductive material layer is made of, for example, a chromium (Cr) layer having a thickness of about 0.2 μm formed by a sputtering method.

[Step-110] Next, the cathode electrode 11
The carbon nanotubes 20 are arranged on the surface of a desired region (corresponding to a substrate) (a region where an electron emission portion is to be formed). Specifically, first, after a resist material layer is formed on the entire surface by spin coating, a mask layer 16 in which the surface of the region of the cathode electrode 11 where the electron emission portion is to be formed is exposed is formed based on the lithography technique. Yes ((B) of FIG. 3)
reference). Next, a solution in which carbon nanotubes are dispersed in an organic solvent such as acetone is applied on the mask layer 16 including the exposed surface of the cathode electrode 11 by spin coating, and then the organic solvent is removed (FIG. 3 (C)). Although the carbon nanotubes 20 are shown by circles (circles) for simplification of the drawing, in practice, the carbon nanotubes 20 have, for example, an average diameter of 1 nm to 30 nm and an average length of 0.1 μm to 10 μm. It has a tube structure and is manufactured by an arc discharge method.
The carbon nanotubes 20 may be randomly oriented with respect to the cathode electrode 11 (that is, may be arranged on the cathode electrode 11 in an entangled state, for example), or may be oriented in one direction. .

After the carbon nanotubes 20 are arranged, a heat treatment or various kinds of plasma treatments may be performed to release gas from the carbon nanotubes 20, or the surface of the carbon nanotubes 20 may be intentionally applied. The carbon nanotubes 20 may be exposed to a gas containing a substance to be adsorbed in order to adsorb the adsorbate. In order to purify the carbon nanotubes 20, an oxygen plasma treatment or a fluorine plasma treatment may be performed. The same applies to the following embodiments. In some cases, the mask layer 16 may be removed once, these processes may be performed, and then the mask layer 16 may be formed again.

[Step-120] Then, diamond-like amorphous carbon 21 is deposited as a binder material on the exposed region of the cathode electrode 11 and on the carbon nanotubes 20. As a result, the carbon nanotubes 20 can be fixed on a desired area of the cathode electrode 11 (an area where an electron emission portion is to be formed). Table 1 below shows conditions for forming the diamond-like amorphous carbon 21 (average film thickness: 30 nm) based on the plasma CVD method. Thereafter, by removing the mask layer 16, a field emission device having the structure shown in FIG. 3D can be obtained. Incidentally, the wavelength is 514.5 nm.
In the Raman spectrum using the laser light of the above, the diamond-like amorphous carbon 21 has a wave number of 1460.
The peak had a half-value width of 50 cm ^-1 or more in the range of ¹ to 1630 cm ^-1 . Specifically, in the wave number 1520 cm ^-1, it has a peak half-width 180cm ^-1.

[Table 1] Gas used: CH ₄ = 100 sccm Plasma excitation power: 1 kW Pressure: 0.1 Pa Temperature: room temperature

[Step-130] Thereafter, the display device is assembled. Specifically, the anode panel AP and the cathode panel CP are arranged so that the phosphor layer 31 and the field emission device face each other, and the anode panel AP and the cathode panel CP (more specifically, the substrate 30 and the support 10) are joined at the peripheral portion via the frame 34. At the time of joining, frit glass is applied to a joint portion between the frame body 34 and the anode panel AP and a joint portion between the frame body 34 and the cathode panel CP, and the anode panel AP, the cathode panel CP, and the frame body 34 are bonded to each other. , After drying the frit glass by pre-firing,
Perform main firing for 0 minutes. Thereafter, the space surrounded by the anode panel AP, the cathode panel CP, the frame 34, and the frit glass is evacuated through a through-hole (not shown) and a chip tube (not shown), and the pressure of the space becomes 10 ^-4. Pa
At this point, the tip tube is sealed off by heating and melting. Thus, the space surrounded by the anode panel AP, the cathode panel CP, and the frame 34 can be evacuated. After that, wiring to necessary external circuits is performed to complete the display device.

An example of a method for manufacturing the anode panel AP in the display device shown in FIG. 1 will be described below with reference to FIG.

First, a luminescent crystal particle composition is prepared.
For this purpose, for example, a dispersant is dispersed in pure water, and the mixture is stirred for 1 minute at 3000 rpm using a homomixer. Next, the luminescent crystal particles are put into pure water in which the dispersant is dispersed, and the mixture is stirred at 5000 rpm for 5 minutes using a homomixer. Thereafter, for example, polyvinyl alcohol and ammonium bichromate are added, sufficiently stirred, and filtered.

In the manufacture of the anode panel AP, the photosensitive film 50 is formed on the entire surface of the substrate 30 made of, for example, glass.
Is formed (applied). Then, the photosensitive film 50 formed on the substrate 30 is exposed to ultraviolet rays emitted from an exposure light source (not shown) and passed through the holes 54 provided in the mask 53 to form a photosensitive region 51 ( FIG. 4 (A)
reference). Thereafter, the photosensitive film 50 is selectively removed by developing, and the remaining portion of the photosensitive film (photosensitive film after exposure and development)
52 is left on the substrate 30 (see FIG. 4B). next,
After applying a carbon agent (carbon slurry) to the entire surface, drying and baking, the remaining portion 5 of the photosensitive film is formed by a lift-off method.
By removing the carbon material 2 and the carbon material thereon, a black matrix 32 made of the carbon material is formed on the exposed substrate 30, and at the same time, the remaining portion 52 of the photosensitive film is removed (see FIG. 4C). ). Thereafter, red, green, and blue phosphor layers 31 are formed on the exposed substrate 30 (see FIG. 4D). Specifically, a luminescent crystal particle composition prepared from each luminescent crystal particle (phosphor particle) is used. For example, a red photosensitive luminescent crystal particle composition (phosphor slurry) is applied to the entire surface. Coating, exposing and developing, then applying a green photosensitive luminescent crystal particle composition (phosphor slurry) over the entire surface, exposing and developing, and further, a blue photosensitive luminescent crystal particle composition (Phosphor slurry) may be applied to the entire surface, exposed and developed. Then, the phosphor layer 3
An anode electrode 33 made of an aluminum thin film having a thickness of about 0.07 μm is formed on the black matrix 1 and the black matrix 32 by a sputtering method. Note that the respective phosphor layers 31 can also be formed by a screen printing method or the like.

The anode electrode may be a type in which the effective area is covered with one sheet of conductive material, or may correspond to one or a plurality of electron-emitting portions or one or a plurality of pixels. An anode electrode of a type in which anode electrode units are assembled may be used.

One pixel is constituted by a stripe-shaped cathode electrode, an electron emission portion formed thereon, and a phosphor layer arranged in an effective area of the anode panel so as to face the electron emission portion. Is also good. In this case, the anode electrode also has a stripe shape. The projected image of the striped cathode electrode is orthogonal to the projected image of the striped anode electrode. Electrons are emitted from the electron emission portion located in a region where the projected image of the anode electrode and the projected image of the cathode electrode overlap. The display device having such a configuration is driven by a so-called simple matrix method. That is, a relatively negative voltage is applied to the cathode electrode, and a relatively positive voltage is applied to the anode electrode. As a result, selection is made from the electron emission portion located in the anode electrode / cathode electrode overlap region of the column-selected cathode electrode and the row-selected anode electrode (or the row-selected cathode electrode and the column-selected anode electrode). Electrons are discharged into the vacuum space, and the electrons are attracted to the anode electrode and collide with the phosphor layer forming the anode panel, thereby exciting and emitting light from the phosphor layer.

In manufacturing the field emission device having such a structure, in [Step-100], a cathode electrode made of, for example, a chromium (Cr) layer formed by a sputtering method on a support 10 made of, for example, a glass substrate After forming the conductive material layer for formation, the conductive material layer is patterned based on the well-known lithography technique and RIE method, so that the stripe-shaped cathode electrode 11 is formed on the support 10 instead of the rectangular cathode electrode. It may be formed.

(Embodiment 2) In Embodiment 2, a carbon nanotube structure and a method of manufacturing the same according to the present invention, a field emission device according to a second embodiment, and a method of manufacturing the same (Part 2A)
And a so-called three-electrode display device according to the second aspect and a method for manufacturing the same. The field emission device according to the second embodiment has the first structure.

FIG. 9 is a schematic partial end view of the field emission device according to the second embodiment, and FIG. 5 is a schematic partial end view of the display device.
FIG. 6 shows a schematic partial perspective view when P is disassembled. The field emission device includes a cathode electrode 11 (corresponding to a base) formed on a support 10,
Gate electrode 1 formed above gate electrode and having opening 14A
3 and an electron-emitting portion 15 formed on the cathode electrode 11. Note that the opening 14A provided in the gate electrode 13 is referred to as a first opening 14A for convenience. An insulating layer 12 is formed on the support 10 and the cathode electrode 11, and a second opening 14 B communicating with the first opening 14 A provided in the gate electrode 13 is formed on the insulating layer 12.
, And the electron-emitting portion 15 is located at the bottom of the second opening 14B. The electron-emitting portion 15 has a diamond-like amorphous carbon 21 (D
The carbon nanotube 20 is fixed on the cathode electrode 11 using the LC 21). Note that the carbon nanotube structure is placed on the substrate (also in the second embodiment,
Specifically, diamond-like amorphous carbon 21 (DL) is formed on the cathode electrode 11) as a binder material.
The carbon nanotubes 20 are fixed using C21).

The display device comprises a cathode panel CP in which a large number of the above-mentioned field emission devices are formed in an effective area, and an anode panel AP, and is composed of a plurality of pixels. And an anode electrode 33 and a phosphor layer 31 provided on the substrate 30 so as to face the field emission device. The cathode panel CP and the anode panel AP are joined via a frame 34 at their peripheral edges. In the partial end view shown in FIG. 5, in the cathode panel CP, the openings 14A and 14B and the electron emission portions 15 for one cathode electrode 11 are provided.
Are shown two by two for simplicity of the drawings, but the present invention is not limited to this, and the basic configuration of the field emission device is as shown in FIG. Furthermore, a through-hole 36 for evacuation is provided in an ineffective area of the cathode panel CP, and a chip tube 37 that is sealed off after evacuation is connected to the through-hole 36. However, FIG.
Indicates a completed state of the display device, and the illustrated chip tube 37 is already sealed off. Illustration of the spacer is omitted.

The structure of the anode panel AP can be the same as the structure of the anode panel AP described in the first embodiment, and a detailed description thereof will be omitted.

When a display is performed in this display device, a relative negative voltage is applied to the cathode electrode 11 from the cathode electrode control circuit 40, and a relative positive voltage is applied to the gate electrode 13. , And a higher positive voltage than the gate electrode 13 is applied to the anode electrode 33 from the acceleration power supply 42. When displaying on such a display device, for example, a scanning signal is input to the cathode electrode 11 from the cathode electrode control circuit 40, and a video signal is input to the gate electrode 13 from the gate electrode control circuit 41. Alternatively, a video signal may be input to the cathode electrode 11 from the cathode electrode control circuit 40, and a scanning signal may be input to the gate electrode 13 from the gate electrode control circuit 41. Due to an electric field generated when a voltage is applied between the cathode electrode 11 and the gate electrode 13, electrons are emitted from the electron emitting portion 15 based on the quantum tunnel effect, and the electrons are attracted to the anode electrode 33, and the fluorescent layer 31 Collide with As a result, the phosphor layer 31 is excited to emit light, and a desired image can be obtained.

Hereinafter, a method for manufacturing a carbon nanotube structure, a method for manufacturing a field emission device, and a method for manufacturing a display device according to the second embodiment will be described with reference to FIGS.

[Step-200] First, a conductive material layer for forming a cathode electrode is formed on a support 10 made of, for example, a glass substrate, and then a known lithography technique and RI
By patterning the conductive material layer based on the E method, a striped cathode electrode 11 (corresponding to a base) is formed on the support 10 (see FIG. 7A).
The striped cathode electrode 11 extends in the left-right direction on the drawing sheet. The conductive material layer is made of, for example, chromium (Cr) having a thickness of about 0.2 μm formed by a sputtering method.
Consists of layers.

[Step-210] Next, an insulating layer 12 is formed on the support 10 and the cathode electrode 11. Specifically, for example, by a CVD method using TEOS (tetraethoxysilane) as a source gas, a thickness of about 3 μm
m of insulating layers 12 are formed.

[Step-220] Thereafter, the gate electrode 13 having the first opening 14A is formed on the insulating layer 12. Specifically, after a conductive material layer made of chromium (Cr) for forming a gate electrode is formed on the insulating layer 12 by a sputtering method, a first mask material layer ( (Not shown), the conductive material layer is etched using the first mask material layer as an etching mask, and the conductive material layer is patterned in a stripe shape, and then the first mask material layer is removed. . Next, a patterned second mask material layer (not shown) is formed on the conductive material layer and the insulating layer 12, and the conductive material layer is etched using the second mask material layer as an etching mask. Thereby, the gate electrode 13 having the first opening 14A on the insulating layer 12 is formed.
Can be obtained. Striped gate electrode 13
Extend in a direction different from that of the cathode electrode 11 (for example, a direction perpendicular to the plane of the drawing).

[Step-230] Subsequently, a second opening 14B communicating with the first opening 14A formed in the gate electrode 13 is formed in the insulating layer 12. Specifically, after the insulating layer 12 is etched by RIE using the second mask material layer as an etching mask, the second
Is removed. Thus, the structure shown in FIG. 7B can be obtained. In the second embodiment, the first opening 14A and the second opening 14B have a one-to-one correspondence. That is, one first opening 14
One second opening 14B is formed corresponding to A. The planar shape of the first and second openings 14A and 14B is, for example, a circle having a diameter of 1 μm to 30 μm. For example, one or more of these openings 14A and 14B are provided for one pixel.
About 3,000 pieces may be formed.

[Step-240] Then, the second opening 1
The carbon nanotubes 20 are arranged on the surface of the portion of the cathode electrode 11 located at the bottom of 4B. for that reason,
First, a mask layer 116 in which the surface of the cathode electrode 11 is exposed is formed at the center of the bottom of the second opening 14B (see FIG. 7C). Specifically, after a resist material layer is formed on the entire surface including the insides of the openings 14A and 14B by a spin coating method, the second opening 1 is formed based on a lithography technique.
By forming a hole in the resist material layer located at the center of the bottom of 4B, mask layer 116 can be obtained. In the second embodiment, the mask layer 116 is
Of the cathode electrode 11 located at the bottom of the opening 14B, the side wall of the second opening 14B, and the first opening 14A.
, The gate electrode 13 and the insulating layer 12. Thereby, in the subsequent steps, the second opening portion 14B
A carbon nanotube 20 and a diamond-like amorphous carbon 21 are formed on the surface of a portion of the cathode electrode 11 located at the center of the bottom of the cathode electrode 11.
And the gate electrode 13 can be reliably prevented from being short-circuited by these.

Next, on the mask layer 116 including the exposed surface of the cathode electrode 11, the [Step-11] of the first embodiment is applied.
0], the carbon nanotubes 20 are arranged.

[Step-250] Then, similarly to [Step-120] of the first embodiment, the mask layer 116, the carbon nanotubes 20, and the exposed cathode electrode 11 are formed.
After depositing diamond-like amorphous carbon 21 as a binder material thereon, the mask layer 116 is removed. As a result, the carbon nanotubes 20 can be fixed on a desired area of the cathode electrode 11 (an area where an electron emission portion is to be formed). FIGS. 8A and 8B show this state. FIG. 8A is a schematic partial end view of the field emission device viewed from the direction in which the gate electrode 13 extends. FIG. 8B shows a cathode electrode 1.
FIG. 2 is a schematic partial end view of the field emission element viewed from a direction in which the field emission device extends.

[Step-260] Thereafter, the side wall surface of the second opening 14B provided in the insulating layer 12 is recessed by isotropic etching to expose the opening end of the gate electrode 13. Is preferred. Thus, the field emission device shown in FIG. 9 can be completed.
The isotropic etching can be performed by dry etching using radicals as a main etching species, such as chemical dry etching, or wet etching using an etchant. As an etching solution, for example, a 49% hydrofluoric acid aqueous solution and pure water 1: 100
(Volume ratio) A mixed solution can be used.

[Step-270] Thereafter, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Embodiment 3) Embodiment 3 is a modification of Embodiment 2. FIG. 10 is a schematic partial end view of the field emission device according to the third embodiment. This field emission device also has a cathode electrode 11 formed on the support 10, a gate electrode 13 formed above the cathode electrode 11 and having a first opening 14A, and an electron formed on the cathode electrode 11. It consists of a discharge section 15. And the opening 14
An electron emitting portion 15 is formed on the surface of the portion of the cathode electrode 11 located at the bottom of A and 14B. Note that, unlike the field emission device described in the second embodiment, the carbon nanotubes 20 and the diamond-like amorphous carbon 21 covering the carbon nanotubes 20 are:
It extends into the insulating layer 12. However, depending on the state of formation of the carbon nanotubes 20 and the diamond-like amorphous carbon 21 covering the carbon nanotubes 20, the carbon nanotubes 20 and The diamond-like amorphous carbon 21 covering the carbon nanotubes 20 may be formed only on the surface of the portion of the cathode electrode 11 located at the bottom of the openings 14A and 14B, or the entire surface of the stripe-like cathode electrode 11 may be formed. May be formed.

Also in the field emission device of the third embodiment,
An insulating layer 12 is formed on the support 10 and the cathode electrode 11, and a second opening 14B communicating with the first opening 14A provided in the gate electrode 13 is provided in the insulating layer 12. The electron-emitting portion 15 is located at the bottom of the second opening 14B.

The display device of the third embodiment is substantially the same as that of FIG.
Since the display device is the same as that described above, detailed description is omitted.

Hereinafter, the method for manufacturing the carbon nanotube structure according to the third embodiment and the method for manufacturing the field emission device (second example)
B and a method for manufacturing the display device will be described with reference to FIGS.

[Step-300] First, in the same manner as in [Step-200] of the second embodiment, a conductive material layer for forming a cathode electrode is formed on a support 10 made of, for example, a glass substrate. By patterning the conductive material layer based on the lithography technology and the RIE method,
A striped cathode electrode 11 is formed on the support 10 (see FIG. 3A). The striped cathode electrode 11 extends in the left-right direction on the drawing sheet. The conductive material layer is made of, for example, a chromium (Cr) layer having a thickness of about 0.2 μm formed by a sputtering method.

[Step-310] Then, carbon nanotubes 20 are formed on the surface of cathode electrode 11 in the same manner as in [Step-110] of the first embodiment.

[Step-320] Thereafter, diamond-like amorphous carbon 21 is deposited on the carbon nanotubes 20 and the exposed cathode electrode 11 in the same manner as in [Step-120] of the first embodiment, and electron emission is performed. The part 15 is obtained. This state is shown in FIG.

[Step-330] Next, the gate electrode 13 having the first opening 14A is provided above the electron-emitting portion 15. Specifically, the insulating layer 12 is formed on the entire surface in the same manner as in [Step-210] of the second embodiment.
In the same manner as in [Step-220], the first
The gate electrode 13 having the opening 14A is formed. Then, in the same manner as in [Step-230] of the second embodiment,
A second opening (14B) communicating with the first opening (14A) provided in the gate electrode (13) is formed in the insulating layer (12), and the electron emitting section (15) is exposed at the bottom of the second opening (14B). Also in the third embodiment, the first opening 14A and the second opening 14B have a one-to-one correspondence. That is, one second opening 14B is formed corresponding to one first opening 14A. The first and second openings 14
The plane shape of A, 14B is, for example, 1 μm to 30 μm in diameter.
Is circular. These openings 14A and 14B may be formed, for example, in a number of about 1 to 3000 per pixel. Thus, the field emission device shown in FIG. 10 can be obtained.

[Step-340] Then, similarly to [Step-260] of the second embodiment, the side wall surface of the second opening 14B provided in the insulating layer 12 is receded by isotropic etching. It is preferable from the viewpoint that the opening end of the gate electrode 13 is exposed. Next, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Embodiment 4) Embodiment 4 is also a modification of Embodiment 2. The field emission device according to the fourth embodiment has a second structure. That is, the field emission device according to the fourth embodiment includes a strip-shaped gate electrode support 112 made of an insulating material provided on the support 10, a cathode electrode 11 formed on the support 10, and a plurality of openings 114. The gate electrode 113 is formed of a band-shaped material 113A on which is formed, and the electron emission portion 15 is formed on the cathode electrode 11. The electron emission portion 15 is in contact with the top surface of the gate electrode support portion 112. The strip-shaped material 113A is stretched so that the opening 114 is located above. The electron emission portion 15 includes a carbon nanotube 20 formed on the surface of the portion of the cathode electrode 11 located at the bottom of the opening 114, and a diamond-like amorphous material deposited on the carbon nanotube 20 and the exposed cathode electrode 11. It is made of carbon 21.

The belt-like material 113A is formed on the gate electrode support 1
12 is fixed to the top surface with a thermosetting adhesive (for example, an epoxy-based adhesive). FIG. 11A is a schematic partial cross-sectional view of the field emission device according to the fourth embodiment, in which a cathode electrode 11, a band-shaped material 113A, a gate electrode 113,
FIG. 11B is a schematic layout view of the gate electrode support portion 112.

Hereinafter, an example of a method of manufacturing the field emission device of Embodiment 4 (2C manufacturing method) will be described.

[Step-400] First, the gate electrode support 112 is formed on the support 10 by, for example, a sandblast method.

[Step-410] Thereafter, the electron-emitting portion 15 is formed on the support 10. Specifically, Embodiment 1
In the same manner as in [Step-100] to [Step-120],
A carbon nanotube 20 is formed on the surface of the cathode electrode 11.
Is formed, and diamond-like amorphous carbon 21 is deposited on the carbon nanotubes 20 and the exposed cathode electrode 11. However, the cathode electrode 11
Has a stripe shape, and is formed on a portion of the support 10 located between the gate electrode support portions 112.

[Step-420] Thereafter, the plurality of openings 1
The strip-shaped material 113A in which 14 is formed is
The plurality of openings 114 are disposed in a state supported by the gate electrode support 112 so as to be positioned above the electron-emitting portion 15, and are thus made of the strip-shaped material 113A. Gate electrode 1 having 114
13 is positioned above the electron emission section 15. The strip-shaped strip material 113A can be fixed to the top surface of the gate electrode support 112 with a thermosetting adhesive (for example, an epoxy-based adhesive). The projected image of the striped cathode electrode 11 is orthogonal to the projected image of the strip-shaped material 113A.

In the fourth embodiment, the support 10
After the cathode electrode 11 is formed thereon, the gate electrode support 112 may be formed on the support 10 based on, for example, a sandblast method. Also, the gate electrode support 11
2 may be formed based on, for example, a combination of a CVD method and an etching method.

Further, as shown in FIG. 12, both ends of the strip-shaped strip material 113 A are fixed to the periphery of the support 10, as shown in a schematic partial cross-sectional view near the end of the support 10. Structure. More specifically, for example, a protrusion 117 is formed in advance on the periphery of the support 10, and a thin film 118 of the same material as the material forming the belt-shaped material 113 </ b> A is formed on the top surface of the protrusion 117. deep.
Then, with the strip-shaped strip material 113A stretched, the thin film 118 is welded to the thin film 118 using, for example, a laser. The protrusion 117 can be formed, for example, simultaneously with the formation of the gate electrode support.

Further, the planar shape of the opening 114 in the field emission device of the fourth embodiment is not limited to a circle. Modifications of the shape of the opening 114 provided in the belt-shaped material 113A are illustrated in FIGS. 13A, 13B, 13C, and 13D.

The present invention has been described based on the embodiments, but the present invention is not limited to these embodiments. Various conditions described in the embodiment, the materials used, the configuration and structure of the field emission device and the display device, the manufacturing method is an example, and can be changed as appropriate, production of carbon nanotubes and diamond-like amorphous carbon, The formation method and the deposition conditions are also examples, and can be appropriately changed. In some cases, diamond-like amorphous carbon may be deposited over the entire effective area.

In the field emission device, one electron emission portion corresponds to one opening portion. However, depending on the structure of the field emission device, a plurality of electron emission portions may be provided in one opening portion. Corresponding form or multiple openings
It is also possible to adopt a form in which two electron emitting portions correspond. Alternatively, a plurality of first openings are provided in the gate electrode, and one second opening communicating with the plurality of first openings in the insulating layer is provided.
, And one or more electron-emitting portions may be provided.

In the cold cathode field emission device of the present invention, a second insulating layer 62 may be further provided on the gate electrode 13 and the insulating layer 12, and a focusing electrode 63 may be provided on the second insulating layer 62. . FIG. 14 shows a schematic partial end view of a field emission device having such a structure. Second insulating layer 62
Has a third opening 64 communicating with the first opening 14A.
Is provided. For example, in the second embodiment, the converging electrode 63 is formed by forming the stripe-shaped gate electrode 13 on the insulating layer 12 and then forming the second insulating layer 62 in [Step-220]. Then, after forming a patterned converging electrode 63 on the second insulating layer 62, the converging electrode 63 and the third opening 6 are formed in the second insulating layer 62.
4 and a first opening 14A in the gate electrode 13.
May be provided. Incidentally, depending on the patterning of the focusing electrode, a focusing electrode of a type in which one or a plurality of electron-emitting portions or a focusing electrode unit corresponding to one or a plurality of pixels can be formed, or an effective area can be obtained. Can be formed as a focusing electrode of a type in which is covered with one sheet of conductive material.

The focusing electrode is formed not only by such a method but also by, for example, a 42% Ni—
After forming an insulating film made of, for example, SiO _{2 on} both sides of a metal plate made of an Fe alloy, a focusing electrode can be formed by forming an opening by punching or etching a region corresponding to each pixel. . Then, the cathode panel, the metal plate, and the anode panel are stacked, and a frame body is arranged on the outer peripheral portion of both panels, and a heat treatment is performed. The display device can also be completed by bonding, bonding the insulating film formed on the other surface of the metal plate and the anode panel, integrating these members, and then sealing them in a vacuum.

The gate electrode may be a type in which the effective area is covered with one sheet of conductive material (having an opening). In this case, the cathode electrode has the same structure as that described in the first embodiment.
Then, a positive voltage (for example, 160 volts) is applied to the gate electrode.
Is applied. Further, for example, a switching element composed of a TFT is provided between the cathode electrode constituting each pixel and the cathode electrode control circuit, and the operation of the switching element controls the state of application to the cathode electrode constituting each pixel. Then, the light emission state of the pixel is controlled.

Alternatively, the cathode electrode may be a cathode electrode in which the effective area is covered with one sheet of conductive material. In this case, an electron emission region composed of a field emission element and constituting each pixel is formed in a predetermined portion of one sheet of conductive material. And
A voltage (for example, 0 volt) is applied to such a cathode electrode. Further, for example, a switching element composed of a TFT is provided between the rectangular gate electrode forming each pixel and the gate electrode control circuit, and the operation of the switching element causes a connection to the electron-emitting portion forming each pixel. A state where an electric field is applied is controlled, and a light emitting state of the pixel is controlled.

The carbon nanotube structure of the present invention can be applied to an active matrix, which is an electron passage in a transistor. FIG. 15 shows a schematic partial end view of such a transistor. This transistor is a bottom-gate type field effect transistor, and has a gate electrode 71 formed on a base 70 made of an insulating material, an insulating film (gate insulating film) 72 formed on the gate electrode 71, and a gate insulating film. It is composed of a source / drain region 73 formed on 72 and one carbon nanotube 74 arranged so as to bridge the source / drain region 73. And carbon
On the nanotubes 74, the source / drain regions 73 and the gate insulating film 72 (these correspond to the base), a diamond-like amorphous carbon
5, the carbon nanotube 74 is fixed. The substance adsorbed on the surface of the carbon nanotube 74 causes electric noise. Such electrical noise is unfavorable due to the characteristics of the transistor, and is a fatal defect particularly for a transistor that operates with a smaller electrical signal such as a single electron tunnel. However, as shown in FIG. 15, by coating the carbon nanotubes 74 with the same diamond-like amorphous carbon 75, it is possible to suppress the adsorption of different kinds of substances on the surface of the carbon nanotubes 74. It is possible to prevent the occurrence of noise.

[0111]

According to the present invention, carbon nanotubes are fixed to a substrate or a cathode electrode with diamond-like amorphous carbon as a binder material, and the diamond-like amorphous carbon has extremely excellent fixing force (adhesive force). The carbon nanotubes can be securely fixed to the base or the cathode electrode, and the binder material is thermally decomposed by subsequent heat treatment, etc., and the fixing force is not reduced. It does not cause degradation of the properties of the nanotube. In addition, since the carbon nanotube and the binder material are essentially composed of the same substance, the crystallinity of the carbon nanotube portion through which electrons pass is changed, or the bonding of atoms in such a portion. There is no change in the state, and no change occurs in the electrical characteristics of the carbon nanotube.

Furthermore, diamond-like amorphous carbon is a chemically stable substance, can prevent foreign substances from adsorbing and adhering to the surface of carbon nanotubes, and has excellent mechanical properties. Therefore, it is possible to prevent the carbon nanotube from being physically damaged. Further, since the thermal conductivity is high, even when the temperature of the carbon nanotube is increased due to resistance heat or the like, the heat radiation effect is excellent. Furthermore, diamond-like amorphous carbon has a very small electron affinity, which is extremely advantageous for field emission applications. In addition, since diamond-like amorphous carbon has a relatively wide band gap, electrons are preferentially transmitted through the carbon nanotube, and there is no risk of electric leakage.

[Brief description of the drawings]

FIG. 1 is a schematic partial cross-sectional view of a cold cathode field emission display according to a first embodiment of the present invention.

FIG. 2 is a schematic perspective view of one electron emission unit in the cold cathode field emission display according to the first embodiment of the invention;

FIG. 3 is a schematic partial cross-sectional view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 1 of the present invention.

FIG. 4 is a schematic partial cross-sectional view of a substrate and the like for describing a method for manufacturing an anode panel in the cold cathode field emission display according to the first embodiment of the invention;

FIG. 5 is a schematic partial cross-sectional view of a cold cathode field emission display according to a second embodiment of the present invention.

FIG. 6 is a schematic partial perspective view of a cold cathode field emission display according to a second embodiment of the present invention when a cathode panel and an anode panel are disassembled.

FIG. 7 is a schematic partial cross-sectional view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 2 of the present invention.

8 is a schematic partial cross-sectional view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 2 of the invention, following FIG. 7;

FIG. 9 is a schematic partial cross-sectional view of a support and the like for explaining the method for manufacturing the cold cathode field emission device according to the second embodiment of the invention, following FIG. 8;

FIG. 10 is a schematic partial end view of a cold cathode field emission device according to a third embodiment of the present invention.

FIG. 11 is a schematic partial cross-sectional view of a cold cathode field emission device according to a fourth embodiment of the present invention, and a schematic layout diagram of a gate electrode and the like.

FIG. 12 is a schematic partial cross-sectional view of a cold cathode field emission device according to a modification of the fourth embodiment of the present invention.

FIG. 13 is a schematic plan view showing a plurality of openings of a gate electrode according to Embodiment 4 of the present invention.

FIG. 14 is a schematic partial end view of a cold cathode field emission device having a focusing electrode, which is a modification of the cold cathode field emission device according to the second embodiment of the invention.

FIG. 15 is a schematic partial cross-sectional view of a transistor showing an example in which the carbon nanotube structure of the present invention is applied to an active matrix which is a passage of electrons in the transistor.

[Explanation of symbols]

CP: cathode panel, AP: anode panel, 10: support, 11A: wiring, 11 ...
Cathode electrode, 12: insulating layer, 112: gate electrode support, 13, 113: gate electrode, 113A
... Band-shaped material, 14A, 114 ... Opening (first opening), 14B ... Second opening, 15 ... Emitting part, 16,116 ... Mask layer, 117 ... projecting part, 118 ... thin film, 20, 74 ... carbon
Nanotube, 21, 75 ... diamond-like amorphous carbon (DLC), 30 ... substrate, 31, 3
1R, 31G, 31B ... phosphor layer, 32 ... black matrix, 33 ... anode electrode, 34 ...
Frame, 35 spacer, 36 through hole, 37
... Chip tube, 40, 40A ... Cathode electrode control circuit, 41 ... Gate electrode control circuit, 42 ... Acceleration power supply, 62 ... Second insulating layer, 63 ... Converging electrode,
64: third opening, 71: gate electrode, 72
... Insulating film (gate insulating film), 73 ... Source / drain region

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 29/04 H01J 31/12 C 31/12 1/30 F

Claims (16)

[Claims] 1. A carbon nanotube structure wherein a carbon nanotube is fixed on a substrate using diamond-like amorphous carbon as a binder material. 2. The diamond-like amorphous carbon has a peak having a half width of 30 cm ^-1 or more in a wave number range of 1400 to 1630 cm ^-1 in a Raman spectrum using a laser beam having a wavelength of 514.5 nm. The carbon nanotube structure according to claim 1. (A) disposing a carbon nanotube on a substrate; and (b) depositing diamond-like amorphous carbon as a binder material on the substrate and the carbon nanotube. Fixing a nanotube. A method for producing a carbon nanotube structure, comprising: 4. The diamond-like amorphous carbon has a peak having a half width of 30 cm ^-1 or more in a wave number range of 1400 to 1630 cm ^-1 in a Raman spectrum using a laser beam having a wavelength of 514.5 nm. The method for producing a carbon nanotube structure according to claim 3. 5. A cold cathode field emission device comprising: (A) a cathode electrode provided on a support; and (B) an electron emission portion provided on the cathode electrode. A cold cathode field emission device, wherein carbon nanotubes are fixed on a cathode electrode using diamond-like amorphous carbon as a binder material. 6. A cathode electrode provided on a support, B an electron-emitting portion provided on the cathode electrode, and an opening portion provided above the electron-emitting portion. A cold cathode field emission device, wherein the electron emission portion comprises a carbon nanotube fixed on a cathode electrode using diamond-like amorphous carbon as a binder material. 7. An insulating layer is formed on the support and the cathode electrode, a gate electrode is formed on the insulating layer, and the insulating layer has a second opening communicating with an opening provided in the gate electrode.
The cold cathode field emission device according to claim 6, wherein an opening is formed, and an electron emission portion is exposed at a bottom of the second opening. 8. The diamond-like amorphous carbon has a peak having a half width of 30 cm ^-1 or more in a wave number range of 1400 to 1630 cm ^-1 in a Raman spectrum using a laser beam having a wavelength of 514.5 nm. The cold cathode field emission device according to any one of claims 5 to 7. 9. A cold cathode field emission display in which a cathode panel provided with a plurality of cold cathode field emission devices and an anode panel provided with a phosphor layer and an anode electrode are joined at their peripheral edges. A cold cathode field emission device comprising: (A) a cathode electrode provided on a support; and (B) an electron emission portion provided on the cathode electrode. A cold cathode field emission display comprising carbon nanotubes fixed on a cathode electrode using diamond-like amorphous carbon as a binder material. 10. A cold cathode field emission display in which a cathode panel provided with a plurality of cold cathode field emission devices and an anode panel provided with a phosphor layer and an anode electrode are joined at their peripheral edges. A cold cathode field emission device comprising: (A) a cathode electrode provided on a support; (B) an electron emission portion provided on the cathode electrode; and (C) an upper portion of the electron emission portion. And a gate electrode having an opening, wherein the electron-emitting portion is formed by fixing carbon nanotubes on the cathode electrode using diamond-like amorphous carbon as a binder material. Field emission display. 11. A cold cathode field emission device wherein an insulating layer is formed on a support and a cathode electrode, a gate electrode is formed on the insulating layer, and the insulating layer is provided on the gate electrode. 11. The cold cathode field emission display according to claim 10, wherein a second opening communicating with the opening is formed, and an electron emission portion is exposed at a bottom of the second opening. 12. The method according to claim 11, wherein said diamond-like amorphous carbon is a Raman laser having a wavelength of 514.5 nm.
In the spectrum, wave numbers 1400 to 1630 cm ^-1
The cold cathode field emission display according to any one of claims 9 to 11, wherein the cold cathode field emission display has a peak having a half width of 30 cm- ¹ or more in the range of (1) to (12). 13. A method of manufacturing a cold cathode field emission device comprising: (A) a cathode electrode provided on a support; and (B) an electron emission portion provided on the cathode electrode. (A) disposing the carbon nanotube on a desired region of the cathode electrode; and (b) placing the carbon nanotube on the cathode electrode and the carbon nanotube.
Depositing diamond-like amorphous carbon as a binder material, and fixing carbon nanotubes on the desired region of the cathode electrode, thereby forming a cold cathode field emission device. (A) a cathode electrode provided on a support; (B) an electron-emitting portion provided on the cathode electrode; and (C) an electron-emitting portion provided above the electron-emitting portion. A method for manufacturing a cold cathode field emission device comprising: a gate electrode comprising: (a) arranging a carbon nanotube on a desired region of a cathode electrode; On carbon nanotubes,
Depositing diamond-like amorphous carbon as a binder material, and fixing carbon nanotubes on the desired region of the cathode electrode, thereby forming a cold cathode field emission device. 15. A cold cathode field emission display in which a cathode panel provided with a plurality of cold cathode field emission devices and an anode panel provided with a phosphor layer and an anode electrode are joined at their peripheral edges. A method of manufacturing a device, comprising:
The cold cathode field emission device comprises: (A) a cathode electrode provided on a support; and (B) an electron emission portion provided on the cathode electrode. Arranging the carbon nanotubes on a desired area; (b) placing the carbon nanotubes on the cathode electrode and the carbon nanotubes;
Depositing diamond-like amorphous carbon as a binder material, and fixing carbon nanotubes on the desired region of the cathode electrode, thereby forming a cold cathode field emission display device. 16. A cold cathode field emission display in which a cathode panel provided with a plurality of cold cathode field emission devices and an anode panel provided with a phosphor layer and an anode electrode are joined at their peripheral portions. A method of manufacturing a device, comprising:
A cold cathode field emission device comprising: (A) a cathode electrode provided on a support; (B) an electron emission portion provided on the cathode electrode; and (C) an electron emission portion provided above the electron emission portion. A gate electrode having an opening, comprising: (a) disposing a carbon nanotube on a desired region of the cathode electrode; and (b) forming a carbon nanotube on the cathode electrode and the carbon nanotube.
Depositing diamond-like amorphous carbon as a binder material, and fixing carbon nanotubes on the desired region of the cathode electrode, thereby forming a cold cathode field emission display.