JP2003045317A - Electron emission body and manufacturing method, cold- cathode field electron emission element and manufacturing method, as well as cold-cathode field electron emission display device and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cold-cathode field electron emission element which can form a carbon thin film even at low temperature, and yet with excellent cold- cathode field electron emission characteristics. SOLUTION: The cold-cathode field electron emission element consists of (A) a cathode electrode 11 set up on a support body 10 and (B) a plurality of conical electron emission bodies 26 formed on the cathode electrode 11, and the electron emission bodies 26 is structured with a base part 24 made of a conical metal silicide 23 formed on the cathode electrode and a carbon thin film 25 formed on the surface of the base part 24.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron emitter and a manufacturing method thereof, a cold cathode field emission device and a manufacturing method thereof, and a cold cathode field emission display device and a manufacturing method thereof.

[0002]

2. Description of the Related Art When an electric field having a strength higher than 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 by a quantum tunnel effect, and even at room temperature. Electrons are emitted into the vacuum. Electron emission based on such a principle is called cold cathode field emission, or simply field emission. In recent years, a flat type cold cathode field emission display device, so-called field emission display (FED), in which the principle of field emission is applied to image display has been proposed, and has advantages such as high brightness and low power consumption. Therefore, it is expected as an image display device that replaces the conventional cathode ray tube (CRT).

A cold cathode field emission display device (hereinafter sometimes simply referred to as a display device) is generally arranged in a two-dimensional matrix and has a cathode panel having an electron emission region corresponding to each pixel and an electron emission region. It has a configuration in which an anode panel having a phosphor layer that emits light when excited by collision with electrons emitted from the emission region is arranged to face each other with a vacuum layer interposed therebetween. Usually, a plurality of electron emitting portions are formed in each electron emitting region, and a gate electrode for drawing out electrons from the electron emitting portions is further formed. The minimum structural unit involved in electron emission (here, the portion having an electron emission portion and a gate electrode) is a cold cathode field emission device (hereinafter,
It may be simply referred to as a field emission device).

In recent years, attempts to apply carbon to electronic and electric devices have been actively made, which was inspired by the discovery of carbon nanotubes. One of such attempts is the field emission device described above. Carbon-based materials such as diamond, graphite, diamond-like amorphous carbon (DLC), and cluster carbon have a lower threshold electric field and higher electron emission efficiency than refractory metals, and are materials that form the electron emission portion of a field emission device. As an excellent material.

By the way, at present, as a method for forming a carbonaceous material, a chemical vapor deposition method (CVD method) and a filtered cathodic vacuum arc method (FCVA) are used.
Method), laser ablation method, etc. are being studied.
The mainstream is the easy CVD method applicable to a large area. CVD
Regarding the formation of carbon-based materials based on the law, see, for example, the document "Electron field emission and structural properti
es of carbon chemically vapor-deposited films ", A.
N. Obraztsov, et al., Diamond and Related Material
s, 8 (1999), pp814-819 and "Well-aligned graphite n
anofibers synthesized by plasma-assisted chemical
vapor deposition ", Y. Chen, et al., Chemical Physi
See cs Letters, 272 (1997), pp178-182.

[0006]

Diamond, graphite, and carbon nanotubes, which are carbon materials having excellent crystallinity, are currently realized only by a high temperature process of 500 ° C. or higher. That is, the diamond forming temperature is 700 to 900 ° C, the graphite forming temperature is 900 to 1200 ° C, and the carbon nanotube forming temperature is about 550 to 900 ° C.

Since the carbon-based material is formed at such a high temperature, it is difficult to use a glass substrate. The use of a glass substrate is important for reducing the manufacturing cost of a display device. Further, when trying to apply the carbon-based material to various electronic devices, it is difficult to use a material such as aluminum or gold having a low resistance value and a low melting point for the wiring and the like.

Attempts have been made to lower the formation temperature of the carbonaceous material by using nickel, cobalt, iron or the like as a kind of catalyst, but they have not yet reached the stage of practical application. In particular, it is currently difficult to form a carbon-based material at 500 ° C or lower.

Therefore, an object of the present invention is to form a carbon thin film even at a relatively low temperature, and to provide an electron emitter excellent in cold cathode field emission properties, a method for producing the same, and an application of such an electron emitter. Another object of the present invention is to provide a cold cathode field emission device and a manufacturing method thereof, a cold cathode field emission display device incorporating the cold cathode field emission device, and a manufacturing method thereof.

[0010]

An electron emitter of the present invention for achieving the above object is formed by a pyramidal base formed of a metal silicide on a substrate, and a surface of the base. It is characterized by being composed of a carbon thin film.

A method of manufacturing an electron emitter of the present invention for achieving the above object is a method of manufacturing the electron emitter of the present invention described above, wherein (a) a metal silicide layer is formed on a substrate. And (b) forming a carbon thin film on the metal silicide layer by chemical vapor deposition.

By the electron emitter of the present invention or the method for manufacturing the same, an electron emitting portion of a cold cathode field emission device, an electron beam source in an electron gun incorporated in a cathode ray tube, and a fluorescent display tube can be obtained.

A first aspect of the present invention for achieving the above object
The cold cathode field emission device according to the aspect of (1) is an electron emission device including (A) a cathode electrode provided on a support and (B) a plurality of pyramidal electron emission members formed on the cathode electrode. And a cold cathode field emission device comprising:
The electron emitter is characterized by being formed of a pyramidal base formed of a metal silicide on the cathode electrode, and a carbon thin film formed on the surface of the base.

The first aspect of the present invention for achieving the above object
In the cold cathode field emission display according to this aspect, 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 are joined at their peripheral portions. In the so-called two-electrode type cold cathode field emission display device, the cold cathode field emission device is formed on (A) a cathode electrode provided on a support and (B) a cathode electrode. A plurality of pyramidal electron emitters, the electron emitters being pyramidal bases made of metal silicide formed on the cathode electrode, and the electron emitters formed on the surfaces of the bases. It is characterized in that it is composed of a carbon thin film.

Second aspect of the present invention for achieving the above object
The cold cathode field emission device according to the aspect of (1) is an electron emission device including (A) a cathode electrode provided on a support and (B) a plurality of pyramidal electron emission members formed on the cathode electrode. And a gate electrode (C) having an opening, which is disposed above the electron-emitting portion, and the electron-emitting body has a pyramidal base formed of metal silicide on the cathode electrode, and It is characterized by comprising a carbon thin film formed on the surface of the base.

Second aspect of the present invention for achieving the above object
In the cold cathode field emission display according to this aspect, 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 are joined at their peripheral portions. In the so-called three-electrode type cold cathode field emission display, the cold cathode field emission device is formed on a cathode electrode provided on a support (A) and a cathode electrode (B). A plurality of conical electron emitters, and (C) a gate electrode disposed above the electron emitters and having an opening, the electron emitters on the cathode electrode. It is characterized in that it is composed of a pyramidal base formed of a metal silicide formed on the substrate and a carbon thin film formed on the surface of the base.

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 an 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. The structure can 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 according to the second aspect of the present invention or the cold cathode field emission device in the cold cathode field emission display device, a strip shape or a cross-shaped shape made of an insulating material is used. The gate electrode supporting portion is formed on the support, and the gate electrode made of a band-shaped material having a plurality of openings is formed so as to contact the top surface of the gate electrode supporting portion and above the electron emitting portion. It is also possible to have a structure that is stretched so that Note that such a structure is referred to as a cold cathode field emission device having the second structure for convenience.

The electron emitter of the present invention, the cold cathode field emission device according to the first or second aspect of the present invention, or the cold cathode field emission device of the cold cathode field emission display device comprises: Depending on the formation conditions of the carbon thin film, a structure in which carbon nanotubes are formed at the tip of the electron emitter or in the vicinity thereof can be obtained.

The first aspect of the present invention for achieving the above object
The method of manufacturing a cold cathode field emission device according to the aspect of
(A) a cathode electrode provided on a support; and (B) an electron emitting portion composed of a plurality of cone-shaped electron emitters formed on the cathode electrode, wherein the electron emitter is a cathode. A method of manufacturing a cold cathode field emission device, comprising a pyramidal base formed of a metal silicide formed on an electrode, and a carbon thin film formed on the surface of the base, wherein the electron emitter is: It is characterized in that (a) a step of forming a metal silicide layer on the cathode electrode and (b) a step of forming a carbon thin film on the metal silicide layer by a chemical vapor deposition method.

A first aspect of the present invention for achieving the above object
In the method for manufacturing a cold cathode field emission display device according to the aspect, 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 have their peripheral portions. The cold cathode field emission device is composed of (A) a cathode electrode provided on a support and (B) a plurality of cone-shaped electron emission devices formed on the cathode electrode. The so-called two-electrode structure is composed of an electron emitting portion, and the electron emitting body is composed of a pyramidal base formed of a metal silicide on a cathode electrode and a carbon thin film formed on the surface of the base. Type cold cathode field emission display, the method comprising: (a) forming a metal silicide layer on the cathode electrode; and (b) chemically vapor-depositing the metal silicide layer on the metal silicide layer. Based on growth method And forming the step of forming the carbon thin film.

In the method of manufacturing a cold cathode field emission device according to the first aspect of the present invention or the method of manufacturing a cold cathode field emission display device according to the first aspect, a method of forming an electron emitter is used. More specifically, (a) a step of forming a cathode electrode in which a silicon-containing layer and a metal layer are sequentially formed in a surface region where an electron emitting portion is to be formed,
(B) a step of reacting the silicon-containing layer and the metal layer to form a metal silicide layer on the cathode electrode, and (c)
A carbon thin film is formed on the metal silicide layer based on a chemical vapor deposition method, and thus a plurality of pyramid-shaped bases are formed of a pyramidal base made of metal silicide and a carbon thin film formed on the surface of the base. And a step of obtaining an electron emitting portion composed of the electron emitting body on the cathode electrode (hereinafter, sometimes referred to as a first manufacturing method).

Examples of the silicon-containing layer include a single crystal silicon layer, an amorphous silicon layer, a single crystal silicon carbide layer and an amorphous silicon carbide layer. The same applies to the following.

Second aspect of the present invention for achieving the above object
The method of manufacturing a cold cathode field emission device according to the aspect of
(A) a cathode electrode provided on the support; (B) an electron emitting portion composed of a plurality of cone-shaped electron emitting members formed on the cathode electrode; and (C) above the electron emitting portion. And a gate electrode having an opening, and the electron emitter comprises a pyramidal base formed of metal silicide on the cathode electrode, and a carbon thin film formed on the surface of the base. A method for manufacturing a cold cathode field emission device, comprising: (a) a step of forming a metal silicide layer on a cathode electrode; and (b) a chemical vapor phase on the metal silicide layer. And a step of forming a carbon thin film based on a growth method.

Second aspect of the present invention for achieving the above object
In the method for manufacturing a cold cathode field emission display device according to the aspect, 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 have their peripheral portions. The cold cathode field emission device is composed of (A) a cathode electrode provided on a support and (B) a plurality of cone-shaped electron emission devices formed on the cathode electrode. An electron emitting portion,
(C) A gate electrode having an opening is provided above the electron-emitting portion, and the electron-emitting body has a pyramidal base formed of metal silicide on the cathode electrode, and
A method of manufacturing a so-called three-electrode type cold cathode field emission display device, which comprises a carbon thin film formed on the surface of the base, wherein an electron emitter is (a) a metal silicide layer on the cathode electrode. Is formed, and (b) a step of forming a carbon thin film on the metal silicide layer by a chemical vapor deposition method is performed.

In the method of manufacturing a cold cathode field emission device according to the second aspect of the present invention or the method of manufacturing a cold cathode field emission display device according to the second aspect, a method of forming an electron emitter is used. More specifically, (a) forming an insulating layer on the support and the cathode electrode, forming a gate electrode having an opening on the insulating layer, and then forming an opening on the gate electrode. A step of 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 central portion of the second opening, On the cathode electrode, on the side surface of the second opening,
A step of forming on the side surface of the opening, on the gate electrode, and on the insulating layer, and (c) sequentially forming a silicon-containing layer and a metal layer on the mask layer and the exposed cathode electrode to form the mask layer and the silicon-containing layer thereon. A step of reacting the silicon-containing layer and the metal layer to form a metal silicide layer on the cathode electrode after removing the layer and the metal layer, and (d) a chemical vapor deposition method on the metal silicide layer. On the cathode electrode, a carbon thin film is formed based on a pyramidal base formed of metal silicide and a plurality of pyramidal electron emitters formed of the carbon thin film formed on the surface of the base. The method (hereinafter, sometimes referred to as the 2A production method) including the step of obtaining

In the step (c) of the second manufacturing method, the metal layer and the silicon-containing layer may be sequentially formed on the cathode electrode. In addition, before forming the carbon thin film, a plasma processing method in which a process gas is appropriately selected (described later)
It is preferable to remove the natural oxide film formed on the surface of the metal silicide layer.

Alternatively, (a) a step of forming on the support a cathode electrode in which a silicon-containing layer and a metal layer are sequentially formed in a surface region where an electron emitting portion is to be formed, and (b) a silicon-containing layer. A step of reacting with the metal layer to form a metal silicide layer on the cathode electrode; and (c) forming an insulating layer on the entire surface, forming a gate electrode having an opening on the insulating layer, and then forming the gate electrode. Forming a second opening communicating with the opening provided in the insulating layer in the insulating layer and exposing the metal silicide layer at the bottom of the second opening; and (d) chemical vapor deposition on the metal silicide layer. A carbon thin film is formed on the basis of a phase growth method, and an electron emitting portion is formed of a pyramidal base made of metal silicide and a plurality of pyramidal electron emitters made of the carbon thin film formed on the surface of the base. To obtain on the cathode electrode, Et consisting method (hereinafter sometimes referred to as a manufacturing method of the 2B) can be exemplified.

In the step (a) of the manufacturing method 2B, a metal layer and a silicon-containing layer may be sequentially formed on the surface region where the electron emitting portion is to be formed, and a cathode electrode may be formed on the support. Good. In addition, before forming the carbon thin film, a plasma processing method in which a process gas is appropriately selected (described later)
It is preferable to remove the natural oxide film formed on the surface of the metal silicide layer.

Alternatively, (a) a step of forming on the support a cathode electrode in which a silicon-containing layer and a metal layer are sequentially formed in a surface region where an electron emitting portion is to be formed, and (b) an insulating layer over the entire surface. And forming a gate electrode having an opening on the insulating layer, and then forming a second opening communicating with the opening provided on the gate electrode in the insulating layer, and forming a bottom of the second opening. A step of exposing the metal layer to the cathode, (c) a step of reacting the silicon-containing layer and the metal layer to form a metal silicide layer on the cathode electrode, and (d) a chemical vapor phase on the metal silicide layer. A carbon thin film is formed based on the growth method,
Thus, a step of obtaining, on the cathode electrode, an electron emitting portion composed of a pyramidal base made of metal silicide and a plurality of pyramidal electron emitters made of a carbon thin film formed on the surface of the base. (Hereinafter, it may be referred to as a 2C manufacturing method).

In the second manufacturing method C, if the metal silicide layer is formed by the plasma treatment method (described later) in which the process gas is appropriately selected in the step (c), the surface of the metal layer is formed. This is preferable since the formed natural oxide film can be removed and the metal layer can be silicidized at the same time. Moreover, in the step (a) of the manufacturing method of the second C,
A cathode electrode having a metal layer and a silicon-containing layer sequentially formed on a surface region where an electron emitting portion is to be formed is formed on a support, and in the step (b), a silicon-containing layer is formed on the bottom of the second opening. It may be exposed.

Alternatively, (a) a step of forming a cathode electrode having a silicon-containing layer formed on a surface region where an electron emitting portion is to be formed on a support, and (b) forming an insulating layer on the entire surface, Forming a gate electrode having an opening on the insulating layer,
Then, a second electrode communicating with the opening provided in the gate electrode
Forming an opening in the insulating layer and exposing the silicon-containing layer at the bottom of the second opening; and (c) a mask layer having a hole in the center of the second opening, the silicon-containing layer. Forming a metal layer on the mask layer and the exposed silicon-containing layer, and forming the metal layer on the mask layer and the exposed silicon-containing layer. And a step of forming a metal silicide layer on the cathode electrode by reacting the silicon-containing layer and the metal layer after removing the metal layer thereon, and (e) chemical vapor deposition on the metal silicide layer. A carbon thin film is formed based on the method, and a cathode is formed of an electron emitting portion including a pyramidal base made of metal silicide and a plurality of pyramidal electron emitters formed of the carbon thin film formed on the surface of the base. The step of obtaining on the electrode, May be referred to as the method of manufacturing)
Can be mentioned.

In the second manufacturing method, in step (a), a cathode electrode having a metal layer formed on a surface region where an electron emitting portion is to be formed is formed on a support, and the step (a) is performed. In d), a silicon-containing layer may be formed on the mask layer and the exposed metal layer. In addition, before forming the carbon thin film, it is preferable to remove the natural oxide film formed on the surface of the metal silicide layer by a plasma treatment method (described later) in which the process gas is appropriately selected.

Alternatively, (a) a step of forming on the support a cathode electrode in which a silicon-containing layer and a metal layer are sequentially formed in a surface region where an electron emitting portion is to be formed, and (b) a silicon-containing layer. A step of reacting with a metal layer to form a metal silicide layer, and (c) a carbon thin film is formed on the metal silicide layer based on a chemical vapor deposition method. A step of obtaining, on a cathode electrode, an electron-emitting portion composed of a plurality of cone-shaped electron-emitting bodies composed of a base and a carbon thin film formed on the surface of the base;
(D) An insulating layer is formed on the entire surface, a gate electrode having an opening is formed on the insulating layer, and then a second opening communicating with the opening provided in the gate electrode is formed in the insulating layer, The step and method of exposing the electron emitting portion to the bottom of the second opening (hereinafter, sometimes referred to as the 2E manufacturing method) can be mentioned.

In the step (a) of the manufacturing method 2E, even if a cathode electrode in which a metal layer and a silicon-containing layer are sequentially formed on a surface region where an electron emitting portion is to be formed is formed on a support. Good. In addition, before forming the carbon thin film, a plasma processing method in which a process gas is appropriately selected (described later)
It is preferable to remove the natural oxide film formed on the surface of the metal silicide layer.

The cold cathode field emission device having the first structure can be obtained by these manufacturing methods 2A to 2E.

Alternatively, in the method for manufacturing the cold cathode field emission device according to the second aspect of the present invention or the method for manufacturing the cold cathode field emission display device according to the second aspect, (a) insulation A step of forming a band-shaped or double-sided gate electrode support made of a material on a support, and forming a cathode electrode and an electron emission part on the support; and (b) a band having a plurality of openings. A step of stretching the strip-shaped material such that the gate electrode made of the material is in contact with the top surface of the gate electrode supporting portion and the opening is located above the electron emission portion (hereinafter referred to as 2F May be referred to as a manufacturing method). Thereby, the cold cathode field emission device having the second structure can be obtained. Incidentally, the formation of the cathode electrode and the electron emitting portion can be basically carried out based on the above-mentioned first manufacturing method.

In the manufacturing method of the 2nd F, when the gate electrode supporting portion is a region between adjacent stripe-shaped cathode electrodes, or when a plurality of cathode electrodes form one cathode electrode group, adjacent cathode electrodes are formed. It may be formed in a region between the electrode groups. A conventionally known insulating material can be used as a material forming the gate electrode supporting portion. For example, a widely used low melting glass mixed with a metal oxide such as alumina, or an insulating material such as SiO ₂ can be used. Materials can be used. Examples of the method of forming the gate electrode support 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 photosensitizing method. The dry film method is to laminate a photosensitive film on a support, remove the photosensitive film at the site where the gate electrode support is to be formed by exposure and development, and form the gate electrode support in the opening created by the removal. This is a method of burying an insulating material for baking and firing.
The photosensitive film is burned and removed by firing, and the insulating material for forming the gate electrode supporting portion, which is buried in the opening, remains to serve as the gate electrode supporting portion. 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, the insulating material is patterned by exposure and development, and then baking is performed.

The cold cathode field emission device or the manufacturing method thereof according to the first or second aspect of the present invention, and the cold cathode field emission display device or the manufacturing method thereof according to the first or second aspect. In, the base is formed on the cathode electrode.
(1) A structure in which the base is directly formed on the cathode electrode, (2) A structure in which the base is formed on the cathode electrode via a metal silicide layer, and (3) A base is a silicon-containing layer on the cathode electrode. A structure formed through
(4) The structure in which the base is formed on the cathode electrode via the silicon-containing layer and the metal silicide layer, and (5) the structure in which the base is formed on the cathode electrode via the metal layer and the metal silicide layer. Included.

Electron emitter of the present invention or method of manufacturing the same, cold cathode field according to the first or second aspect Electron emitting device or method of manufacturing the same, cold cathode electric field according to the first or second aspect In the electron emission display device or the manufacturing method thereof (hereinafter, these may be collectively referred to simply as the present invention), the carbon thin film is composed of graphite or fullerene having sp ² bond,
Alternatively, it is composed of amorphous carbon. The thickness of the carbon thin film on the base is 1 nm to 0.3 μm, preferably 5 n
It is preferably m to 30 nm. The carbon atom having the sp ² bond usually forms a 6-membered ring from 6 carbon atoms, and the 6-membered ring is collected to form a graphite sheet. Further, the graphite sheet is rolled to form a tube structure. This is a carbon nanotube. Carbon nanotubes include single-walled carbon nanotubes having a structure in which one layer of carbon graphite sheet is wound and multi-walled carbon nanotubes having a structure in which two or more layers of carbon graphite sheet are wound. Carbon formed at or near the tip of the emitter
Nanotubes are of either type depending on the formation conditions.

In the present invention, nickel (Ni), cobalt (Co), titanium (Ti), tantalum (as metal forming the metal silicide or metal silicide layer, or metal forming the metal layer) At least one material selected from the group consisting of Ta), molybdenum (Mo), iron (Fe), platinum (Pt), palladium (Pt), gold (Au), chromium (Cr) and alloys of these metals. Can be mentioned. Here, silicide is silicon (Si) and an element that is more electrically positive than silicon (Si).
The original compound is meant. The metal silicide forming the base of the electron emitter may contain a small amount of carbon or oxygen when the electron emitter is manufactured, but due to the characteristics of the electron emitter,
No problems arise. The thickness of the metal silicide layer before forming the carbon thin film is 1 nm or more, preferably 5 nm or more.

The upper limit of the reaction temperature at the time of reacting the silicon-containing layer and the metal layer to form the metal silicide layer is
It is necessary to make the temperature that the support can withstand. Further, the lower limit of the reaction temperature needs to be a temperature at which silicidation can be achieved.

The metal layer is formed by various well-known physical vapor deposition (PVD) methods such as sputtering and vapor deposition.
Method), a CVD method, a coating method, or an electrodeposition method. Further, the reaction between the silicon-containing layer and the metal layer can be achieved by, for example, heating, or can also be achieved by an ion beam method, an ion implantation method, or a plasma treatment method. In the case of heating, as the atmosphere, a vacuum atmosphere or a reduced pressure atmosphere, an inert gas atmosphere such as helium gas, neon gas, argon gas, or nitrogen gas, a hydrogen gas atmosphere, an ammonia gas atmosphere,
An oxygen gas atmosphere can be mentioned. Further, as process gas in the plasma processing method (or the sputtering processing method), helium, argon, neon, nitrogen, oxygen,
At least one gas selected from the group consisting of ammonia and hydrogen may be mentioned. In this case, the substance forming the gas may be contained as an impurity in the obtained metal silicide layer, but There is no problem in the characteristics of the electron emitter obtained in 1. As conditions for plasma excitation, a temperature from room temperature to a temperature that the support can withstand for 1 minute or more, bias power: 0 W to 600 W, DC
Power: 0 W to 600 W, process gas flow rate: 1 to 10
00 sccm, pressure: 1 × 10 ⁻⁴ Pa to 1 × 10 ² Pa
Can be illustrated. In some cases, during the formation of the metal layer, the support may be heated so that the metal layer is silicided together with the formation of the metal layer. Further, by appropriately selecting the process gas, the natural oxide in the metal layer or the metal silicide layer can be removed by the plasma processing method (or the sputtering processing method).

When the carbon thin film is formed on the metal silicide layer by the chemical vapor deposition method, the upper limit of the temperature of the support needs to be a temperature that the support can withstand. Further, the lower limit of the temperature is the lowest temperature at which the carbon thin film is formed, and specifically, it is desirable to set it to 150 ° C or higher, preferably 200 ° C or higher. CV for forming carbon thin film
As a hydrocarbon-based gas that is a raw material gas in the D method, methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C
₃ H ₈ ), butane (C ₄ H ₁₀ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), etc., hydrocarbon-based gas, mixed gas thereof, and mixture of hydrocarbon-based gas and hydrogen gas Gas can be mentioned. Furthermore, a gas obtained by vaporizing methanol, ethanol, acetone, benzene, toluene, xylene, naphthalene, or the like, or a mixed gas of these gases and hydrogen can be used. Further, in order to stabilize the discharge and promote plasma dissociation, a dilution gas such as helium (He) or argon (Ar) may be mixed, or a doping gas such as nitrogen or ammonia may be mixed. Good.
As a CVD condition, bias power: 0 W to 600 W,
Alternatively, DC power: 0 W to 600 W, film formation time: 1 to
30 minutes, pressure: 1 * 10 < ^-4 > Pa-1 * 10 < ² > Pa can be illustrated.

As a material for the substrate or the cathode electrode in the cold cathode field emission device, tungsten (W), niobium (Nb), tantalum (Ta), molybdenum (Mo), chromium (Cr), aluminum (A) is used.
l), metals such as copper (Cu); alloys or compounds containing these metal elements (for example, nitrides such as TiN); semiconductors such as silicon (Si); or ITO (indium tin oxide). it can. Examples of the method of forming the cathode electrode include vapor deposition methods such as electron beam vapor deposition method and hot filament vapor deposition method, sputtering method, combination of CVD method, ion plating method and etching method, screen printing method, plating method, lift-off method and the like. be able to. By the screen printing method or the plating method, it is possible to directly form the stripe-shaped cathode electrode.

As a material forming the gate electrode in the cold cathode field emission device having the first structure, tungsten (W), niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum (Mo), chromium is used. (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 (eg, nitrides such as TiN); or semiconductors such as silicon (Si); ITO (indium tin oxide); Examples thereof include conductive metal oxides such as indium oxide and zinc oxide. Known methods for forming a gate electrode include CVD, sputtering, vapor deposition, ion plating, electroplating, electroless plating, screen printing, laser ablation, and sol-gel method. Thus, a thin film made of the above-mentioned constituent materials is formed on the insulating layer. When the thin film is formed on the entire surface of the insulating layer, the thin film is patterned using a known patterning technique,
A stripe-shaped gate electrode is formed. After forming the stripe-shaped gate electrode, the opening may be formed in the gate electrode, or the opening may be formed in the gate electrode simultaneously with the formation of the stripe-shaped gate electrode. Further, by forming a resist pattern on the insulating layer before forming the gate electrode conductive material layer, the gate electrode can be formed by the lift-off method. Furthermore, when 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. Also,
The gate electrode can be provided by appropriately selecting a band-shaped material having an opening from the above-described materials and manufacturing it in advance, and fixing the band-shaped material on the gate electrode support section, whereby the second structure can be provided. It is possible to obtain a cold cathode field emission device having.

In the cold cathode field emission display according to the present invention, the anode panel comprises a substrate, a phosphor layer and an anode electrode. The surface irradiated with electrons is composed of a phosphor layer depending on the structure of the anode panel, or alternatively,
It is composed 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 transmissive type (the anode panel corresponds to the display surface) and the anode electrode and the phosphor layer are laminated on the substrate in this order, the substrate is Originally, the anode electrode itself must also 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 a reflection type (the cathode panel corresponds to the display surface),
And, even if it is a transmissive type, if the phosphor layer and the anode electrode are laminated in this order on the substrate, in addition to ITO,
The materials described above in connection with the cathode electrode and the gate electrode can be appropriately selected and used.

As the phosphor constituting the phosphor layer, a phosphor for fast electron excitation or a phosphor for slow electron excitation can be used. When the cold cathode field emission display is a single color 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 a constitutional example of the anode electrode and the phosphor layer,
(1) A structure in which 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 a substrate, and an anode electrode is formed on the phosphor layer The configuration can be mentioned. 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 addition, in the configuration of (2), a metal back film may be formed on the anode electrode.

From the viewpoint of simplifying the structure of the cold cathode field emission display, 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. It should be noted that the electron emitting portion (1 is a region for one pixel or a region for one subpixel) in which the projected images of the striped cathode electrode and the projected image of the striped gate electrode overlap each other Alternatively, a plurality of cold cathode field emission devices) are provided, and such an overlapping region is usually formed in an effective region (region that functions 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 (the shape when the opening is cut by a virtual plane parallel to the surface of the support) 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
The opening may be directly formed depending on the method of forming the gate electrode. 1 opening provided in the gate electrode and communicating with 1 opening provided in the gate electrode 1
Two second opening portions may be provided in the insulating layer, and one electron emitting portion may be provided in the second opening portion provided in the insulating layer. Alternatively, a plurality of opening portions may be provided in the gate electrode. One second opening communicating with the plurality of openings provided in the insulating layer may be provided in the insulating layer, and one or a plurality of electron emitting portions may be provided in the 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 to form the insulating layer.
Known processes such as a coating 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 emitting portion. 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 material containing silicon such as amorphous silicon or silicon carbide (silicon carbide, SiC), S
Examples thereof include refractory metal oxides such as iN, 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 can be exemplified.
The resistance value may be approximately 1 × 10 ⁵ to 1 × 10 ⁷ Ω, preferably several MΩ. If the resistor layer is made of amorphous silicon or silicon carbide, it can also serve as the silicon-containing layer.

At least the surface of the support constituting the cathode panel should be made of an insulating material, and a glass substrate, a glass substrate having an insulating film formed on the surface thereof, a quartz substrate, and an insulating film formed on the surface thereof. Examples thereof include a quartz substrate and a semiconductor substrate having an insulating film formed on the surface thereof. However, from the viewpoint of manufacturing cost reduction, it is preferable to use a glass substrate or a glass substrate having an insulating film formed on the surface. The substrate that constitutes the anode panel can also be configured in the same manner as the support. Also in the electron emitter of the present invention, the substrate needs to be formed on the support, and the support may be made of an insulating material or the above-mentioned material.

When the cathode panel and the anode panel are joined at their peripheral portions, the joining may be performed by using an adhesive layer, or a frame body made of an insulating rigid material such as glass or ceramics and an adhesive layer may be used together. 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 to be longer than that when only the adhesive layer is used. It is possible to Although frit glass is generally used as a constituent material of the adhesive layer, a so-called low melting point metal material having a melting point of about 120 to 400 ° C. may be used. Such low melting point metal materials include In (indium: melting point 157 ° C.); indium-gold low melting point alloy; Sn ₈₀ Ag ₂₀ (melting point 220 to 370 ° C.), S
Tin (Sn) such as n ₉₅ Cu ₅ (melting point 227 to 370 ° C)
System 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; Zn ₉₅ Al ₅ (melting point 380 ° C) and other zinc (Zn) -based high temperature solder; Sn ₅ Pb ₉₅ (melting point 300-
314 ° C.), Sn ₂ Pb ₉₈ (melting point 316 to 322 ° C.) and other standard tin-lead solder; Au ₈₈ Ga ₁₂ (melting point 38
1 ° C) brazing filler metal (the above subscripts all represent atomic%)
Can be illustrated.

When the cathode panel, the anode panel and the frame body are joined together, they may be joined at the same time,
Alternatively, either the cathode panel or the anode panel may be joined to the frame in the first step, and the other cathode panel or the anode panel may be joined to the frame in the second step. If the three-way 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 becomes a vacuum at the same time as the bonding. Alternatively, after the three members are joined together, the space surrounded by the cathode panel, the anode panel, the frame body, and the adhesive layer can be evacuated to create a vacuum. When exhausting is performed after joining, the pressure of the atmosphere during joining may be either normal pressure or reduced pressure, and the gas forming the atmosphere may be atmospheric air, or nitrogen gas or Group 0 of the periodic table. It may be an inert gas containing a gas belonging to (for example, Ar gas).

When the exhaust is carried out after the joining, the exhaust can be carried out through a tip tube previously connected to the cathode panel and / or the anode panel. The tip tube is typically constructed using a glass tube, and the cathode panel and / or
Alternatively, frit glass or the above-mentioned low-melting point metal material is used to join the periphery of the through-hole provided in the invalid area (area that does not function as the actual display area) of the anode panel, and the space reaches a predetermined vacuum degree. After that, it is sealed off by heat fusion. It should be noted that if the entire cold cathode field emission display is once heated and then cooled before the sealing, residual gas can be released into the space, and this residual gas can be removed to the outside of the space by exhaust. Therefore, it is preferable.

In the present invention, since the carbon thin film is formed on the metal silicide layer based on the chemical vapor deposition method, the carbon thin film can be formed at a lower temperature than before due to a kind of catalytic effect of the metal silicide layer. It will be possible.

[0060]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to the drawings on the basis of an embodiment of the invention (hereinafter, simply referred to as an embodiment).

(Embodiment 1) Embodiment 1 is an electron emitter of the present invention, a method for manufacturing the same, and a cold cathode field emission device according to the first aspect (hereinafter abbreviated as field emission device).
The present invention also relates to a manufacturing method thereof (first manufacturing method), a so-called two-electrode type cold cathode field emission display device (hereinafter abbreviated as a display device) according to the first aspect, and a manufacturing method thereof.

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

The electron emitter 26 in the first embodiment is
A pyramidal base portion 24 made of a metal silicide 23 formed on the base body (specifically, on the cathode electrode 11 in the first embodiment), and formed on the surface of the base portion 24 (that is, the base portion 24). A carbon thin film 25).

In addition, the field emission device according to the first embodiment is an electron composed of the cathode electrode 11 provided on the support 10 and a plurality of cone-shaped electron emitters 26 formed on the cathode electrode 11. It consists of the discharge part 15. And
The electron emitter 26 is formed on the surface of the pyramidal base 24 made of the metal silicide 23 formed on the cathode electrode 11 and the base 24 (that is, covering the base 24).
It is composed of a carbon thin film 25. Here, the carbon thin film 2
5 is composed of graphite having sp ² bonds. Further, the electron emitting portion 15 is macroscopically in the form of a thin film. Further, in the display device according to the first embodiment, the cathode panel CP provided with a plurality of field emission devices, and the phosphor layer 31 (red light emitting phosphor layer 31R, green light emitting phosphor layer 31G, blue light emitting phosphor layer). 31B) and the anode electrode 3
And an anode panel AP having a plurality of pixels. In the cathode panel CP of the display device of the first embodiment, a large number of electron emission regions each including a plurality of field emission devices as described above are formed in a two-dimensional matrix in the effective region.

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

Specifically, the anode panel AP covers the entire surface of the substrate 30, the phosphor layer 31 formed on the substrate 30, and having a predetermined pattern (for example, stripe shape or dot shape) and covering the entire surface. The anode electrode 33 is made of an aluminum thin film. Phosphor layer 31
A black matrix 32 is formed on the substrate 30 between the and the phosphor layer 31. The black matrix 32 may be omitted. Further, in the case of assuming a single color display device, the phosphor layer 31 does not necessarily have to be provided according to a predetermined pattern. Further, an anode electrode made of a transparent conductive film such as ITO may be provided between the substrate 30 and the phosphor layer 31, or an anode electrode 33 made of a transparent conductive film provided on the substrate 30 and an anode A light-reflecting conductive film that is composed of a phosphor layer 31 and a black matrix 32 formed on the electrode 33 and aluminum formed on the phosphor layer 31 and the black matrix 32 and is electrically connected to the anode electrode 33. It can also be configured.

One pixel is arranged in the effective region of the anode panel AP so as to face the cathode electrode 11 having a rectangular shape on the cathode panel side, the electron emitting portion 15 formed thereon, and the electron emitting portion 15. And the phosphor layer 31. In the effective area, such pixels are arranged in the order of, for example, hundreds of thousands to millions.

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

In this display device, one pixel unit
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 of the cathode electrodes 11 has a substantially rectangular shape, and is connected to the cathode electrode control circuit 40A via the wiring 11A and a switching element (not shown) including, for example, a transistor. Further, the anode electrode 33 is connected to the acceleration power source 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 emitter 26 forming the electron emitter 15 based on the quantum tunnel effect based on the electric field formed by the anode electrode 33. Electrons are attracted to the anode electrode 33, and the phosphor layer 3
Clash with 1. The brightness is controlled by the voltage applied to the cathode electrode 11.

Hereinafter, the electron emitter according to the first embodiment,
A method of manufacturing a field emission device and a display device will be described with reference to FIGS.
Will be described with reference to.

[Step-100] First, a conductive material layer for forming a cathode electrode is formed on the support 10 made of, for example, a glass substrate. The conductive material layer is made of, for example, an aluminum (Al) layer formed by a sputtering method. Then, the rectangular cathode electrode 11 is formed on the support 10 by patterning the conductive material layer based on the well-known lithography technique and reactive ion etching method (RIE method) (see FIG. 3A). ). at the same time,
Wiring 11A connected to the cathode electrode 11 (see FIG. 2)
Are formed on the support 10. Next, after a silicon-containing layer 20 made of amorphous silicon is formed on the entire surface by a CVD method, a metal layer 21 made of nickel (Ni) is further formed on the entire surface by a sputtering method. After that, the metal layer 21 and the silicon-containing layer 2 are formed on the surface of the cathode electrode 11.
Well known lithographic techniques and RI so that 0 is left
The metal layer 21 and the silicon-containing layer 20 are patterned based on the E method (see FIG. 3B). In this way, it is possible to obtain the cathode electrode 11 in which the silicon-containing layer 20 and the metal layer 21 are sequentially formed on the surface region where the electron emitting portion is to be formed.

[Step-110] After that, the support 10 is loaded into the vacuum chamber, and the inside of the vacuum chamber is once made into a vacuum atmosphere of 1 × 10 ⁻⁴ Pa or less. Then, after introducing nitrogen gas to change the atmosphere in the vacuum chamber to a nitrogen gas atmosphere of about 1 Pa, 4
After heat treatment at 00 ° C for 10 minutes, the silicon-containing layer 2
0 reacts with the metal layer 21 to form the metal silicide layer 22.
Are formed (see FIG. 3C). All the silicon-containing layers 20 reacted with the metal layer 21, and the thickness of the metal silicide layer 22 was 0.1 μm to 1 μm.

[Step-120] Next, CV is performed from the vacuum chamber.
The support 10 is transported to the D apparatus, and the carbon thin film 25 is formed on the metal silicide layer 22 based on the CVD conditions exemplified in Table 1 below. Since the anode electrode 11 is made of aluminum (Al), no carbon thin film is formed on the cathode electrode 11.

[Table 1] Gas used: CH ₄ / H ₂ = 10 to 50/50 to 100 sccm Bias power: 300 to 600 W (13.56 MHz) Film formation time: 5 minutes or more Pressure: 0.1 to 10 Pa

Under such CVD conditions, although the mechanism has not been clarified at present, a conical pyramidal base 24 made of the metal silicide 23 is formed from the metal silicide layer 22 having a flat surface, and this A carbon thin film 25 is deposited on the surface of the base 24, and a plurality of cone-shaped electron emitters 26 are formed.
It is possible to obtain the electron emitting portion 15 consisting of (1) on the cathode electrode 11 (see FIG. 3D). In the figure,
Although the electron emitters 26 are shown as being regularly formed, they are actually randomly formed. Also,
The metal silicide layer 22 is exposed between the electron emitters 26.

[Step-130] Then, 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 body). And 10) are joined at the peripheral edge via the frame 34. At the time of joining, frit glass is applied to a joining portion between the frame 34 and the anode panel AP and a joining portion between the frame 34 and the cathode panel CP, and the anode panel AP, the cathode panel CP and the frame 34 are bonded together. After frit glass is dried by preliminary firing, 10 ~ 3 at about 450 ° C
Perform main firing for 0 minutes. Then, the space surrounded by the anode panel AP, the cathode panel CP, the frame 34, and the frit glass is exhausted through a through hole (not shown) and a tip tube (not shown), and the pressure of the space is 10 ^−4. Pa
When the degree is reached, the tip tube is sealed by heating and melting. In this way, the space surrounded by the anode panel AP, the cathode panel CP, and the frame 34 can be evacuated. After that, wiring with necessary external circuits is performed to complete the display device.

An example of a method of 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 that purpose, for example, a dispersant is dispersed in pure water, and stirring is performed for 1 minute at 3000 rpm using a homomixer. Next, the luminescent crystal particles are put into pure water in which a dispersant is dispersed, and agitated at 5000 rpm for 5 minutes using a homomixer. Then, for example, polyvinyl alcohol and ammonium dichromate are added, sufficiently stirred, and filtered.

In the manufacture of the anode panel AP, the photosensitive coating 50 is formed on the entire surface of the substrate 30 made of glass, for example.
Is formed (applied). Then, the photosensitive film 50 formed on the substrate 30 is exposed by the ultraviolet rays emitted from the exposure light source (not shown) and passed through the hole 54 provided in the mask 53 to form the photosensitive area 51 ( FIG. 4 (A)
reference). Then, the photosensitive film 50 is developed and selectively removed, and the remaining portion of the photosensitive film (the photosensitive film after exposure and development)
52 is left on the substrate 30 (see FIG. 4B). next,
The carbon agent (carbon slurry) is applied to the entire surface, dried and baked, and then the remaining 5 of the photosensitive film is formed by the lift-off method.
By removing 2 and the carbon agent thereon, a black matrix 32 made of the carbon agent 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). ). Then, the 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, and, for example, a red photosensitive luminescent crystal particle composition (phosphor slurry) is applied to the entire surface. After coating, exposing and developing, then coating the whole surface with a green photosensitive luminescent crystal particle composition (phosphor slurry), exposing and developing, and further blue photosensitive luminescent crystal particle composition. (Phosphor slurry) may be applied over the entire surface, exposed and developed. After that, 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. Each phosphor layer 31 can also be formed by a screen printing method or the like.

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

When the structure of the base portion 24 was observed with a transmission electron microscope, it had a conical shape. Further, from the electron beam diffraction image, it was confirmed that the base portion 24 was composed of NiSi and Ni ₃₁ S ₁₂ , that is, was composed of metal silicide. The average thickness of the carbon thin film 25 on the base 24 was 5 nm to 50 nm.

For comparison, a nickel layer was formed on a cathode electrode made of aluminum, and a carbon thin film was formed thereon under the CVD conditions shown in Table 1. The carbon thin film thus obtained did not have any characteristic structure, and only an amorphous carbon film having a very smooth surface was formed.

In the silicidation in [Step-110], instead of the heat treatment, hydrogen plasma treatment (treatment atmosphere pressure: about 1 Pa) at 400 ° C. for 10 minutes, ammonia at 400 ° C. for 10 minutes in a CVD apparatus. Treatment (treatment atmosphere pressure: about 1 Pa), argon plasma treatment (treatment atmosphere pressure: about 1 Pa) at 400 ° C. for 10 minutes were performed. Before the plasma treatment, the inside of the CVD device was once
A vacuum atmosphere of 10 ⁻⁴ Pa or less was used. It was confirmed by electron diffraction that the silicidation could be achieved by these three types of plasma treatments. Note that these processes may be referred to as modified examples of the first embodiment. Furthermore, when a carbon thin film was formed under the CVD conditions shown in Table 1, the same electron emitter 26 could be obtained.

In [Step-120], a carbon thin film was formed under the CVD conditions shown in Table 2 below. As a result, carbon nanotubes extending upward from the tip of the electron emitter 26 or in the vicinity thereof became the carbon thin film 25. Formed integrally.

[Table 2] Gas used: CH ₄ / H ₂ = 20 to 50/20 to 100 sccm Bias power: 300 to 600 W (13.56 MHz) Film formation time: 5 minutes or more Pressure: 0.1 to 10 Pa

One pixel is composed of a striped cathode electrode, an electron emitting portion formed thereon, and a phosphor layer arranged in the effective region of the anode panel so as to face the electron emitting portion. Good. In this case, the anode electrode also has a stripe shape. The projected image of the striped cathode electrode and the projected image of the striped anode electrode are orthogonal to each other. Electrons are emitted from the electron emitting portion located in a region where the projected image of the anode electrode and the projected image of the cathode electrode overlap. The cold cathode field emission display device having such a structure is driven by a so-called simple matrix system. 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,
Selective vacuum 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 emitted into the space, and the electrons are attracted to the anode electrode and collide with the phosphor layer forming the anode panel to excite / emit the phosphor layer.

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

(Embodiment 2) Embodiment 2 is an electron emitter of the present invention and a method for manufacturing the same, a field emission device according to a second aspect and a method for manufacturing the same (manufacturing method 2A), and a second embodiment. The present invention relates to a so-called three-electrode type display device according to the second aspect and a manufacturing method thereof. The field emission device according to the second embodiment has the first structure.

A schematic partial end view of the field emission device according to the second embodiment is shown in FIG. 9, and a schematic partial end view of the display device is shown in FIG. 5, and the cathode panel CP and the anode panel A are shown.
FIG. 6 shows a schematic partial perspective view when P is disassembled. This field emission device includes a cathode electrode 11 (corresponding to a base body), a cathode electrode 11 formed on a support 10.
Gate electrode 1 formed above the gate and having an opening 14A
3 and an electron emitting portion 15 formed on the cathode electrode 11. The opening 14A provided in the gate electrode 13 is referred to as a first opening 14A for convenience. Then, the insulating layer 12 is formed on the support 10 and the cathode electrode 11, and the second opening 14B communicating with the first opening 14A provided in the gate electrode 13 has the insulating layer 12 formed therein.
The electron emitting portion 15 is located at the bottom of the second opening 14B. The electron emitting portion 15 is composed of a plurality of cone-shaped electron emitting bodies 26 formed on the cathode electrode 11. The electron emitter 26 is composed of a pyramidal base 24 made of metal silicide 23 formed on the cathode electrode 11, and a carbon thin film 25 formed on the surface of the base 24. Here, the carbon thin film 25 is s
It is composed of graphite with p ² bonds. Further, the electron emitting portion 15 is macroscopically in the form of a thin film.

The display device is composed of a cathode panel CP having a large number of field emission devices as described above formed in the effective region and an anode panel AP, and is composed of a plurality of pixels, each pixel being a field emission device. 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 at their peripheral portions with the frame 34 interposed therebetween. In the partial end view shown in FIG. 5, in the cathode panel CP, one cathode electrode 11 has openings 14A and 14B and an electron emitting portion 15.
2 are shown for simplification of the drawing, but the present invention is not limited to this, and the basic structure of the field emission device is as shown in FIG. Further, a through hole 36 for vacuum evacuation is provided in the ineffective region of the cathode panel CP, and a chip tube 37 which is closed off after vacuum evacuation is connected to the through hole 36. However, FIG.
Shows the completed state of the display device, and the illustrated tip tube 37 is already sealed. Further, the illustration of the spacer is omitted.

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

When displaying 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 in the gate electrode control circuit 41. A positive voltage higher than that of the gate electrode 13 is applied to the anode electrode 33 from the acceleration power supply 42. When displaying is performed in 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. An electric field generated when a voltage is applied between the cathode electrode 11 and the gate electrode 13 causes electrons to be emitted from the electron emitting portion 15 based on the quantum tunnel effect, and the electrons are attracted to the anode electrode 33, so that the phosphor layer 31. Clash with. As a result, the phosphor layer 31 is excited and emits light, and a desired image can be obtained.

Hereinafter, a method of manufacturing an electron emitter, a method of manufacturing a field emission device (manufacturing method of 2A) and a method of manufacturing a display device according to the second embodiment will be described with reference to FIGS. 7 to 9.

[Step-200] First, a conductive material layer for forming a cathode electrode is formed on the support 10 made of, for example, a glass substrate, and then the well-known lithography technique and RI are used.
By patterning the conductive material layer based on the E method, the stripe-shaped cathode electrode 11 (corresponding to the base) is formed on the support 10 (see FIG. 7A).
The striped cathode electrode 11 extends in the left-right direction of the drawing sheet. The conductive material layer is made of, for example, an aluminum (Al) layer formed by a sputtering method.

[Step-210] Next, the 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 is formed on the entire surface.
m insulating layer 12 is formed.

[Step-220] After that, the gate electrode 13 having the first opening 14A is formed on the insulating layer 12. Specifically, a conductive material layer made of aluminum (Al) for forming a gate electrode is formed on the insulating layer 12 by a sputtering method, and then the patterned first mask material layer ( (Not shown),
The conductive material layer is etched using the first mask material layer as an etching mask to pattern the conductive material layer 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 by 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 can be obtained. The stripe-shaped gate electrode 13 extends in a direction different from that of the cathode electrode 11 (for example, a direction perpendicular to the paper surface of the drawing).

[Step-230] Then, 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 the RIE method using the second mask material layer as an etching mask,
The masking material layer 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
Corresponding to A, one second opening 14B is formed. 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. These openings 14A and 14B are, for example, one per pixel.
It is sufficient to form about 3000 pieces.

[Step-240] Then, the second opening 1
An electron emitter is formed on the surface of the portion of the cathode electrode 11 located at the bottom of 4B. For that purpose, first, the mask layer 116 in which the surface of the cathode electrode 11 is exposed is formed in the central portion 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 inside of the openings 14A and 14B by a spin coating method, the resist material located at the center of the bottom of the second opening 14B is formed based on the lithography technique. The mask layer 116 can be obtained by forming holes in the layer. In the second embodiment, the mask layer 116 has the second opening 14
It covers a part of the cathode electrode 11 located at the bottom of B, the side wall of the second opening 14B, the side wall of the first opening 14A, the gate electrode 13 and the insulating layer 12. Thereby, in the subsequent steps, the electron emitter is formed on the surface of the portion of the cathode electrode 11 located in the central portion of the bottom of the second opening 14B, but the cathode electrode 11 and the gate electrode 13 are When forming the body, it is possible to reliably prevent a short circuit.

[Step-250] Next, on the mask layer 116 including the exposed surface of the cathode electrode 11, in the same manner as in [Step-100] of the first embodiment, a silicon-containing layer made of amorphous silicon and nickel. A metal layer made of (Ni) is sequentially formed. Then, the mask layer 116 and the silicon-containing layer and the metal layer thereon are removed.

[Step-260] Then, in the same manner as in [Step-110] of the first embodiment or by the same method as described in the modification of the first embodiment, the silicon-containing layer and the metal are formed. Exposed cathode electrode 1 by reacting with the layer
1 on the surface of the metal silicide layer 22 (NiSi and Ni ₃₁
It consists S ₁₂₎ to form a reference ((A in FIG. 8)). All the silicon-containing layers 20 reacted with the metal layer 21, and the thickness of the metal silicide layer 22 was 0.1 μm to 1 μm.

[Step-270] Then, the carbon thin film 25 is formed on the metal silicide layer 22 by the CVD method in the same manner as in [Step-120] of the first embodiment. This state is shown in FIG. Thus, an electron emission is formed by a plurality of cone-shaped electron emitters 26 formed of the pyramidal base 24 made of the metal silicide 23 and the carbon thin film 25 formed on the surface of the base 24 (that is, covering the base 24). The part 15 can be obtained on the cathode electrode 11.
Here, since the anode electrode 11 and the gate electrode 13 are made of aluminum (Al), the carbon thin film is not formed on the cathode electrode 11 and the gate electrode 13.

Incidentally, in [Step-270], when a carbon thin film was formed under the CVD conditions shown in Table 2,
The carbon nanotubes extending upward from the tip of the electron emitter 26 or its vicinity were formed integrally with the carbon thin film.

[Step-280] After that, the side wall surface of the second opening 14B formed in the insulating layer 12 is made to recede by isotropic etching so that the opening end of the gate electrode 13 is exposed. Therefore, it is preferable. In this way, the field emission device shown in FIG. 9 can be completed.
The isotropic etching can be performed by dry etching that uses radicals as a main etching species, such as chemical dry etching, or wet etching that uses an etching solution. The etching liquid is, for example, a 49% hydrofluoric acid aqueous solution and 1: 100 of pure water.
(Volume ratio) A mixed solution can be used.

[Step-290] Then, as in [Step-130] of the first embodiment, the display device is assembled.

When the characteristics of the display device thus obtained were evaluated, a threshold electric field of 10 V / μm or less could be obtained when the electric field when the field emission current was 1 μA / cm ² was taken as the threshold electric field. .

(Embodiment 3) Embodiment 3 is a modification of Embodiment 2. A schematic partial end view of the field emission device of the third embodiment is shown in FIG. This field emission device is also 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 the discharge part 15. Openings 14A, 14
An electron emitting portion 15 is formed on the surface of the portion of the cathode electrode 11 located at the bottom of B. Note that, unlike the field emission device described in the second embodiment, the metal silicide layer 22
Extend into the insulating layer 12. However, depending on the formation state of the metal silicide layer 22, as in the field emission device described in the second embodiment, the metal silicide layer 22 is
Cathode electrode 1 located at the bottom of the openings 14A and 14B
It may be formed only on the surface of part 1.

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 according to the third embodiment is substantially the same as that shown in FIG.
Since the display device is the same as that shown in, the detailed description is omitted.

Hereinafter, a method of manufacturing an electron emitter, a method of manufacturing a field emission device (method of manufacturing 2B) and a method of manufacturing a display device according to the third embodiment will be described with reference to FIGS. 10 and 11.

[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 the support 10 made of, for example, a glass substrate, and then well-known. Patterning the conductive material layer based on the lithographic technique and RIE method of
Striped cathode electrodes 11 are formed on the support 10. The striped cathode electrode 11 extends in the left-right direction of the drawing sheet. The conductive material layer is made of, for example, an aluminum (Al) layer formed by a sputtering method.

[Step-310] Thereafter, in the same manner as in [Step-100] of the first embodiment, a silicon-containing layer 20 made of amorphous silicon and a metal layer 21 made of nickel (Ni) are sequentially formed to form a cathode. The electrode 11 is patterned to have substantially the same shape (see FIG. 10A), or alternatively, the silicon-containing layer 20 and the metal layer 21 are left on the portion of the cathode electrode where the electron emitting portion is to be formed. .

[Step-320] Next, in the same manner as in [Step-110] of the first embodiment, or by the same method as described in the modification of the first embodiment, the silicon-containing layer 20 is formed. To react with the metal layer 21 to form the cathode electrode 1
1 on the surface of the metal silicide layer 22 (NiSi and Ni ₃₁
It consists S ₁₂₎ to form a reference ((B in FIG. 10)).

[Step-330] After that, the insulating layer 12 is formed on the entire surface in the same manner as in [Step-210] of the second embodiment, and in the same manner as in [Step-220] in the second embodiment.
The gate electrode 13 having the first opening 14A is formed on the insulating layer 12. Then, [Step-23 of the second embodiment.
[0], the second opening 14B communicating with the first opening 14A provided in the gate electrode 13 is formed in the insulating layer 1.
2 and expose the metal silicide layer 22 at the bottom of the second opening 14B. Thus, the structure shown in FIG. 10C can be obtained. Also in the third embodiment,
The first opening 14A and the second opening 14B have a one-to-one correspondence relationship. That is, one second opening 14B is formed corresponding to one first opening 14A.
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. These openings 14A and 14B are, for example, one to three per pixel.
About 000 pieces may be formed.

[Step-340] Then, the carbon thin film 25 is formed on the metal silicide layer 22 by the CVD method in the same manner as in [Step-120] of the first embodiment. This state is shown in FIG. In this way, an electron emission is formed of a pyramidal base 24 made of the metal silicide 23 and a plurality of pyramidal electron emitters 26 made of the carbon thin film 25 formed on the surface of the base 24 (that is, covering the base 24). Part 1
5 can be obtained on the cathode electrode 11.

Incidentally, in [Step-340], when a carbon thin film was formed under the CVD conditions shown in Table 2,
The carbon nanotubes extending upward from the tip of the electron emitter 26 or its vicinity were formed integrally with the carbon thin film.

[Step-350] Thereafter, similarly to [Step-280] of the second embodiment, the side wall surface of the second opening 14B provided in the insulating layer 12 is made to recede by isotropic etching. This is preferable from the viewpoint of exposing the open end of the gate electrode 13. Then, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Fourth Embodiment) The fourth embodiment is also a modification of the second embodiment. Hereinafter, a method for manufacturing an electron emitter, a method for manufacturing a field emission device (method for manufacturing 2C) and a method for manufacturing a display device according to the fourth embodiment will be described with reference to FIG.

[Step-400] 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 the support 10 made of, for example, a glass substrate, and then well-known. By patterning the conductive material layer based on the lithographic technique and RIE method of
Striped cathode electrodes 11 are formed on the support 10. The striped cathode electrode 11 extends in the left-right direction of the drawing sheet. The conductive material layer is made of, for example, an aluminum (Al) layer formed by a sputtering method.

[Step-410] Thereafter, in the same manner as in [Step-100] of the first embodiment, a silicon-containing layer 20 made of amorphous silicon and a metal layer 21 made of nickel (Ni) are sequentially formed to form a cathode. The electrode 11 is patterned into substantially the same shape (see FIG. 12A), or alternatively, the silicon-containing layer 20 and the metal layer 21 are left on the portion of the cathode electrode where the electron emitting portion is to be formed. .

[Step-420] After that, the insulating layer 12 is formed on the entire surface in the same manner as in [Step-210] of the second embodiment, and in the same manner as in [Step-220] in the second embodiment.
The gate electrode 13 having the first opening 14A is formed on the insulating layer 12. Then, [Step-23 of the second embodiment.
[0], the second opening 14B communicating with the first opening 14A provided in the gate electrode 13 is formed in the insulating layer 1.
2 and expose the metal layer 21 at the bottom of the second opening 14B. Thus, the structure shown in FIG. 12B can be obtained. Also in the fourth embodiment, the first opening 14A and the second opening 14B have a one-to-one correspondence. That is, corresponding to one first opening 14A,
One second opening 14B is formed. 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. These openings 14
For example, about 1 to 3000 A and 14B may be formed in one pixel.

[Step-430] Next, in the same manner as in [Step-110] of the first embodiment, or by the same method as described in the modification of the first embodiment, the silicon-containing layer 20. And the metal layer 21 are reacted with each other to form a metal silicide layer 22 (made of NiSi and Ni ₃₁ S ₁₂ ) (see FIG. 12C). Depending on the silicidation method, the metal silicide layer 22 may be formed only on the exposed surface of the cathode electrode 11. Further, if the metal silicide layer 22 is formed by a plasma processing method such as a microwave plasma reduction processing, or a sputtering processing method in an argon gas atmosphere, for example, the metal layer 21.
This is preferable since the metal layer can be silicidated at the same time as the removal of the natural oxide film formed on the surface of.

[Step-440] After that, the carbon thin film 25 is formed on the metal silicide layer 22 by the CVD method in the same manner as in [Step-120] of the first embodiment. Thus, as shown in FIG. 11, a plurality of pyramid-shaped bases 24 made of the metal silicide 23 and a plurality of pyramid-shaped carbon thin films 25 formed on the surface of the base 24 (that is, covering the base 24) are formed. Electron emitting portion 1 including electron emitter 26
5 can be obtained on the cathode electrode 11.

Incidentally, in [Step-440], when a carbon thin film was formed under the CVD conditions exemplified in Table 2,
The carbon nanotubes extending upward from the tip of the electron emitter 26 or its vicinity were formed integrally with the carbon thin film.

[Step-450] Then, similarly to [Step-280] 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 of exposing the open end of the gate electrode 13. Then, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Fifth Embodiment) The fifth embodiment is also a modification of the second embodiment. Hereinafter, a method for manufacturing an electron emitter, a method for manufacturing a field emission device (manufacturing method for 2D) and a method for manufacturing a display device according to the fifth embodiment will be described with reference to FIGS. 13 and 14.

[Step-500] First, in the same manner as in [Step-200] of the second embodiment, the stripe-shaped cathode electrodes 11 are formed on the support 10. After that, in the same manner as in [Step-110] of the first embodiment, except that only the silicon-containing layer 20 made of amorphous silicon is formed and then patterned to have substantially the same shape as the cathode electrode 11 ((A) in FIG. 13). Alternatively, a silicon-containing layer 20 is formed on the portion of the cathode electrode where the electron emitting portion is to be formed.
Patterning is performed so that In this way, it is possible to obtain the cathode electrode 11 in which the silicon-containing layer 20 is formed on the surface region where the electron emitting portion is to be formed.

[Step-510] Next, the insulating layer 12 is formed on the entire surface in the same manner as in [Step-210] of the second embodiment, and in the same manner as in [Step-220] in the second embodiment.
The gate electrode 13 having the first opening 14A is formed on the insulating layer 12. Then, [Step-23 of the second embodiment.
[0], the second opening 14B communicating with the first opening 14A provided in the gate electrode 13 is formed in the insulating layer 1.
2 to expose the silicon-containing layer 20 at the bottom of the second opening 14B. Thus, the structure shown in FIG. 13B can be obtained. Also in the fifth 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. still,
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. These openings 14A and 14B are, for example, 1 to 3000 per pixel.
It suffices to form about one piece.

[Step-520] Then, in the same manner as in [Step-240] of the second embodiment, the mask layer 116 in which the silicon-containing layer 20 is exposed is formed at the center of the bottom of the second opening 14B. (See FIG. 13C). Specifically, the resist material layer is formed on the opening 14 by spin coating.
After forming a film on the entire surface including A and 14B, a mask layer 116 is obtained by forming a hole in the resist material layer located at the center of the bottom of the second opening 14B based on the lithography technique. You can In the fifth embodiment, the mask layer 116 has a portion of the silicon-containing layer 20 located at the bottom of the second opening 14B, that is, the second opening 14.
B side wall, first opening 14A side wall, gate electrode 13
And the insulating layer 12 is covered.

[Step-530] Next, nickel (N) is formed on the mask layer 116 including the exposed surface of the silicon-containing layer 20 in the same manner as in [Step-100] of the first embodiment.
The metal layer 21 composed of i) is formed. After that, the mask layer 116 and the metal layer 21 thereon are removed (see FIG. 14A). [Step-11 of the first embodiment
[0] or by a method similar to that described in the modification of the first embodiment, the silicon-containing layer 20 and the metal layer 21 are caused to react with each other to form a metal on the exposed surface of the cathode electrode 11. Silicide layer 22 (NiSi and Ni ₃₁ S ₁₂
Is formed) (see (B) of FIG. 14).

[Step-540] Then, the carbon thin film 25 is formed on the metal silicide layer 22 by the CVD method in the same manner as in [Step-120] of the first embodiment. Thus, as shown in FIG. 8B, a plurality of pyramidal bases 24 made of the metal silicide 23 and a plurality of carbon thin films 25 formed on the surface of the base 24 (that is, covering the base 24) are formed. The electron emitting portion 15 composed of the pyramidal electron emitting body 26 can be obtained on the cathode electrode 11.

Incidentally, in [Step-540], when a carbon thin film was formed based on the CVD conditions exemplified in Table 2,
The carbon nanotubes extending upward from the tip of the electron emitter 26 or its vicinity were formed integrally with the carbon thin film.

[Step-550] After that, similarly to [Step-280] of the second embodiment, the side wall surface of the second opening 14B provided in the insulating layer 12 is made to recede by isotropic etching. This is preferable from the viewpoint of exposing the open end of the gate electrode 13. Then, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Sixth Embodiment) The sixth embodiment is also a modification of the second embodiment. Hereinafter, a method for manufacturing an electron emitter, a method for manufacturing a field emission device (method for manufacturing 2E), and a method for manufacturing a display device according to the sixth embodiment will be described with reference to FIGS. 3 and 15.

[Step-600] 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 the support 10 made of, for example, a glass substrate, and then well-known. Patterning the conductive material layer based on the lithographic technique and RIE method of
Striped cathode electrodes 11 are formed on the support 10 (see FIG. 3A). The striped cathode electrode 11 extends in the left-right direction of the drawing sheet. The conductive material layer is made of, for example, an aluminum (Al) layer formed by a sputtering method.

[Step-610] Thereafter, in the same manner as in [Step-100] of the first embodiment, a silicon-containing layer 20 made of amorphous silicon and a metal layer 21 made of nickel (Ni) are sequentially formed, and an electron is formed. Patterning is performed so that the silicon-containing layer 20 and the metal layer 21 are left on the portion of the cathode electrode where the emission portion is to be formed (FIG. 3B).
Pattern), or alternatively, the cathode electrode 11 is patterned into substantially the same shape.

[Step-620] Thereafter, the silicon-containing layer 20 is formed in the same manner as in [Step-110] of the first embodiment or by the same method as described in the modification of the first embodiment. By reacting with the metal layer 21, a metal silicide layer 22 (made of NiSi and Ni ₃₁ S ₁₂ ) is formed on the exposed surface of the cathode electrode 11 (see FIG. 3C).

[Step-630] Next, the carbon thin film 25 is formed on the metal silicide layer 22 by the CVD method in the same manner as in [Step-120] of the first embodiment ((D) of FIG. 3). reference). Thus, an electron emission is formed by a plurality of cone-shaped electron emitters 26 formed of the pyramidal base 24 made of the metal silicide 23 and the carbon thin film 25 formed on the surface of the base 24 (that is, covering the base 24). The part 15 can be obtained on the cathode electrode 11.

In the process [630], a carbon thin film was formed under the CVD conditions shown in Table 2.
The carbon nanotubes extending upward from the tip of the electron emitter 26 or its vicinity were formed integrally with the carbon thin film.

[Step-640] After that, the insulating layer 12 is formed on the entire surface in the same manner as in [Step-210] of the second embodiment, and in the same manner as in [Step-220] in the second embodiment.
A gate electrode 13 having a first opening 14A is formed on the insulating layer 12 (see FIG. 15A). After that, in the same manner as in [Step-230] of the second embodiment, the second opening 14B communicating with the first opening 14A provided in the gate electrode 13 is formed in the insulating layer 12, and the second opening 14B is formed. Opening 14
The electron emission portion 15 is exposed at the bottom of B. Thus, the structure shown in FIG. 15B can be obtained. Incidentally, FIG.
5B shows a structure in which some of the electron emitters 26 are covered with the insulating layer 12, but all the electron emitters 26 are covered.
May be exposed, or the electron emitter 26 may be formed on the entire surface of the cathode electrode 11. Also in the sixth embodiment, the first opening 14A and the second opening 14B have a one-to-one correspondence. That is, one second opening is provided corresponding to one first opening 14A.
14B is formed. The planar shape of the first and second openings 14A and 14B is, for example, 1 μm to 3 mm in diameter.
It has a circular shape of 0 μm. These openings 14A, 14B
, For example, about 1 to 3000 may be formed in one pixel.

[Step-650] After that, similarly to [Step-280] of the second embodiment, the side wall surface of the second opening 14B provided in the insulating layer 12 is set back by isotropic etching. This is preferable from the viewpoint of exposing the open end of the gate electrode 13. Then, the display device is assembled in the same manner as in [Step-130] of the first embodiment.

(Embodiment 7) Embodiment 7 is also a modification of Embodiment 2. The field emission device according to the seventh embodiment has the second structure. That is, in the field emission device according to the seventh embodiment, a strip-shaped gate electrode support portion 112 made of an insulating material is disposed on the support body 10, a cathode electrode 11 formed on the support body 10, and a plurality of openings 114. The gate electrode 113 made of the strip-shaped material 113A and the electron emitting portion 15 formed on the cathode electrode 11 are in contact with the top surface of the gate electrode supporting portion 112, and the electron emitting portion 15 The strip-shaped material 113A is stretched so that the opening 114 is located above. The electron emitting portion 15 is composed of a plurality of cone-shaped electron emitting bodies 26 formed on the surface of the portion of the cathode electrode 11 located at the bottom of the opening 114.

The strip-shaped material 113A corresponds to the gate electrode supporting portion 1
It is fixed to the top surface of 12 with a thermosetting adhesive (for example, an epoxy adhesive). A schematic partial cross-sectional view of the field emission device according to the seventh embodiment is shown in FIG. 16 (A), in which the cathode electrode 11, the strip-shaped material 113A and the gate electrode 113,
In addition, a schematic layout of the gate electrode support portion 112 is shown in FIG.

An example of the method of manufacturing the field emission device according to the seventh embodiment (method of manufacturing the second F) will be described below.

[Step-700] First, the gate electrode support 112 is formed on the support 10 by, for example, a sandblast method.

[Step-710] After that, the electron emitting portion 15 is formed on the support 10. Specifically, the first embodiment
[Step-100] to [Step-120] of
Cathode electrode 11 and a plurality of cone-shaped electron emitters 26
The electron emitting portion 15 is formed. However, the cathode electrode 11 has a stripe shape, and the gate electrode support portion 112
Support 10 positioned between the gate electrode support 112 and the gate electrode support 112
Is formed in the part of.

[Step-720] Then, the plurality of openings 1
Stripe-shaped material 113A in which 14 is formed,
The plurality of openings 114 are arranged in a state of being supported by the gate electrode supporting portion 112 so that the plurality of openings 114 are located above the electron emitting portion 15, and thus the plurality of openings 114 are composed of the strip-shaped strip-shaped material 113A. Gate electrode 1 having 114
13 is positioned above the electron emitting portion 15. The strip-shaped strip-shaped material 113A can be fixed to the top surface of the gate electrode support portion 112 with a thermosetting adhesive (for example, an epoxy adhesive). The projection image of the striped cathode electrode 11 and the projection image of the striped strip material 113A are orthogonal to each other.

In the seventh embodiment, the support 10
After forming the cathode electrode 11 thereon, the gate electrode support portion 112 may be formed on the support 10 by, for example, a sandblast method. In addition, the gate electrode support portion 11
2 may be formed based on, for example, a combination of the CVD method and the etching method. Furthermore, [Step-700] may be executed after executing [Step-710]. Alternatively, after performing [Step-700], [Step-710]
In the same step as the above, the stripe-shaped cathode electrode is formed, the silicon-containing layer is formed, the metal layer is formed, and further, the metal silicide layer is formed, and then [Step-720].
Then, a carbon thin film may be formed. Alternatively, after performing [Step-700], [Step-71
0], the cathode electrode in a stripe shape is formed, the silicon-containing layer is formed, the metal layer is formed, [Step-720] is performed, and then a metal silicide layer is further formed. A carbon thin film may be formed.

Further, as shown in FIG. 17 which is a schematic partial sectional view in the vicinity of the end of the support 10, both ends of the strip-shaped strip material 113A are fixed to the periphery of the support 10. It can also have a structure. More specifically, for example, a protrusion 117 is formed in advance on the peripheral portion of the support 10, and a thin film 118 of the same material as the material forming the strip-shaped material 113A is formed on the top surface of the protrusion 117. deep.
Then, in a state where the striped strip material 113A is stretched, the thin film 118 is welded by using, for example, a laser. The protrusion 117 can be formed at the same time as the formation of the gate electrode support portion, for example.

The planar shape of the opening 114 in the field emission device of the seventh embodiment is not limited to the circular shape. Modifications of the shape of the opening 114 provided in the strip material 113A are illustrated in FIGS. 18A, 18B, 18C and 18D.

The present invention has been described above based on the embodiments, but the present invention is not limited to these. The various conditions, materials used, configurations and structures of field emission devices and display devices, and manufacturing methods described in the embodiments are examples, and can be changed as appropriate, and constituent materials and forming methods of metal silicide and carbon thin film. The formation conditions of are also examples,
It can be changed appropriately. The carbon thin film is formed exclusively by C
The VD method was used, but instead, the filtered Casodiac vacuum arc method (FCVA method, for example, the document "Properties of filtered-ion-beam-deposite") was used.
d diamondlikecarbon as a function of ion energy ",
PJ Fallon, et al., Phys. Rev. B48 (1993), pp 47
77-4782), arc discharge method, laser ablation method, ion beam method, vapor deposition method, and sputtering method.

When the cathode electrode is made of a metal or metal alloy capable of silicidation, in some cases,
The formation of the metal layer can be omitted. That is, if the cathode electrode is formed from such a material and the silicon-containing layer is formed thereon, the metal silicide layer can be formed by the reaction between the cathode electrode and the silicon-containing layer. Alternatively, when the cathode electrode is made of low-resistance polysilicon or the like doped with impurities, the formation of the silicon-containing layer can be omitted in some cases. That is, if a cathode electrode is formed from such a material and a metal layer is formed thereon, a metal silicide layer can be formed by the reaction between the cathode electrode and the metal layer.

In the field emission device, one electron emission part corresponds to one opening, but a plurality of electron emission parts may be formed in one opening depending on the structure of the field emission device. Corresponding form, or 1 for multiple openings
It is also possible that the two electron emitting portions correspond to each other. 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.
It is also possible to adopt a mode in which the opening portion is provided and one or a plurality of electron emitting portions are provided.

In the cold cathode field emission device of the present invention, the second insulating layer 62 may be further provided on the gate electrode 13 and the insulating layer 12, and the converging electrode 63 may be provided on the second insulating layer 62. . A schematic partial end view of a field emission device having such a structure is shown in FIG. Second insulating layer 62
The third opening 64 communicating with the first opening 14A.
Is provided. The formation of the converging electrode 63 is, for example, in the second embodiment, in [Step-220], after forming the stripe-shaped gate electrode 13 on the insulating layer 12, the second insulating layer 62 is formed. Then, after forming a patterned focusing electrode 63 on the second insulating layer 62, the third opening 6 is formed in the focusing electrode 63 and the second insulating layer 62.
4 is provided, and further the first opening 14A is formed in the gate electrode 13.
Should 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 are assembled may be used, or an effective area may be used. It is also possible to form a focusing electrode of the type in which is coated with one sheet of conductive material.

The focusing electrode is not only formed by such a method, but also, for example, 42% Ni- having a thickness of several tens of μm.
It is also possible to form the focusing electrode by forming an insulating film made of, for example, SiO _{2 on} both surfaces of a metal plate made of Fe alloy, and then punching or etching the region corresponding to each pixel to form an opening. . Then, by stacking the cathode panel, the metal plate, and the anode panel, disposing the frame bodies on the outer peripheral portions of both panels, and applying heat treatment, the insulating film and the insulating layer 12 formed on one surface of the metal plate are separated. It is also possible to complete the display device by adhering the insulating film formed on the other surface of the metal plate to the anode panel, adhering these members together, and then vacuum-sealing.

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

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

[0157]

According to the present invention, since the carbon thin film is formed on the metal silicide layer by the chemical vapor deposition method,
The carbon thin film can be formed at a lower temperature than before due to a kind of catalytic effect of the metal silicide layer. Therefore, the glass substrate can be used, and the manufacturing cost of the cold cathode field emission display can be reduced. Moreover, although the mechanism has not been clarified at present, a pyramidal base made of metal silicide is formed from the metal silicide layer having a flat surface, and further, a carbon thin film is deposited on the surface of the metal silicide to form a cone-shaped electron. As a result of the formation of the emitter,
Electrons are efficiently emitted from the tip of the electron emitter.

[Brief description of drawings]

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

FIG. 2 is a schematic perspective view of one electron emitting portion 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 explaining the method of manufacturing the cold cathode field emission device according to the first embodiment of the invention.

FIG. 4 is a schematic partial cross-sectional view of a substrate and the like for explaining the method of manufacturing the 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 invention.

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

FIG. 7 is a schematic partial cross-sectional view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the second embodiment of the invention.

FIG. 8 is a schematic partial cross-sectional view of the support body 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. 7;

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

FIG. 11 is a schematic partial cross-sectional view of the support body and the like for explaining the method for manufacturing the cold cathode field emission device according to the third embodiment of the invention, following FIG.

FIG. 12 is a schematic partial cross-sectional view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the fourth embodiment of the invention.

FIG. 13 is a schematic partial cross-sectional view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the fifth embodiment of the invention.

14 is a continuation of FIG. FIG. 16 is a schematic partial cross-sectional view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the fifth embodiment of the invention.

FIG. 15 is a schematic partial cross-sectional view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the sixth embodiment of the invention.

FIG. 16 is a schematic partial cross-sectional view of a cold cathode field emission device according to a seventh embodiment of the invention, and a schematic layout diagram of a gate electrode and the like.

FIG. 17 is a schematic partial cross-sectional view of a cold cathode field emission device according to a modification of the seventh embodiment of the invention.

FIG. 18 is a schematic plan view showing a plurality of openings of a gate electrode according to a seventh embodiment of the invention.

FIG. 19 is a schematic partial end view of a modification of the cold cathode field emission device of Embodiment 2 of the present invention, which is a cold cathode field emission device provided with a focusing electrode.

[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
・ ・ ・ Strip material, 14A, 114 ・ ・ ・ Opening portion (first opening portion), 14B ・ ・ ・ Second opening portion, 15 ・ ・ ・ Electron emitting portion, 16,116 ・ ・ ・ Mask layer 117 ... Protrusions, 118 ... Thin film, 20 ... Silicon-containing layer,
21 ... Metal layer, 22 ... Metal silicide layer, 23
... metal silicide, 24 ... base, 25 ... carbon thin film, 26 ... electron emitter, 30 ... substrate, 3
1, 31R, 31G, 31B ... Phosphor layer, 32 ...
・ Black matrix, 33 ... Anode electrode, 3
4 ... Frame body, 35 ... Spacer, 36 ... Through hole, 37 ... Chip tube, 40, 40A ... Cathode electrode control circuit, 41 ... Gate electrode control circuit, 42 ...
..Acceleration power source, 62 ... second insulating layer, 63 ... focusing electrode, 64 ... third opening

Claims (14)

[Claims] 1. An electron emitter comprising a pyramidal base formed of a metal silicide on a substrate and a carbon thin film formed on the surface of the base. 2. A method comprising: (a) forming a metal silicide layer on a substrate; and (b) forming a carbon thin film on the metal silicide layer by chemical vapor deposition. Method for manufacturing electron emitter. 3. A cold cathode electric field comprising: (A) a cathode electrode provided on a support; and (B) an electron emitting portion composed of a plurality of cone-shaped electron emitters formed on the cathode electrode. An electron-emitting device, wherein the electron-emitting body comprises a pyramidal base formed of a metal silicide formed on a cathode electrode, and a carbon thin film formed on the surface of the base. Cold cathode field emission device. 4. (A) a cathode electrode provided on a support; (B) an electron emitting portion composed of a plurality of cone-shaped electron emitters formed on the cathode electrode; and (C) an electron. A gate electrode having an opening is disposed above the emitting portion, and the electron emitter is formed on a cathode electrode by a pyramidal base formed of metal silicide and on a surface of the base. A cold cathode field emission device comprising a thin carbon film. 5. 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 portion communicating with an opening formed in the gate electrode.
5. The cold cathode field emission device according to claim 4, wherein the opening is formed and the electron emission part is exposed at the bottom of the second opening. 6. The cold cathode field emission device according to claim 3, wherein carbon nanotubes are formed at or near the tip of the electron emitter. 7. A cold cathode field emission display in which a cathode panel having a plurality of cold cathode field emission devices and an anode panel having a phosphor layer and an anode electrode are joined together at their peripheral portions. In the apparatus, a cold cathode field emission device is an electron composed of (A) a cathode electrode provided on a support, and (B) a plurality of cone-shaped electron emission devices formed on the cathode electrode. The electron-emitting body is composed of a pyramidal base formed of metal silicide formed on the cathode electrode, and a carbon thin film formed on the surface of the base. Cold cathode field emission display. 8. A cold cathode field emission display in which a cathode panel having a plurality of cold cathode field emission devices and an anode panel having a phosphor layer and an anode electrode are joined at their peripheral portions. In the apparatus, a cold cathode field emission device is an electron composed of (A) a cathode electrode provided on a support, and (B) a plurality of cone-shaped electron emission devices formed on the cathode electrode. An electron emitting portion; and (C) a gate electrode provided above the electron emitting portion and having an opening, wherein the electron emitting body is a pyramidal base formed of a metal silicide on the cathode electrode, and A cold cathode field emission display comprising a carbon thin film formed on the surface of the base. 9. In a cold cathode field emission device, 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. 9. The cold cathode field emission display according to claim 8, wherein a second opening communicating with the opening is formed, and the electron emitting portion is exposed at the bottom of the second opening. 10. The cold cathode field emission display according to claim 7, wherein carbon nanotubes are formed at or near the tip of the electron emitter. . 11. An electron emitting section comprising: (A) a cathode electrode provided on a support; and (B) an electron emitting portion formed of a plurality of cone-shaped electron emitting bodies formed on the cathode electrode. The emitter is a conical pyramidal base formed on the cathode electrode, and a method for manufacturing a cold cathode field emission device including a carbon thin film formed on the surface of the base, Forming an electron emitter by (a) forming a metal silicide layer on the cathode electrode; and (b) forming a carbon thin film on the metal silicide layer by chemical vapor deposition. A method of manufacturing a cold cathode field emission device, which is characterized. 12. (A) a cathode electrode provided on a support; (B) an electron emitting portion composed of a plurality of cone-shaped electron emitters formed on the cathode electrode; and (C) an electron. A gate electrode having an opening is disposed above the emitting portion, and the electron emitter is formed on a cathode electrode by a pyramidal base formed of metal silicide and on a surface of the base. A method of manufacturing a cold cathode field emission device comprising a carbon thin film, comprising: (a) forming a metal silicide layer on a cathode electrode; and (b) forming a metal silicide layer on the metal silicide layer. And a step of forming a carbon thin film based on the chemical vapor deposition method, and forming the cold cathode field emission device. 13. A cold cathode field electron emission device comprising a cathode panel having a plurality of cold cathode field emission devices and an anode panel having a phosphor layer and an anode electrode joined together at their peripheral portions. The element comprises (A) a cathode electrode provided on a support, and (B) an electron emitting portion composed of a plurality of cone-shaped electron emitters formed on the cathode electrode. Is a method for manufacturing a cold cathode field emission display comprising a conical pyramidal base formed on a cathode electrode and a carbon thin film formed on the surface of the base. The emitter is formed by (a) forming a metal silicide layer on the cathode electrode, and (b) forming a carbon thin film on the metal silicide layer by chemical vapor deposition. A method of manufacturing a cold cathode field emission display device. 14. A cold cathode field electron emission device comprising a cathode panel having a plurality of cold cathode field emission devices and an anode panel having a phosphor layer and an anode electrode joined together at their peripheral portions. The device includes (A) a cathode electrode provided on a support, (B) an electron emitting portion composed of a plurality of cone-shaped electron emitting bodies formed on the cathode electrode, and (C) an electron emitting portion. Which is a gate electrode having an opening, and the electron emitter is a pyramidal base formed of a metal silicide formed on the cathode electrode, and a carbon thin film formed on the surface of the base. A method of manufacturing a cold cathode field emission display, comprising: (a) a step of forming a metal silicide layer on a cathode electrode; and (b) a chemical step on the metal silicide layer. Physical phase The manufacturing method of a cold cathode field emission display, and forming the process of forming the carbon film on the length method.