JP2002134017A - Method of manufacturing cold-cathode field electron emission display device and method of manufacturing anode panel for cold-cathode field electron emission display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an anode panel for a cold- cathode field electron emission display panel, which can form an anode as flat as possible. SOLUTION: The method for manufacturing the anode panel comprises: a step (A), where partitions 21 are formed on an substrate 20; a step (B), where fluorescent substance forming layers 22R', 22G', and 22B' made of resin and fluorescent substance particles are formed at spaces between a pair of the partitions 21 respectively; a step (C), where an anode 25 made of a metal thin- film is formed over the partitions and the fluorescent substance forming layers; and a step (D), where the resin as a component of the fluorescent substance forming layers is removed by heat treatment, for fluorescent substance layers 22R, 22G and 22B to be formed at spaces between the pair of the partitions 21 on the substrate respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an anode panel for a cold cathode field emission display, and a method for manufacturing a cold cathode field emission display to which the manufacturing method is applied.

[0002]

2. Description of the Related Art In the field of display devices used for television receivers and information terminal equipment, the conventional mainstream cathode ray tubes (C
RT) to a flat-panel (flat-panel) display device that can meet the demands for thinner, lighter, larger screen, and higher definition. As such a flat display device, a liquid crystal display device (LCD), an electroluminescence display device (ELD), a plasma display device (PD)
P), a cold cathode field emission display (FED: field emission display). Among them, the liquid crystal display device is widely used as a display device for information terminal equipment, but there is still a problem in high brightness and large size for application to a stationary television receiver. . On the other hand, a cold cathode field emission display device is a cold cathode field emission device (hereinafter, referred to as a field emission device) capable of emitting electrons from a solid into a vacuum based on a quantum tunnel effect without using thermal excitation. (Which may be referred to as an element), and has attracted attention in terms of high luminance and low power consumption.

FIG. 3 is a schematic partial end view of a cold cathode field emission display device (hereinafter, may be referred to as a display device) using a field emission device, and a schematic partial view of a cathode panel CP. FIG. 4 shows a perspective view. The illustrated field emission device is a so-called Spindt-type field emission device having a conical electron emission portion 15. The field emission device includes a cathode electrode 11 formed on a support 10, an insulating layer 12 formed on the support 10 and the cathode electrode 11, a gate electrode 13 formed on the insulating layer 12, Electrode 13 and insulating layer 1
2, and a conical electron emitting portion 15 formed on the cathode electrode 11 located at the bottom of the opening 14. Generally, the cathode electrode 11
And the gate electrode 13, the projected images of these two electrodes are formed in stripes in directions orthogonal to each other,
Usually, a plurality of field emission elements are arranged in a region corresponding to a portion where the projected images of these two electrodes overlap (corresponding to a region of one pixel. This region is hereinafter referred to as an overlap region). . Further, such an overlapping area is the cathode panel CP
Are usually arranged in a two-dimensional matrix in the effective area (area functioning as an actual display screen).

On the other hand, the anode panel AP is
And a phosphor layer 22 formed on a substrate 20 and having a predetermined pattern, and an anode electrode 25 formed thereon. One pixel includes a group of a predetermined number of field emission elements arranged in an overlapping area of the cathode electrode 11 and the gate electrode 13 on the cathode panel CP side, and a phosphor on the anode panel AP side facing the group of these field emission elements. And a layer 22. In the effective area, such pixels are arranged, for example, in the order of several hundred thousand to several million. Note that a partition 21 is formed on the substrate 20 between the phosphor layers 22. The partition 2
FIG. 4 schematically shows the arrangement of the first, partition 21 and phosphor layers 22.
6 is shown.

Anode panel AP and cathode panel CP
Are arranged so that the field emission element and the phosphor layer 22 face each other, and are joined via the frame 30 at the peripheral edge, whereby a display device can be manufactured. An ineffective area surrounding the effective area and having a peripheral circuit for selecting a pixel formed therein is provided with a through-hole (not shown) for evacuation, which is sealed after evacuation. The connected tip tube (not shown) is connected. That is, the space surrounded by the anode panel AP, the cathode panel CP, and the frame 30 is in a vacuum.

A relative negative voltage is applied to the cathode electrode 11 from the scanning circuit 40, a relative positive voltage is applied to the gate electrode 13 from the control circuit 41, and the anode electrode 25
A positive voltage higher than that of the gate electrode 13
2 is applied. When displaying on such a display device, for example, a scanning signal is input to the cathode electrode 11 from the scanning circuit 40, and a video signal is input to the gate electrode 13 from the control circuit 41. Cathode electrode 11 and gate electrode 1
An electron is emitted from the electron-emitting portion 15 by a quantum tunnel effect due to an electric field generated when a voltage is applied between the electron-emitting device 3 and the electron-emitting device 3. As a result, the phosphor layer 22 is excited to emit light, and a desired image can be obtained. That is,
The operation of the display device is basically controlled by a voltage applied to the gate electrode 13 and a voltage applied to the electron emission unit 15 through the cathode electrode 11.

The anode electrode 25 has a function of reflecting light emitted from the phosphor layer 22 and a function of reflecting electrons recoiled from the phosphor layer 22 or emitted secondary electrons. In addition, the partition wall 21 prevents electrons recoiled from the phosphor layer 22 or emitted secondary electrons from being incident on another phosphor layer 22 to cause so-called optical crosstalk (color turbidity). Has functions.

Referring to FIGS. 45 and 46, an outline of a method for manufacturing the anode panel AP in the conventional display device will be described.

[Step-10] First, a partition 21 is formed on a substrate 20 made of a glass substrate (see FIG. 45A). The planar shape of the partition is substantially rectangular.

[Step-20] Next, in order to form a red light emitting phosphor layer, for example, polyvinyl alcohol (PV)
A) Dispersing red light-emitting phosphor particles in resin and water;
After applying the red light-emitting phosphor slurry to which ammonium bichromate is added to the entire surface, the red light-emitting phosphor slurry is dried, exposed to light, and developed to obtain a predetermined partition wall 2.
The red light-emitting phosphor layer 22R is formed between the two (see FIG. 45B). This operation is performed using a green light-emitting phosphor slurry,
By performing the same process for the blue light emitting phosphor slurry, a red light emitting phosphor layer 22R, a green light emitting phosphor layer 22G, and a blue light emitting phosphor layer 22B are finally formed between the predetermined partitions 21 (FIG. 45 (C) and a schematic partial plan view of FIG. 46).

[Step-30] After that, each phosphor layer 22
An intermediate film 24 mainly made of an acrylic resin is formed on R, 22G, and 22B (these may be collectively simply referred to as a phosphor layer 22) (see FIG. 45D).
Specifically, the substrate 2 on which the phosphor layer 22 is formed in the water tank
By submerging 0 and forming an acrylic resin film on the water surface, the water in the water tank is drained, whereby the intermediate film 24 made of acrylic resin can be formed on the phosphor layer 22.
The hardness and elongation of the acrylic resin film can be changed by changing the amount of the plasticizer added to the acrylic resin and the conditions for forming the acrylic resin film on the water surface. As a result, the intermediate film 24 is
2 can be formed.

[Step-40] Thereafter, an anode electrode 25 made of aluminum is formed on the entire surface by vacuum evaporation (see FIG. 45 (E)). Finally, when the intermediate film 24 is baked by performing a heat treatment at about 400 ° C., a structure as shown in FIG. 45F can be obtained.

[0013]

As described above, the anode electrode 25 made of aluminum is used for the phosphor layer 2.
Since it has a function of reflecting light emitted from the light source 2, it is required to be as smooth as possible. Incidentally, the smoothness of the anode electrode 25 largely depends on the smoothness of the intermediate film 24. Therefore, it is necessary to form the intermediate film 24 as smooth as possible on the phosphor layer 22. However, in the above-described method for manufacturing the anode panel AP, in [Step-30], the partition wall 21 is formed as if formed at the bottom of the well.
The intermediate film 24 must be formed between them. Therefore,
With the above-described manufacturing method, it is difficult to form a smooth intermediate film 24. It is difficult to employ a spin coating method such as that employed in the formation of an intermediate film in the manufacture of a cathode ray tube because the partition wall 21 exists.

Accordingly, it is an object of the present invention to provide a method of manufacturing an anode panel for a cold cathode field emission display device, which can form an anode electrode as smooth as possible, and a cold cathode to which such a manufacturing method is applied. An object of the present invention is to provide a method of manufacturing a field emission display.

[0015]

According to the present invention, there is provided a method of manufacturing an anode panel for a cold cathode field emission display device, which comprises the steps of: (A) forming a partition on a substrate; B) a step of forming a phosphor forming layer composed of a resin and phosphor particles between partition walls; (C) a step of forming an anode electrode made of a metal thin film on the partition wall and the phosphor forming layer; Removing the resin constituting the phosphor-forming layer by performing a heat treatment, thereby obtaining a phosphor layer on the substrate between the partition walls.

According to a method of manufacturing a cold cathode field emission display of the present invention for achieving the above object, a cathode panel on which a cold cathode field emission device is formed and an anode panel are mounted on the outer periphery thereof. A method for manufacturing a cold cathode field emission display device by bonding, comprising:
(A) a step of forming a partition on a substrate, (B) a step of forming a phosphor forming layer composed of a resin and phosphor particles between the partition, and (C) a metal on the partition and the phosphor forming layer. A step of forming an anode electrode composed of a thin film; and (D) a step of removing a resin constituting the phosphor-forming layer by performing a heat treatment, thereby obtaining a phosphor layer on a substrate between partition walls. It is characterized by being manufactured through

The cold cathode field emission display of the present invention or the method of manufacturing an anode panel for a cold cathode field emission display (hereinafter sometimes collectively referred to simply as the present invention) is provided. In the step (B),
It is preferable to form a phosphor forming layer composed of a resin and phosphor particles between the partition walls based on a printing method from the viewpoint of simplification of the process. As the printing method, any printing method can be adopted as long as a phosphor layer having a desired size can be formed. However, a metal mask printing method using a metal mask having a through hole (metal mask) can be used. It is desirable to employ.

In the present invention, in the step (B), it is preferable to form a phosphor-forming layer in which the upper layer is mainly occupied by the resin and the lower layer is mainly occupied by the phosphor particles. Such a state of the phosphor forming layer can be achieved by appropriately selecting the composition, viscosity, and the like of a material for forming the phosphor forming layer.

In the present invention, the phosphor layer is composed of a red light-emitting phosphor layer, a green light-emitting phosphor layer, and a blue light-emitting phosphor layer. A phosphor forming layer for forming a, a phosphor forming layer for forming a green light emitting phosphor layer, a phosphor forming layer for forming a blue light emitting phosphor layer in any order, based on a printing method, It is preferable to form between predetermined partition walls.

In the present invention, the substrate or the support is
At least the surface only needs to be made of an insulating member, and a glass substrate, a glass substrate having an insulating film formed on the surface, a quartz substrate, a quartz substrate having an insulating film formed on the surface, and an insulating film formed on the surface A semiconductor substrate can be used.

The partition can be formed, for example, from a photosensitive polyimide resin.

As a phosphor material constituting the phosphor particles
Is used by appropriately selecting from conventionally known phosphor materials.
be able to. In case of color display, color purity is NTSC
Close to the prescribed three primary colors, white rose when mixing the three primary colors
The afterglow time is short and the afterglow time of the three primary colors is almost
It is preferred to combine equal phosphor materials.
As a phosphor material constituting the red light emitting phosphor layer, (Y_Two
O_Three: Eu), (Y_TwoO_TwoS: Eu), (YBO)_ThreeEu),
(YVO_Four: Eu), (Y_0.96P_0.60V_0.40O_Four: Eu
_0.04), [(Y, Gd) BO_Three: Eu], (GdBO_Three:
Eu), (ScBO) _Three: Eu), (3.5MgO.0.
5MgF_Two・ GeO_Two: Mn).
As a phosphor material constituting the green light-emitting phosphor layer, (Zn
SiO_Two: Mn), (BaAl)₁₂O₁₉: Mn), (Ba)
Mg_TwoAl₁₆O₂₇: Mn), (MgGa_TwoO_Four: Mn),
(YBO_Three: Tb), (LuBO)_Three: Tb), (Sr_FourS
i_ThreeO₈Cl_Four: Eu) and (ZnS: Cu, Al)
can do. Phosphor constituting blue phosphor layer
As a material, (Y_TwoSiO_Five: Ce), (CaWO)_Four: P
b), CaWO_Four, YP_0.85V_0.15O_Four, (BaMgAl
₁₄O_{twenty three}: Eu), (Sr _TwoP_TwoO₇: Eu), (Sr_TwoP_Two
O₇: Sn) and (ZnS: Ag, Al)
Can be.

As the resin, any resin can be used as long as it can remove the resin constituting the phosphor-forming layer by performing a heat treatment. For example, polyvinyl alcohol (P
VA) Resins, acrylic resins and nitrocellulose resins can be mentioned. It is preferable to use a mixture of a PVA resin and an acrylic resin.

As the metal thin film constituting the anode electrode,
An aluminum thin film having a thickness of 70 to 100 nm can be given.

The condition of the heat treatment for removing the resin constituting the phosphor forming layer may be a temperature and a time such that the substrate, the partition walls and the phosphor layer are not damaged. Note that the heat treatment may be performed under conditions such that a part of the resin remains.

In the method of manufacturing a cold cathode field emission display according to the present invention, the cold cathode field emission device constituting the cathode panel can be any type of cold cathode field emission device, for example, a conical shape. A so-called Spindt type cold cathode field emission device having an electron emission portion, a so-called crown type cold cathode field emission device having a crown-shaped electron emission portion, a so-called flat type cold cathode field emission device having a flat electron emission portion, A flat type cold cathode field emission device and a crater type cold cathode field emission device can be exemplified.

In the present invention, a phosphor-forming layer composed of a resin and phosphor particles is formed between the partitions, and in a later step, the resin is removed by heat treatment, so that a smooth anode electrode is formed on the phosphor layer. Can be easily formed.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on embodiments of the invention with reference to the drawings.

The structure of the display device manufactured by the method of manufacturing a cold cathode field emission display device (hereinafter, may be simply referred to as a display device) of the present invention is substantially the same as the display device shown in FIG. Is the same as Also, the cathode panel CP
Is a schematic partial perspective view similar to FIG. Therefore,
Detailed description of the display device is omitted.

Referring to FIGS. 1 and 2 which are schematic partial cross-sectional views of a substrate and the like, a method of manufacturing a display device of the present invention and a method of manufacturing an anode panel AP for the display device will be described. And a method of manufacturing the display device will be described.

[Step-100] First, a partition 21 is formed on a substrate 20 made of a glass substrate (see FIG. 1A). The planar shape of the partition is substantially rectangular. Specifically, after forming a photosensitive polyimide resin layer on the entire surface of the substrate 20, by exposing and developing such a photosensitive polyimide resin layer, a width of about 40 μm, a length of about 200 μm,
The partition 21 having a height of about 50 μm is formed. The space between the partitions 21 is set to 70 to 80 μm. It is preferable that a black matrix made of, for example, chromium oxide is formed on the surface of the substrate 20 before forming the partition 21.

[Step-110] Next, in order to form a red light emitting phosphor layer, for example, a red light emitting phosphor forming material in which red light emitting phosphor particles are dispersed in a polyvinyl alcohol resin, an acrylic resin and water. And forming a red light emitting phosphor forming layer 22R ′ made of resin and phosphor particles between predetermined partition walls 21 based on a metal mask printing method using a metal mask having through holes (dots). (See FIG. 1B). When the total of the polyvinyl alcohol resin, the acrylic resin, and water (these are collectively referred to as a resin composition) is 100 parts by weight, the ratio of the polyvinyl alcohol resin is 12 parts by weight, and the ratio of the acrylic resin is 5 parts by weight. The viscosity of the resin composition at 20 ° C. was set to 8 to 10 N · s / m ² (0.8 to 1.0 poise). Over time, the phosphor particles settle in the phosphor forming layer, and the upper layer is mainly occupied by the resin,
A state in which the resin layer 23 is formed and the lower layer is mainly occupied by the phosphor particles can be obtained. Then 45-5
The red light-emitting phosphor forming layer 22R ′ is dried at 0 ° C. for 10 minutes, the moisture is evaporated, and the red light-emitting phosphor forming layer 22R ′ is dried.
R 'is in a tack-free state.

In the embodiment, the phosphor layer 22
Are the red light emitting phosphor layer 22R and the green light emitting phosphor layer 22
G, a blue light emitting phosphor layer 22B. Therefore,
By repeating the above operation a total of three times, the phosphor forming layer 22R 'for forming the red light emitting phosphor layer, the phosphor forming layer 22G' for forming the green light emitting phosphor layer, and the blue light emitting phosphor Phosphor forming layer 22B 'for forming a body layer
Are formed in predetermined order between predetermined partition walls based on a metal mask printing method (see FIG. 1C and a schematic partial plan view of FIG. 2).

Unlike the conventional method of manufacturing the anode panel AP, in the embodiment, the phosphor forming layers 22R ', 22G', and 22B 'can be formed by printing three times, so that the process is greatly simplified. Can be achieved.

[Step-120] Thereafter, the anode electrode 25 made of a metal thin film is formed on the partition wall 21 and the phosphor forming layers 22R ', 22G', 22B '. In particular,
An anode electrode 25 made of aluminum having a thickness of 70 nm is formed on the entire surface by vacuum evaporation (FIG. 1D).
reference).

[Step-130] Next, heat treatment is performed at 400 ° C. to form the phosphor forming layers 22R ′ and 22R ′.
The resin constituting G ′, 22B ′ is removed, so that the partition walls 2
The phosphor layers 22 (red light-emitting phosphor layer 22R, green light-emitting phosphor layer 22G, blue light-emitting phosphor layer 2
2B) (see FIG. 1E).

In the embodiment, [Step-110]
, A phosphor-forming layer 22 composed of a resin and phosphor particles
Since R ′, 22G ′, and 22B ′ are formed between the partition walls 21 and the resin is removed by heat treatment in [Step-130], the smooth anode electrode 25 can be easily formed on the phosphor layer 22. Can be.

[Step-140] A cathode panel CP on which cold cathode field emission devices (hereinafter sometimes referred to as field emission devices) are formed is prepared. Then, the display device is assembled. Specifically, the anode panel AP and the cathode panel CP are arranged so that the phosphor layer 22 and the field emission element face each other, and the anode panel AP and the cathode panel CP (more specifically, the substrate 20 and the support 10) and a height of about 1 mm made of ceramics or glass
Are joined at the peripheral portion through the frame body 30 of FIG. In joining, frit glass is applied to a joint between the frame 30 and the anode panel AP and a joint between the frame 30 and the cathode panel CP, and the anode panel AP, the cathode panel CP, and the frame 30 are attached to each other. , After drying the frit glass by pre-firing,
Perform main firing for 0 minutes. Thereafter, the space surrounded by the anode panel AP, the cathode panel CP, the frame 30 and the adhesive layer (not shown) is evacuated through a through-hole (not shown) and a chip tube (not shown). Pressure is 10 ^-4 P
When the temperature reaches about a, the tip tube is sealed off by heating and melting. Thus, the space surrounded by the anode panel AP, the cathode panel CP, and the frame 30 can be evacuated. Alternatively, for example, the frame 30, the anode panel AP, and the cathode panel CP may be bonded in a high vacuum atmosphere. Alternatively, depending on the structure of the display device, the anode panel AP and the cathode panel CP may be bonded without a frame. Thereafter, wiring connection with a necessary external circuit is performed to complete the display device.

Hereinafter, various field emission devices will be described.

The field emission devices can be classified into the following three categories. That is, the field emission device of the first structure includes (a) a support, (b) a striped cathode electrode provided on the support, and (c) an insulating material formed on the support and the cathode electrode. (D) a striped gate electrode provided on the insulating layer, (e) an opening penetrating the gate electrode, and a hole penetrating the insulating layer and communicating with the opening. A) an electron emission portion provided on a portion of the cathode electrode located at the bottom of the hole, and having a structure in which electrons are emitted from the electron emission portion exposed at the bottom of the hole.

As a field emission device having such a first structure, a Spindt type (field emission device in which a conical electron emission portion is provided on a portion of a cathode electrode located at the bottom of a hole), Crown type (a field emission element in which a crown-shaped electron emission portion is provided on a portion of a cathode electrode located at the bottom of a hole), flat type (an approximately flat electron emission portion is located at the bottom of a hole) (A field emission device provided on the portion of the cathode electrode to be formed).

The field emission device having the second structure is formed on (a) a support, (b) a striped cathode electrode provided on the support, and (c) a support and the cathode electrode. An insulating layer, (d) a striped gate electrode provided on the insulating layer, (e) an opening penetrating the gate electrode, and an opening penetrating the insulating layer and communicating with the opening, and a cathode electrode at the bottom. The cathode electrode portion exposed at the bottom of the hole corresponds to an electron emission portion, and has a structure in which electrons are emitted from the cathode electrode portion exposed at the bottom of the hole.

As the field emission device having such a second structure, a flat field emission device that emits electrons from a flat cathode electrode surface, and an electron emission from a projection on the cathode electrode surface having irregularities are formed. Crater type field emission device.

The field emission device of the third structure comprises (a) a support, (b) a striped cathode electrode having an edge portion provided above the support, and (c) at least a cathode electrode. The formed insulating layer, (d) a stripe-shaped gate electrode provided on the insulating layer, and (e) at least an opening penetrating the gate electrode, and penetrating the insulating layer and communicating with the opening. The cathode electrode exposed at the bottom or side wall of the hole corresponds to an electron emission portion, and has a structure in which electrons are emitted from the edge of the cathode electrode exposed at the bottom or side wall of the hole. .
A field emission device having such a structure is also called an edge type field emission device.

In the Spindt-type field emission device, the materials constituting the electron-emitting portion include tungsten, tungsten alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, niobium, niobium alloy, tantalum, tantalum alloy, chromium, and chromium. At least one material selected from the group consisting of alloys and silicon containing impurities (polysilicon or amorphous silicon) can be given. The electron emission portion of the Spindt-type field emission device can be formed by, for example, an evaporation method, a sputtering method, or a CVD method.

In the crown-type field emission device, conductive particles or
Combinations of conductive particles and a binder can be given.
As the conductive particles, carbon-based materials such as graphite; refractory metals such as tungsten (W), niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum (Mo), and chromium (Cr); or ITO ( And a transparent conductive material such as indium tin oxide. As the binder, for example, glass such as water glass or a general-purpose resin can be used. As general-purpose resin, vinyl chloride resin,
Examples thereof include thermoplastic resins such as polyolefin resins, polyamide resins, cellulose ester resins, and fluorine resins, and thermosetting resins such as epoxy resins, acrylic resins, and polyester resins. In order to improve the electron emission efficiency, it is preferable that the particle size of the conductive particles is sufficiently smaller than the size of the electron emission portion. The shape of the conductive particles is spherical, polyhedral, plate-like, needle-like, columnar, amorphous, etc.
Although not particularly limited, it is preferable that the conductive particles have such a shape that the exposed portions of the conductive particles can be sharp projections. Conductive particles having different dimensions and shapes may be mixed and used. The electron emission portion of the crown type field emission device can be formed by, for example, a coating method, a vapor deposition method, or a sputtering method in combination with a lift-off method.

In the flat type field emission device, it is preferable that the material forming the electron emitting portion is made of a material having a work function Φ smaller than that of the material forming the cathode electrode. This may be determined based on the work function of the material constituting the cathode electrode, the potential difference between the gate electrode and the cathode electrode, the required magnitude of the emitted electron current density, and the like. Representative materials for forming the cathode electrode in the field emission device include tungsten (Φ = 4.55 eV) and niobium (Φ = 4.02 to 4.8).
7eV), molybdenum (Φ = 4.53-4.95e)
V), aluminum (Φ = 4.28 eV), copper (Φ =
4.6 eV), tantalum (Φ = 4.3 eV), chromium (Φ = 4.5 eV), and silicon (Φ = 4.9 eV). The electron emitting portion preferably has a work function Φ smaller than these materials, and its value is preferably approximately 3 eV or less. As such materials, carbon (Φ <1 eV), cesium (Φ = 2.14)
eV), LaB ₆ (Φ = 2.66 to 2.76 eV), B
aO (Φ = 1.6 to 2.7 eV), SrO (Φ = 1.2
5 to 1.6 eV), Y ₂ O ₃ (Φ = 2.0 eV), CaO
(Φ = 1.6-1.86 eV), BaS (Φ = 2.05
eV), TiN (Φ = 2.92 eV), ZrN (Φ =
(2.92 eV). It is more preferable that the electron emission portion is made of a material having a work function Φ of 2 eV or less. The material constituting the electron emitting portion is as follows.
It is not necessary to have conductivity.

As a particularly preferable constituent material of the electron-emitting portion, carbon, more specifically, diamond, especially amorphous diamond can be mentioned. When the electron emission portion is made of amorphous diamond, 5 × 1
At 0 ⁷ V / m or less of the electric field strength, can be obtained current density of emitted electrons required for the display device. Further, since the amorphous diamond is an electric resistor, the emission electron current obtained from each electron emission portion can be made uniform, and thus, it is possible to suppress the variation in brightness when incorporated into a display device. Further, since amorphous diamond has extremely high resistance to a sputtering action by ions of residual gas in the display device, the life of the field emission device can be extended.

Alternatively, the material constituting the electron-emitting portion is appropriately selected from materials having a secondary electron gain δ of such a material larger than the secondary electron gain δ of the conductive material constituting the cathode electrode. Is also good. That is, silver (Ag),
Aluminum (Al), gold (Au), cobalt (C
o), copper (Cu), molybdenum (Mo), niobium (N
b), nickel (Ni), platinum (Pt), tantalum (T
a), metals such as tungsten (W) and zirconium (Zr); semiconductors such as silicon (Si) and germanium (Ge); inorganic simple substances such as carbon and diamond; and aluminum oxide (Al ₂ O ₃ ) and barium oxide ( BaO), beryllium oxide (BeO), calcium oxide (CaO), magnesium oxide (MgO), tin oxide (SnO ₂ ), barium fluoride (BaF ₂ ), calcium fluoride (CaF ₂ )
And the like can be appropriately selected. still,
The material forming the electron emitting portion does not necessarily need to have conductivity.

In a field emission device having the second structure (a flat field emission device or a crater type field emission device) or a field emission device having the third structure (edge type field emission device), the electron emission As materials constituting the cathode electrode corresponding to the portion, tungsten (W), tantalum (Ta), niobium (Nb), titanium (Ti), molybdenum (Mo), chromium (Cr), aluminum (A)
l), metals such as copper (Cu), gold (Au), silver (Ag),
Alternatively, examples thereof include alloys and compounds thereof (for example, nitrides such as TiN, and silicides such as WSi ₂ , MoSi ₂ , TiSi ₂ , and TaSi ₂ ), semiconductors such as diamond, and carbon thin films. The thickness of such a cathode electrode is approximately 0.05 to 0.5 μm, preferably 0.1 to 0.5 μm.
It is desirable that the thickness be in the range of 1 to 0.3 μm, but it is not limited to such a range. Examples of the method for forming the cathode electrode include a vapor deposition method such as an electron beam vapor deposition method and a hot filament vapor deposition method, a sputtering method, a combination of a CVD method, an ion plating method and an etching method, a screen printing method, and a plating method. . According to the screen printing method or the plating method, it is possible to directly form a striped cathode electrode.

Alternatively, the light emitting device comprises a second structure (a flat field emission device or a crater type field emission device), a field emission device having a third structure (an edge type field emission device), or a flat field emission device. In the field emission device having the first structure, the cathode electrode and the electron emission portion are
It can also be formed using a conductive paste in which conductive fine particles are dispersed. As the conductive fine particles, graphite powder; barium oxide powder, strontium oxide powder,
Graphite powder mixed with at least one of metal powders; diamond particles or diamond-like carbon powder containing impurities such as nitrogen, phosphorus, boron, and triazole; carbon nanotube powder; (Sr, Ba,
Ca) CO ₃ powder; and silicon carbide powder. In particular, it is preferable to select graphite powder as the conductive fine particles from the viewpoint of reduction of the threshold electric field and durability of the electron emitting portion. The shape of the conductive fine particles
In addition to a spherical shape and a scale-like shape, an arbitrary regular shape or an irregular shape can be adopted. The particle size of the conductive fine particles may be equal to or less than the thickness and pattern width of the cathode electrode and the electron emission portion. The smaller the particle size, the more the number of emitted electrons per unit area can be increased. However, if the particle size is too small, the conductivity of the cathode electrode and the electron emitting portion may be deteriorated. Therefore, the preferable range of the particle size is approximately 0.01 to 4.0 μm.
m. Such conductive fine particles are mixed with a glass component or other suitable binder to prepare a conductive paste, a desired pattern is formed by a screen printing method using the conductive paste, and then the pattern is fired to emit electrons. A cathode electrode and an electron-emitting portion functioning as a portion can be formed. Alternatively, a cathode electrode or an electron emitting portion functioning as an electron emitting portion can be formed by a combination of a spin coating method and an etching technique.

In the field emission device having the first structure including the Spindt-type field emission device and the crown-type field emission device, the cathode electrode is made of tungsten (W), niobium (Nb), niobium (Nb), or the like. Tantalum (T
a), metals such as molybdenum (Mo), chromium (Cr), aluminum (Al), copper (Cu), alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , MoSi ₂ , A semiconductor such as TiSi ₂ or TaSi ₂ ) or silicon (Si);
TO (indium tin oxide) can be exemplified.
Examples of the method for forming the cathode electrode include a vapor deposition method such as an electron beam vapor deposition method and a hot filament vapor deposition method, a sputtering method, a combination of a CVD method, an ion plating method and an etching method, a screen printing method, and a plating method. . According to the screen printing method or the plating method, it is possible to directly form a striped cathode electrode.

In the field emission device having the first to third structures, one electron emission portion may be present in one opening and one hole provided in the gate electrode and the insulating layer. A plurality of electron-emitting portions may exist in one opening and a hole provided in the electrode and the insulating layer, or a plurality of openings may be provided in the gate electrode, and one hole communicating with the opening may be provided. One or a plurality of electron-emitting portions may be provided in the insulating layer and in one hole provided in the insulating layer.

Field emission having first to third structures
In the device, the resistance between the cathode electrode and the electron emission section
A body layer may be provided. Alternatively, the surface of the cathode electrode
Or, if the edge part corresponds to the electron emission part,
If the cathode electrode is a conductive material layer, resistor layer,
May be adopted as a three-layer structure of an electron emission layer. Resistor
By providing a layer, the operation of the field emission device can be stabilized,
Electron emission characteristics can be made uniform. Resistor layer
As a constituent material, silicon carbide (SiC)
Carbon-based materials, SiN, amorphous silicon
Semiconductor materials such as ruthenium oxide (RuO_Two), Oxidation
Examples of refractory metal oxides such as tantalum and tantalum nitride
be able to. As a method of forming the resistor layer, sputtering
, CVD and screen printing methods
Can be. The resistance value is approximately 1 × 10 ^Five~ 1 × 10⁷Ω, good
More preferably, it should be several MΩ.

Tungsten (W), niobium (Nb), tantalum (Ta), molybdenum (Mo),
Metals such as chromium (Cr), aluminum (Al), copper (Cu), alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , MoSi ₂ , T
i Si _2, silicides such as TaSi _2), or silicon (Si) or the like of the semiconductor and diamond, carbon, IT
O (indium tin oxide) can be exemplified.

As the constituent material of the insulating layer, SiO ₂ , Si
N, SiON, and SOG (spin on glass) can be used alone or in appropriate combination. Known processes such as a CVD method, a coating method, a sputtering method, and a screen printing method can be used for forming the insulating layer.

Hereinafter, various field emission devices and a method of manufacturing the same will be described.

[Spindt-type field emission device] FIG.
Is a so-called Spindt-type field emission device having a conical electron emission portion 15. The Spindt-type field emission device includes a support 10, a striped cathode electrode 11 provided on the support 10, an insulating layer 12 formed on the support 10 and the cathode electrode 11, and an insulating layer 1.
2, a stripe-shaped gate electrode 13, an opening penetrating the gate electrode 13, an opening penetrating the insulating layer 12 and communicating with the opening, and a cathode electrode located at the bottom of the opening. It has a conical electron emitting portion 15 provided on the portion 11 and has a structure in which electrons are emitted from the electron emitting portion 15 exposed at the bottom of the hole. The outline of the method for manufacturing this Spindt-type field emission device will be described below with reference to FIGS. 5 and 6, which are schematic partial end views of a support and the like.

[Step-A1] First, a striped cathode electrode 11 made of niobium (Nb) is formed on a support 10 made of, for example, glass, and then an insulating layer 12 made of SiO ₂ is formed on the entire surface. Then, a stripe-shaped gate electrode 13 is formed on the insulating layer 12. The formation of the gate electrode 13 can be performed based on, for example, a sputtering method, a lithography technique, and a dry etching technique.

[Step-A2] Next, a resist layer 16 functioning as an etching mask is formed on the gate electrode 13 and the insulating layer 12 by lithography (FIG. 5).
(A)). Thereafter, an opening is formed in the gate electrode 13 by RIE (Reactive Ion Etching), and a hole is formed in the insulating layer 12. In the following description, the opening and the hole are collectively referred to as the opening 14 unless otherwise specified. The cathode electrode 11 is exposed at the bottom of the opening 14 (hole). Then, the resist layer 1
6 is removed by an ashing technique. Thus, FIG.
(B) can be obtained.

[Step-A3] Next, the electron emission portion 15 is formed on the cathode electrode 11 exposed at the bottom of the opening portion 14. Specifically, the release layer 17 is formed by obliquely depositing aluminum. At this time, by selecting a sufficiently large incident angle of the vapor deposition particles with respect to the normal line of the support 10, the release layer 17 is formed on the gate electrode 13 and the insulating layer 12 without depositing aluminum almost at the bottom of the opening 14. Can be formed. This release layer 17
Protrudes like an eave from the opening end of the opening 14,
This substantially reduces the diameter of the opening 14 (see FIG. 5C).

[Step-A4] Next, for example, molybdenum (Mo) is vertically deposited on the entire surface. At this time, FIG.
As the conductive material layer 18 made of molybdenum having an overhang shape grows on the peeling layer 17 as shown in FIG. Are gradually limited to those passing near the center of the opening 14. As a result, a conical deposit is formed at the bottom of the opening 14, and the conical deposit made of molybdenum becomes the electron-emitting portion 15.

[Step-A5] Thereafter, the release layer 17 is separated from the surfaces of the insulating layer 12 and the gate electrode 13 by an electrochemical process and a wet process, and the conductive material layer 18 above the insulating layer 12 and the gate electrode 13 is removed. Selectively remove. As a result, as shown in FIG.
The electron emission portion 15 having a conical shape can be left on the cathode electrode 11 located at the bottom of the substrate. Thereafter, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13. The isotropic etching can be typically performed under wet etching or dry etching conditions in which radicals are the main etching species.

[Crown Field Emission Device] FIG. 8A is a schematic partial end view of a field emission device comprising a crown type field emission device, and FIG. This is shown in FIG. Crown type field emission device
Cathode electrode 11 formed on support 10 and insulating layer 12 formed on support 10 and cathode electrode 11
A gate electrode 13 formed on the insulating layer 12, an opening 14 penetrating the gate electrode 13 and the insulating layer 12, and a portion of the cathode electrode 11 located at the bottom of the opening 14 (hole). It is composed of a crown-type electron emission section 15A provided.

The method of manufacturing the crown type field emission device is described below with reference to FIGS.
This will be described with reference to FIG.

[Step-B1] First, a striped cathode electrode 11 is formed on a support 10 made of, for example, glass. Note that the cathode electrode 11 extends in the left-right direction on the paper of the drawing. The stripe-shaped cathode electrode 11 is formed, for example, by forming an ITO film on the support 10 to a thickness of about 0.2 μm over the entire surface by a sputtering method, and then forming the ITO film.
It can be formed by patterning a film. The cathode electrode 11 may be a single material layer, or may be formed by laminating a plurality of material layers. For example, the surface layer of the cathode electrode 11 can be made of a material having a higher electrical resistivity than the rest in order to suppress the variation in the electron emission characteristics of each electron emission portion formed in a later step. Note that such a configuration of the cathode electrode can be applied to the cathode electrode of another field emission device. Next, an insulating layer 12 is formed on the support 10 and the cathode electrode 11. Here, as an example, a glass paste is screen-printed on the entire surface to a thickness of about 3 μm. Next, moisture and a solvent contained in the insulating layer 12 are removed,
Further, in order to flatten the insulating layer 12, for example, two-stage baking such as temporary baking at 100 ° C. for 10 minutes and main baking at 500 ° C. for 20 minutes are performed. Instead of the screen printing using the glass paste as described above, a SiO ₂ film may be formed by, for example, a plasma CVD method.

Next, a gate electrode 13 in the form of a stripe is formed on the insulating layer 12. The gate electrode 13 extends in the direction perpendicular to the plane of the drawing. That is, the direction in which the projected image of the gate electrode 13 extends is the stripe-shaped cathode electrode 1.
The angle is 90 degrees with the direction in which the projected image 1 extends.

[Step-B2] Next, in the same manner as in [Step-A2], the gate electrode 13 and the insulating layer 12 are etched based on the RIE method to form openings 14 in the gate electrode 13 and the insulating layer 12. Then, the cathode electrode 11 is exposed at the bottom of the opening 14 (hole). The diameter of the opening 14 is about 2
It is 50 μm.

[Step-B3] Next, on the gate electrode 13,
The release layer 51 is formed on the insulating layer 12 and on the side wall surface of the opening 14.
Is formed (see FIG. 7A). In order to form the release layer 51, for example, a photoresist material is applied to the entire surface by spin coating, and patterning is performed so as to remove only a part of the bottom of the opening 14. At this point, the substantial diameter of the opening 14 is about 1-20 μm
The diameter is reduced to

[Step-B4] Next, as shown in FIG. 7B, a conductive composition layer 52 made of a composition material is formed on the entire surface.
To form The composition raw material used here is, for example, graphite particles having an average particle size of about 0.1 μm as conductive particles.
%, And 40% by weight of No. 4 water glass as a binder. This composition material is spin-coated on the entire surface, for example, at 1400 rpm for 10 seconds. The surface of the conductive composition layer 52 in the opening 14 rises along the side wall surface of the opening 14 due to the surface tension of the composition raw material, and becomes concave toward the center of the opening 14. Thereafter, calcination for removing moisture contained in the conductive composition layer 52 is performed, for example, at 400 ° C. for 30 minutes in the air.

In the composition raw material, the binder is (1)
It may itself be a dispersion medium of conductive particles,
(2) The conductive particles may be coated, or (3) a dispersion medium of the conductive particles may be formed by being dispersed or dissolved in an appropriate solvent. A typical example of the case (3) is water glass, which is a Japanese Industrial Standard (JIS) K140.
Nos. 1 to 4 specified in No. 8 or equivalents thereof can be used. Nos. 1 to 4 are four-grade grades based on the difference in the number of moles (about 2 to 4 moles) of silicon oxide (SiO ₂ ) with respect to 1 mole of sodium oxide (Na ₂ O) as a constituent of water glass. , Each greatly differ in viscosity. Therefore, when water glass is used in the lift-off process, various conditions such as the type and content of the conductive particles dispersed in the water glass, affinity with the release layer 51, and the aspect ratio of the opening 14 are taken into consideration. It is preferred to select the optimal grade of water glass or to prepare and use water glass equivalent to these grades.

Since the binder is generally inferior in conductivity, if the content of the binder is too large relative to the content of the conductive particles in the conductive composition, the electric resistance of the electron emitting portion 15A formed will increase. In addition, there is a possibility that electron emission may not be performed smoothly. Therefore, for example, in the case of a composition raw material obtained by dispersing carbon-based material particles as conductive particles in water glass, for example, the ratio of the carbon-based material particles to the total weight of the composition raw material is determined by the ratio of the electron-emitting portion 15A. It is preferable to select approximately 30 to 95% by weight in consideration of characteristics such as the electric resistance value, the viscosity of the composition raw material, and the adhesiveness between the conductive particles.
By selecting the ratio of the carbon-based material particles within such a range, it is possible to sufficiently lower the electric resistance of the electron-emitting portion 15A to be formed and to maintain good adhesion between the carbon-based material particles. . However, when the alumina particles are mixed with the carbon-based material particles as the conductive particles, the adhesiveness between the conductive particles tends to decrease. Therefore, the carbon-based material particles may be adjusted according to the content of the alumina particles. Is preferably increased, and particularly preferably 60% by weight or more. The composition raw material may contain a dispersant for stabilizing the dispersed state of the conductive particles, and additives such as a pH adjuster, a drying agent, a curing agent, and a preservative. A composition raw material obtained by dispersing a powder in which conductive particles are covered with a coating of a binder (binder) in an appropriate dispersion medium may be used.

As an example, when the diameter of the crown-shaped electron emitting portion 15A is approximately 1 to 20 μm and carbon-based material particles are used as the conductive particles, the diameter of the carbon-based material particle is approximately 0.1 μm to 1 μm. It is preferable to set the range. By selecting the particle diameter of the carbon-based material particles in such a range, sufficiently high mechanical strength is provided at the edge of the crown-shaped electron emission portion 15A, and the adhesion of the electron emission portion 15A to the cathode electrode 11 is improved. It will be good.

[Step-B5] Next, as shown in FIG. 7C, the release layer 51 is removed. Peeling is performed by immersing in a 2% by weight aqueous sodium hydroxide solution for 30 seconds. At this time, the peeling may be performed while applying ultrasonic vibration. Thereby, the portion of the conductive composition layer 52 on the release layer 51 together with the release layer 51 is removed, and the opening 14 is formed.
Only the portion of the conductive composition layer 52 on the cathode electrode 11 exposed at the bottom of the (hole) is left. This remaining portion becomes the electron emitting portion 15A. The shape of the electron-emitting portion 15A is such that its surface is depressed toward the center of the opening 14 and has a crown shape. FIG. 8 shows a state at the time when [Step-B5] is completed. FIG. 8B is a schematic perspective view showing a part of the field emission device, and FIG. 8A is a schematic part taken along line AA of FIG. 8B. It is an end view.
In FIG. 8B, a part of the insulating layer 12 and a part of the gate electrode 13 are cut away so that the entire electron emitting portion 15A can be seen. It is sufficient to provide about 5 to 100 electron emitting portions 15A in one electron emitting region. still,
The binder exposed on the surface of the electron-emitting portion 15A may be removed by etching so that the conductive particles are reliably exposed on the surface of the electron-emitting portion 15A.

[Step-B6] Next, the electron emission portion 15A is fired. The firing is performed in a dry atmosphere at 400 ° C. for 30 minutes. In addition, what is necessary is just to select a baking temperature according to the kind of binder contained in a composition raw material. For example, when the binder is an inorganic material such as water glass, heat treatment may be performed at a temperature at which the inorganic material can be fired. When the binder is a thermosetting resin, the heat treatment may be performed at a temperature at which the thermosetting resin can be cured. However, in order to maintain the adhesion between the conductive particles, it is preferable to perform the heat treatment at a temperature at which the thermosetting resin does not excessively decompose or carbonize. Regardless of which binder is used, the heat treatment temperature needs to be a temperature at which no damage or defects occur in the gate electrode, the cathode electrode, and the insulating layer. The heat treatment atmosphere is preferably an inert gas atmosphere so that the electrical resistivity of the gate electrode or the cathode electrode does not increase due to oxidation or a defect or damage does not occur in the gate electrode or the cathode electrode. When a thermoplastic resin is used as a binder, heat treatment may not be required.

[Flat Field Emission Device-1] FIG. 9C is a schematic partial sectional view of a field emission device comprising the flat field emission device-1. The flat type field emission device-1 is
For example, a cathode electrode 11 formed on a support 10 made of glass, an insulating layer 12 formed on the support 10 and the cathode electrode 11, a gate electrode 13, a gate electrode 13, and an insulating layer formed on the insulating layer 12 An opening 14 that penetrates through the opening 12 and a flat electron-emitting portion 15B provided on a portion of the cathode electrode 11 located at the bottom of the opening 14 (hole). Here, the electron-emitting portion 15B is formed on the striped cathode electrode 11 extending in the direction perpendicular to the plane of FIG. 9C. Also, the gate electrode 1
Reference numeral 3 extends in the left-right direction on the paper surface of FIG. The cathode electrode 11 and the gate electrode 13 are made of chromium (Cr). The electron emitting portion 15B is specifically formed of a thin layer made of graphite powder. Further, a resistor layer 60 made of SiC is provided between the cathode electrode 11 and the electron emitting portion 15B for stabilizing the operation of the field emission device and making the electron emission characteristics uniform. In the flat type field emission device 1 shown in FIG. 9C, the resistor layer 60 and the electron emission portion 15B are formed over the entire surface of the cathode electrode 11, but such a configuration is used. The invention is not limited to the structure, but what is essential is that the electron-emitting portion 15 </ b> B is provided at least at the bottom of the opening 14.

Hereinafter, a method for manufacturing the flat field emission device 1 will be described with reference to FIG. 9 which is a schematic partial cross-sectional view of a support and the like.

[Step-C1] First, a cathode electrode conductive material layer made of chromium (Cr) is formed on the support 10 by a sputtering method, and then the cathode electrode conductive material layer is formed based on a lithography technique and a dry etching technique. Pattern the layer. Thus, the striped cathode electrode 11 can be formed on the support 10 (see FIG. 9A). The cathode electrode 11 is shown in FIG.
Extends in the direction perpendicular to the plane of the drawing.

[Step-C2] Next, the electron-emitting portion 15B is formed on the cathode electrode 11. Specifically, first,
Resistor layer 6 made of SiC on the entire surface by sputtering
Then, an electron emitting portion 15B made of graphite powder paint is formed on the resistor layer 60 by spin coating, and the electron emitting portion 15B is dried. Thereafter, the electron-emitting portion 15B and the resistor layer 60 are patterned according to a known method (see FIG. 9B). Electrons are emitted from the electron emitting portion 15B.

[Step-C3] Next, an insulating layer 12 is formed on the entire surface.
Form. Specifically, the electron-emitting portion 15B and the support 1
0, for example, by the sputtering method_TwoConsisting of
An insulating layer 12 is formed. Note that the insulating layer 12 is
Screen printing of pastes, SiO _TwoLayer CV
It can also be formed based on the method of forming by D method.
Then, a stripe-shaped gate electrode 13 is formed on the insulating layer 12.
Formed.

[Step-C4] Next, based on the same method as in [Step-A2], the opening 14 is formed in the gate electrode 13 and the insulating layer 12, and the electron emission is formed at the bottom of the opening 14 (hole). The portion 15B is exposed. Thereafter, a heat treatment is performed at 400 ° C. for 30 minutes in order to remove the organic solvent in the electron emitting portion 15B. Thereafter, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13. Thus, the field emission device-1 shown in FIG. 9C can be obtained.

[Flat Field Emission Device-2] FIG. 10C is a schematic partial sectional view of the flat field emission device-2. In the flat type field emission device-2 shown in FIG. 10C, the structure of the electron emitting portion 15B is slightly different from the flat type field emission device-1 shown in FIG. 9C. Hereinafter, a method of manufacturing the flat field emission device-2 will be described with reference to FIG. 10 which is a schematic partial cross-sectional view of a support and the like.

[Step-D1] First, a conductive material layer for a cathode electrode is formed on the support 10. Specifically, after a resist material layer (not shown) is formed on the entire surface of the support 10, the resist material layer where the cathode electrode is to be formed is removed. Thereafter, a cathode electrode conductive material layer made of chromium (Cr) is formed on the entire surface by a sputtering method. Further, a resistor layer 60 made of SiC is formed on the entire surface by a sputtering method, and then a graphite powder coating layer is formed on the resistor layer 60 by a spin coating method, and the graphite powder coating layer is dried. Thereafter, when the resist material layer is removed using a stripping solution, the cathode electrode conductive material layer, the resistor layer 60 and the graphite powder paint layer formed on the resist material layer are also removed. Thus, based on the so-called lift-off method, the cathode electrode 11,
A structure in which the resistor layer 60 and the electron emitting portion 15B (electron emitting layer) are stacked can be obtained (see FIG. 10A).

[Step-D2] Next, after an insulating layer 12 is formed on the entire surface, a gate electrode 13 in the form of a stripe is formed on the insulating layer 12 (see FIG. 10B). Thereafter, based on the same method as in [Step-A2], an opening 14 is formed in the gate electrode 13 and the insulating layer 12, thereby exposing the electron emitting portion 15B at the bottom of the opening 14 (hole) (FIG. 10 (C)). Thereafter, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13. Electrons are emitted from the electron emitting portion 15B provided on the surface of the cathode electrode 11 exposed at the bottom of the opening 14.

[Flat Field Emission Device-3] FIG. 12B is a schematic partial end view of another modification of the flat field emission device. In this flat type field emission device-3, the electron emission portion 15C is made of a carbon thin film formed based on the CVD method.

It is preferable to form the electron emission portion from a carbon thin film because the work function of carbon (C) is low and a high emission electron current can be achieved. In order to emit electrons from the carbon thin film, the carbon thin film may be placed in an appropriate electric field (for example, an electric field having an intensity of about 10 ⁶ volt / m).

By the way, when a resist material is used as an etching mask and plasma etching of a carbon thin film such as a diamond thin film is performed using oxygen gas,
As a reaction by-product in the etching reaction system, (C
A carbon-based polymer such as an (H _x ) -based or (CF _x ) -based polymer is generated as a deposition material. Generally, when a depositable substance is generated in an etching reaction system in plasma etching,
This deposited substance is deposited on the side wall surface of the resist material having a low probability of ion incidence or on the processed end surface of the object to be etched to form a so-called side wall protective film. Contribute. However, when an oxygen gas is used as an etching gas, the sidewall protective film made of a carbon-based polymer is immediately removed by the oxygen gas even if formed. Also,
When oxygen gas is used as an etching gas,
The consumption of resist material is also severe. For these reasons, in the conventional oxygen plasma processing of a diamond thin film,
The dimensional conversion difference between the diamond thin film and the mask is large, and anisotropic processing is often difficult.

In order to solve such a problem, for example, a structure in which a carbon thin film selective growth region is formed on the surface of the cathode electrode and an electron emission portion made of a carbon thin film is formed on the carbon thin film selective growth region may be adopted. Just fine. That is, in the manufacture of the flat field emission device-3, after forming a cathode electrode on a support, a carbon thin film selective growth region is formed on the surface of the cathode electrode, and thereafter, a carbon thin film selective growth region is formed on the carbon thin film selective growth region. A thin film (corresponding to an electron emitting portion) is formed. The step of forming the carbon thin film selective growth region on the surface of the cathode electrode is called a carbon thin film selective growth region forming step.

Here, the carbon thin film selective growth region is preferably a portion of the cathode electrode having metal particles adhered on the surface or a portion of the cathode electrode having a metal thin film formed on the surface. In order to further secure the selective growth of the carbon thin film in the carbon thin film selective growth region, sulfur (S), boron (B)
Or it is desirable that phosphorus (P) is attached, and these substances are considered to act as a kind of catalyst,
Thereby, the selective growth of the carbon thin film can be further improved. The carbon thin film selective growth region may be formed on the surface of the portion of the cathode electrode located at the bottom of the opening, and may be formed from the portion of the cathode electrode located at the bottom of the opening to the cathode electrode other than the bottom of the opening. May be formed to extend to the surface of the portion. Further, the carbon thin film selective growth region may be formed over the entire surface of the portion of the cathode electrode located at the bottom of the opening, or may be formed partially.

In the step of forming the carbon thin film selective growth region, the surface of the portion of the cathode electrode where the carbon thin film selective growth region is to be formed (hereinafter may be simply referred to as the surface of the cathode electrode).
And a step of forming a metal thin film on the surface, thereby selectively growing a carbon thin film comprising a portion of the cathode electrode having the metal particles attached to the surface or the metal thin film formed on the surface. It is preferable to obtain a region.
In this case, in order to further ensure the selective growth of the carbon thin film in the carbon thin film selective growth region, sulfur (S), boron (B) or phosphorus (P) is added to the surface of the carbon thin film selective growth region. It is desirable that the carbon thin film be adhered, so that the selective growth of the carbon thin film can be further improved. As a method of attaching sulfur, boron or phosphorus to the surface of the carbon thin film selective growth region, for example, a compound layer made of a compound containing sulfur, boron or phosphorus is formed on the surface of the carbon thin film selective growth region, and then, for example, heating is performed. By subjecting the compound layer to treatment, the compound constituting the compound layer is decomposed to leave sulfur, boron, or phosphorus on the surface of the carbon thin film selective growth region. Examples of compounds containing sulfur include thionaphthene, thiophthene, and thiophene. Examples of the compound containing boron include triphenylborane. Examples of the phosphorus-containing compound include triphenylphosphine.

Alternatively, in order to further ensure the selective growth of the carbon thin film in the carbon thin film selective growth region,
After attaching metal particles to the surface of the cathode electrode or forming a metal thin film, it is desirable to remove metal oxide (so-called natural oxide film) on the surface of the metal particles or the surface of the metal thin film. The removal of metal oxide on the surface of metal particles or the surface of a metal thin film can be performed, for example, by a microwave plasma method in a hydrogen gas atmosphere, a trans-coupled plasma method, an inductively-coupled plasma method, an electron cyclotron resonance plasma method, an RF plasma method, or the like. It is preferable to perform the plasma reduction process based on the above, a sputtering process in an argon gas atmosphere, or a cleaning process using an acid or a base such as hydrofluoric acid. In the case where a step of adhering sulfur, boron or phosphorus to the surface of the carbon thin film selective growth region, or a step of removing metal oxide on the surface of the metal particles or the surface of the metal thin film, an opening is formed in the insulating layer. It is preferable to perform these steps after the provision and before the formation of the carbon thin film on the carbon thin film selective growth region.

As a method of attaching metal particles to the surface of the cathode electrode in order to obtain a carbon thin film selective growth region, for example, a region other than the cathode electrode region where the carbon thin film selective growth region is to be formed is made of an appropriate material (for example, After forming a layer composed of a solvent and metal particles on the surface of the portion of the cathode electrode where the carbon thin film selective growth region is to be formed in a state covered with the mask layer), a method of removing the solvent and leaving the metal particles is given. Can be. Alternatively, as a step of attaching metal particles to the surface of the cathode electrode, for example, in a state where a region other than the region of the cathode electrode where the carbon thin film selective growth region is to be formed is covered with an appropriate material (for example, a mask layer), After the metal compound particles containing metal atoms constituting the metal particles are attached to the surface of the cathode electrode, the metal compound particles are decomposed by heating, thereby comprising a portion of the cathode electrode with the metal particles attached to the surface. A method for obtaining a carbon thin film selective growth region can be mentioned. In this case, specifically, a method of forming a layer comprising a solvent and metal compound particles on the surface of the portion of the cathode electrode where the carbon thin film selective growth region is to be formed, and then removing the solvent to leave the metal compound particles is exemplified. can do. The metal compound particles include a metal halide (for example, iodide, chloride,
Preferably, the material is at least one material selected from the group consisting of bromide and the like, oxides, hydroxides and organometallics. In these methods, at an appropriate stage, a material (for example, a mask layer) covering a region other than the region of the cathode electrode where the carbon thin film selective growth region is to be formed is removed.

As a method for forming a metal thin film on the surface of the cathode electrode in order to obtain a carbon thin film selective growth region, for example, a region other than the cathode electrode region where the carbon thin film selective growth region is to be formed is coated with an appropriate material. Including electrolytic plating, electroless plating and MOCVD in the state
Method (chemical vapor deposition), physical vapor deposition (PVD)
Publicly known methods, such as a physical vapor deposition method and the like. In addition, as a physical vapor deposition method,
(A) various vacuum evaporation methods such as electron beam heating method, resistance heating method, flash evaporation, (b) plasma evaporation method, (c) 2
Polar sputtering method, DC sputtering method, DC magnetron sputtering method, high frequency sputtering method,
Various sputtering methods such as magnetron sputtering method, ion beam sputtering method, bias sputtering method, etc., (d) DC (direct current) method, RF method, multi-cathode method, activation reaction method, electric field evaporation method, high frequency ion plating method, Various ion plating methods such as a reactive ion plating method can be used.

Here, the metal particles or metal thin films are made of molybdenum (Mo), nickel (Ni), titanium (T
i), chromium (Cr), cobalt (Co), tungsten (W), zirconium (Zr), tantalum (Ta),
Iron (Fe), copper (Cu), platinum (Pt) and zinc (Z
Preferably, it is composed of at least one metal selected from the group consisting of n).

Examples of the carbon thin film include a graphite thin film, an amorphous carbon thin film, a diamond-like carbon thin film, and a fullerene thin film. As a method of forming a carbon thin film, a microwave plasma method, a trans-coupled plasma method, an inductively-coupled plasma method, an electron cyclotron resonance plasma method, a CVD method based on an RF plasma method, etc., and a CVD method using a parallel plate type CVD apparatus are used. Examples can be given. The form of the carbon thin film includes not only a thin film but also carbon whiskers and carbon nanotubes (including hollow and solid).

The structure of the cathode electrode may be a single layer structure of a conductive material layer, a lower conductive material layer, a resistor layer formed on the lower conductive material layer, and a resistor layer formed on the resistor layer. It is also possible to adopt a three-layer structure of the upper conductive material layer provided. In the latter case, a carbon thin film selective growth region is formed on the surface of the upper conductive material layer. Thus, by providing the resistor layer, the electron emission characteristics in the electron emission portion can be made uniform.

Referring to FIGS. 11 and 12 which are schematic partial end views of a support and the like, a flat type field emission device will now be described.
An example of the manufacturing method 3 will be described.

[Step-E1] First, a conductive material layer for a cathode electrode is formed on a support 10 made of, for example, glass.
Next, the cathode electrode 11 having a stripe shape is formed on the support 10 by patterning the cathode electrode conductive material layer based on a well-known lithography technique and RIE method. The striped cathode electrode 11 extends in the left-right direction on the drawing sheet. The cathode electrode 11 has a thickness of about 0.2 μm formed by, for example, a sputtering method.
m of chromium (Cr) layer.

[Step-E2] Thereafter, the insulating layer 12 is formed on the entire surface, specifically, on the support 10 and the cathode electrode 11.
To form

[Step-E3] Next, after a stripe-shaped gate electrode 13 is formed on the insulating layer 12, [Step-A]
Based on the same method as in [2], an opening 14 is formed in the gate electrode 13 and the insulating layer 12, and the cathode electrode 11 is exposed at the bottom of the opening 14 (hole) (see FIG. 11A). The striped gate electrode 13 extends in a direction perpendicular to the plane of the drawing. The planar shape of the opening 14 is, for example, a circle having a diameter of 1 μm to 30 μm. For example, one to 3000 openings are formed in a region (electron emission region) for one pixel.
What is necessary is just to form about pieces.

[Step-E4] Next, an electron-emitting portion 15C is formed on the cathode electrode 11 exposed at the bottom of the opening 14. Specifically, first, the carbon thin film selective growth region 70 is formed on the surface of the cathode electrode 11 located at the bottom of the opening 14.
To form For this purpose, first, the mask layer 71 having the surface of the cathode electrode 11 exposed at the center of the bottom of the opening 14 is formed.
Is formed (see FIG. 11B). Specifically, after a resist material layer is formed on the entire surface including the inside of the opening 14 by spin coating, a hole is formed in the resist material layer located at the center of the bottom of the opening 14 based on lithography technology. By forming, the mask layer 71 can be obtained. The mask layer 71 covers a part of the cathode electrode 11 located at the bottom of the opening 14, the side wall of the opening 14, the gate electrode 13, and the insulating layer 12. As a result, in the next step, a carbon thin film selective growth region is formed on the surface of the cathode electrode 11 located at the center of the bottom of the opening 14, but the cathode electrode 11 and the gate electrode 13 are short-circuited by metal particles. Can be reliably prevented.

Next, metal particles are adhered on the mask layer 71 including the exposed surface of the cathode electrode 11. Specifically, a solution in which nickel (Ni) fine particles are dispersed in a polysiloxane solution (isopropyl alcohol is used as a solvent) is applied to the entire surface by spin coating to form a cathode thin film selective growth region 70. Electrode 11
A layer composed of a solvent and metal particles is formed on the surface of the portion.
Thereafter, the mask layer 71 is removed, the solvent is removed by heating to about 400 ° C., and the metal particles 72 are left on the exposed surface of the cathode electrode 11, whereby the carbon thin film selective growth region 70 can be obtained. (See FIG. 12A). The polysiloxane is exposed on the exposed cathode electrode 1.
1 has a function of fixing the metal particles 72 to the surface (so-called adhesive function).

[Step-E5] Thereafter, a carbon thin film 73 having a thickness of about 0.2 μm is formed on the carbon thin film selective growth region 70 to obtain an electron emitting portion 15C. This state is shown in FIG. Table 1 below shows conditions for forming the carbon thin film 73 based on the microwave plasma CVD method.

[Table 1] [Film formation conditions for carbon thin film] Gas used: CH ₄ / H ₂ = 100/10 SCCM Pressure: 1.3 × 10 ³ Pa Microwave power: 500 W (13.56 MHz) Film formation temperature: 500 ゜ C

[Flat-Type Field Emission Device-1] FIG. 13C is a schematic partial cross-sectional view of the flat-type field emission device-1. The flat-type field emission device-1 has a stripe-shaped cathode electrode 11 formed on a support 10 made of, for example, glass; an insulating layer 12 formed on the support 10 and the cathode electrode 11; It comprises a gate electrode 13 in the form of a stripe, and an opening 14 penetrating the gate electrode 13 and the insulating layer 12 and exposing the cathode electrode 11 at the bottom. The cathode electrode 11 extends in the direction perpendicular to the plane of the paper of FIG.
3C extends in the left-right direction on the paper surface. The cathode electrode 11 is made of chromium (Cr), and the insulating layer 12 is made of SiO ₂
Consists of Here, the portion of the cathode electrode 11 exposed at the bottom of the opening 14 corresponds to the electron emission portion 15D.

Hereinafter, a method of manufacturing the flat field emission device 1 will be described with reference to FIG. 13 which is a schematic partial cross-sectional view of a support and the like.

[Step-F1] First, the cathode electrode 11 functioning as the electron-emitting portion 15D is formed on the support. Specifically, after a cathode conductive material layer made of chromium (Cr) is formed on the support 10 by a sputtering method, the cathode conductive material layer is patterned based on a lithography technique and a dry etching technique. Thus, the striped cathode electrode 11 can be formed on the support 10 (FIG. 13A).
reference). The cathode electrode 11 extends in a direction perpendicular to the plane of the paper of FIG.

[Step-F2] Next, an insulating layer 12 made of SiO ₂ is formed on the support 10 and the cathode electrode 11 by, for example, a CVD method. Note that the insulating layer 12 can also be formed from a glass paste based on a screen printing method.

[Step-F3] Thereafter, a stripe-shaped gate electrode 13 is formed on the insulating layer 12 (see FIG. 13B). The gate electrode 13 extends in the left-right direction on the paper of FIG. For example, the gate electrode 13 in a stripe shape can be directly formed on the insulating layer 12 by a screen printing method.

[Step-F4] Next, based on the same method as in [Step-A2], the opening 14 is formed in the gate electrode 13 and the insulating layer 12, and the electron emission is formed at the bottom of the opening 14 (hole). The cathode electrode 11 functioning as the portion 15D is exposed (see FIG. 13C). Thereafter, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13.

[Flat-type field emission device-2] FIG. 13 shows a modification of the flat-type field emission device-1 shown in FIG. The difference from the flat-type field emission device 1 shown in FIG. 1C is that a minute uneven portion 11A is formed on the surface (corresponding to an electron emission portion) of the cathode electrode 11 exposed at the bottom of the opening 14. It is in the point. Such a planar type field emission device-2 can be manufactured by the following manufacturing method.

[Step-G1] First, [Step-F1]-
In substantially the same manner as in [Step-F3], the striped cathode electrode 11 is formed on the support 10 and the insulating layer 12 is formed on the entire surface.
Is formed, a stripe-shaped gate electrode 13 is formed on the insulating layer 12. That is, a thickness of about 0.2 μm is formed on a support 10 made of, for example, glass by a sputtering method.
The tungsten layer is formed, and the tungsten layer is patterned in a stripe shape according to a usual procedure to form the cathode electrode 11. Next, an insulating layer 12 is formed on the support 10 and the cathode electrode 11. The insulating layer 12
It can be formed by a CVD method using TEOS (tetraethoxysilane) as a source gas. Further, a gate electrode 13 is formed on the insulating layer 12. The state in which the process up to this point has been completed is substantially the same as that shown in FIG.

[Step-G2] Next, the opening 14 is formed in the gate electrode 13 and the insulating layer 12 in the same manner as in [Step-F4].
Is formed, and the cathode electrode 11 is exposed at the bottom of the opening 14. Thereafter, a minute uneven portion 11A is formed on the portion of the cathode electrode 11 exposed at the bottom of the opening 14. In forming the minute irregularities 11A, RIE is performed by using SF ₆ as an etching gas and setting conditions such that the difference in etching rate between the crystal grains of tungsten constituting the cathode electrode 11 and the grain boundaries becomes large. Dry etching is performed based on. As a result, it is possible to form the minute uneven portions 11A having dimensions substantially reflecting the crystal grain size of tungsten.

In the configuration of such a flat type field emission device-2, the gate electrode 1 is provided on the minute uneven portion 11A of the cathode electrode 11, more specifically, the convex portion of the minute uneven portion 11A.
From 3, a large electric field is applied. At this time, since the electric field concentrated on the convex portion is larger than that when the surface of the cathode electrode 11 is smooth, electrons are efficiently emitted from the convex portion by the quantum tunnel effect. Therefore, compared to the flat field emission device 1 in which the smooth cathode electrode 11 is simply exposed at the bottom of the opening 14, an improvement in luminance when incorporated in a display device can be expected. Therefore, according to the planar type field emission device-2 shown in FIG.
Even if the potential difference between the electrode and the cathode electrode 11 is relatively small, a sufficient emitted electron current density can be obtained, and a high brightness display device can be achieved. Alternatively, the gate voltage required to achieve the same luminance may be low, so that low power consumption can be achieved.

A hole is formed by etching the insulating layer 12, and then the minute uneven portion 11A is formed on the cathode electrode 11 based on the anisotropic etching technique. However, the etching for forming the opening 14 is performed. By
It is also possible to form the minute uneven portions 11A at the same time.
That is, when the insulating layer 12 is etched, anisotropic etching conditions under which a certain degree of ion sputtering action can be expected are adopted, and the etching is continued even after the opening 14 having the vertical wall is formed, so that the opening is improved. The minute uneven portion 11A can be formed on the portion of the cathode electrode 11 exposed at the bottom of the portion 14. After that, isotropic etching of the insulating layer 12 may be performed.

In the same step as in [Step-G1], a cathode conductive material layer made of tungsten is formed on the support 10 by a sputtering method, and then the cathode electrode is formed based on a lithography technique and a dry etching technique. By patterning the conductive material layer for use and then forming the fine unevenness 11A on the surface of the conductive material layer for the cathode electrode, the same steps as [Step-F2] to [Step-F4] are executed to obtain a diagram. A field emission device similar to that shown in FIG. 14A can be manufactured.

Alternatively, in the same step as in [Step-G1], a cathode conductive material layer made of tungsten is formed on the support 10 by a sputtering method, and then formed on the surface of the cathode electrode conductive material layer. Micro unevenness 11
A is formed, and then the conductive material layer for a cathode electrode is patterned based on a lithography technique and a dry etching technique, and then the same steps as [Step-F2] to [Step-F4] are executed, thereby obtaining the structure shown in FIG. A field emission device similar to that shown in FIG.

FIG. 14B shows a modification of the field emission device shown in FIG. In the field emission device shown in FIG. 14B, the average height position of the tip of the minute uneven portion 11A is located closer to the support 10 than the lower surface of the insulating layer 12 (that is, the height is lower). There). In order to form such a field emission device, the duration of the dry etching in [Step-G2] may be extended. According to such a configuration, the electric field intensity near the center of the opening 14 can be further increased.

FIG. 15 shows a flat-type field emission device in which a coating layer 11B is formed on the surface of the cathode electrode 11 corresponding to the electron-emitting portion (more specifically, on at least the minute uneven portion 11A).

The coating layer 11B is preferably made of a material having a work function Φ smaller than that of the material forming the cathode electrode 11. It may be determined based on the function, the potential difference between the gate electrode 13 and the cathode electrode 11, the required magnitude of the emitted electron current density, and the like.
As a constituent material of the coating layer 11B, amorphous diamond can be exemplified. When the coating layer 11B is formed using amorphous diamond, 5 × 10
An emission electron current density required for a display device can be obtained at an electric field strength of ⁷ V / m or less.

The thickness of the coating layer 11B is
Should be selected to reflect the This is because the concave portion of the minute uneven portion 11A is buried by the coating layer 11B, and the surface of the electron emission portion is smoothed.
This is because the meaning of providing is lost. Therefore, depending on the size of the minute unevenness 11A, for example, when the minute unevenness 11A is formed by reflecting the crystal grain size of the electron emitting portion, the thickness of the coating layer 11B is set to about 30 to 100 nm. Is preferably selected. When the average height position of the tip portion of the minute uneven portion 11A is lower than the lower surface position of the insulating layer 12, strictly speaking, the average height position of the tip portion of the coating layer 11B is set to the lower surface position of the insulating layer 12. It is more preferable that the temperature is lower than the above.

Specifically, after [Step-F2], a coating layer 11B made of amorphous diamond may be formed on the entire surface by, eg, CVD. In addition, the coating layer 11B
Is also deposited on a resist layer (not shown) formed on the gate electrode 13 and the insulating layer 12, but this deposited portion is removed at the same time when the resist layer is removed. The coating layer 11B can be formed based on a CVD method using, for example, a CH ₄ / H ₂ mixed gas or a CO / H ₂ mixed gas as a source gas, and a coating made of amorphous diamond is formed by thermal decomposition of a compound containing carbon. The layer 11B is formed.

Alternatively, in the same step as in [Step-F1], a cathode conductive material layer made of tungsten is formed on the support 10 by a sputtering method, and then the cathode is formed based on a lithography technique and a dry etching technique. The conductive material layer for the electrode is patterned, and then the fine irregularities 11 are formed on the surface of the conductive material layer for the cathode electrode.
After forming A and then forming the coating layer 11B, the same steps as [Step-F2] to [Step-F4] are performed, whereby the field emission device shown in FIG. 15 can also be manufactured.

Alternatively, in the same step as that of [Step-F1], a cathode conductive material layer made of tungsten is formed on the support 10 by a sputtering method, and then the cathode electrode conductive material layer is formed on the surface of the cathode electrode conductive material layer. Micro unevenness 11
A, then, after forming the covering layer 11B, patterning the covering layer 11B and the conductive material layer for the cathode electrode based on the lithography technique and the dry etching technique, and then [Step-F2] to [Step-F4]. By performing the same steps, the field emission device shown in FIG. 15 can be manufactured.

Alternatively, as a material constituting the coating layer, a material may be appropriately selected such that the secondary electron gain δ of such a material is larger than the secondary electron gain δ of the conductive material constituting the cathode electrode. it can.

Incidentally, the electron emission portion 15D (the surface of the cathode electrode 11) of the flat field emission device shown in FIG.
May be formed with a coating layer. In this case, [Step-F
4], the cathode electrode 1 exposed at the bottom of the opening 14
1, a coating layer 11B may be formed on the surface of the substrate 1, or in [Step-F1], for example, after forming a conductive material layer for a cathode electrode on the support 10, coating the conductive material layer for a cathode electrode After forming the layer 11B, these layers may be patterned based on the lithography technique and the dry etching technique.

[Crater-Type Field Emission Device-1] FIG. 19B is a schematic partial sectional view of the crater-type field emission device-1. The crater type field emission device-1 has a cathode electrode 111 having a plurality of raised portions 111A for emitting electrons and a concave portion 111B surrounded by each raised portion 111A.
Are provided on the support 10. FIG. 18 is a schematic perspective view in which the insulating layer 12 and the gate electrode 13 are removed.
(B) of FIG.

The shape of the concave portion is not particularly limited, but typically forms a substantially spherical surface. This is because a sphere is used in the method for manufacturing the crater type field emission device, and
Is formed to reflect a part of the shape of the sphere. Therefore, when the concave portion 111B has a substantially spherical surface, the raised portion 111A surrounding the concave portion 111B has an annular shape. In this case, the concave portion 111B and the raised portion 111A have a shape like a crater or a caldera as a whole. Since the raised portion 111A is a portion that emits electrons, it is particularly preferable that the tip portion 111C is sharp from the viewpoint of increasing the electron emission efficiency. Tip 11 of ridge 111A
Even if the profile of 1C has irregular irregularities,
Alternatively, it may be smooth. The arrangement of the protrusions 111A within one pixel may be regular or random. In addition, the concave portion 111B may be surrounded by a raised portion 111A continuous along the circumferential direction of the concave portion 111B, or in some cases, may be surrounded by a discontinuous raised portion 111A along the circumferential direction of the concave portion 111B. You may.

In such a method of manufacturing a crater-type field emission device, the step of forming a striped cathode electrode on a support is more specifically performed by supporting the striped cathode electrode covering a plurality of spheres. Forming on the body and removing the sphere to remove a portion of the cathode electrode covering the sphere, thereby forming a plurality of ridges for emitting electrons, and being surrounded by each ridge, Forming a cathode electrode having a concave portion reflecting a part of the shape.

It is preferable to remove the sphere by a change in the state of the sphere and / or a chemical change. Here, the state change and / or chemical change of the sphere means a change such as expansion, sublimation, foaming, gas generation, decomposition, combustion, and carbonization, or a combination thereof. For example, if the sphere is made of an organic material, it is more preferable to remove the sphere by burning it. It should be noted that the removal of the sphere and the removal of the portion of the cathode electrode covering the sphere need not necessarily occur simultaneously. For example, when a part of the sphere remains after removing the part of the cathode electrode covering the sphere, the remaining sphere may be removed later.

In particular, when the sphere is made of an organic material, when the sphere is burned, for example, carbon monoxide, carbon dioxide, and water vapor are generated, the pressure in the closed space near the sphere increases, and the cathode electrode near the sphere is Explodes when a certain pressure limit is exceeded. Due to the force of the rupture, the portion of the cathode electrode covering the sphere is scattered to form a raised portion and a concave portion, and the sphere is removed. Alternatively, when the sphere is burned, for example, the cathode electrode explodes when a certain pressure limit is exceeded, based on a similar mechanism. Due to the force of the rupture, a portion of the cathode electrode covering the sphere is scattered, a hole is formed simultaneously with the protruding portion and the concave portion, and the sphere is removed. That is, before the sphere is removed, the cathode electrode has no hole, and the hole is formed as the sphere is removed. At this time, since the initial process of burning the sphere proceeds in the closed space, a part of the sphere may be carbonized. It is preferable that the thickness of the portion of the cathode electrode covering the sphere be thin enough to be scattered by bursting.

In the crater-type field emission device-3 or crater-type field emission device-4 described below, the sphere can be removed by a change in the state and / or a chemical change of the sphere, but without rupture of the cathode electrode. In some cases, it is more convenient to perform the removal by an external force. Here, the external force is a physical force such as a blowing pressure of air or an inert gas, a blowing pressure of a cleaning liquid, a magnetic attraction force, an electrostatic force, a centrifugal force, or the like. In the crater-type field emission device-3, unlike the crater-type field emission device-1, there is no need to scatter the portion of the cathode electrode that covers the sphere.
There is an advantage that the residue of the cathode electrode hardly occurs.

The sphere used in the crater type field emission device-3 or crater type field emission device-4 described below is
It is preferable that at least the surface is made of a material having a higher interfacial tension than the interfacial tension (surface tension) of the material forming the cathode electrode. In a crater-type field emission device-3 or a crater-type field emission device-4 described later, at least the surface of the sphere only needs to satisfy this condition regarding interfacial tension. That is, the portion having an interfacial tension higher than the interfacial tension of the cathode electrode may be only the surface of the sphere or the whole, and the surface of the sphere and / or the entire constituent material may be inorganic. Any of a material, an organic material, or a combination of an inorganic material and an organic material may be used. In the crater-type field emission device-3 or crater-type field emission device-4, when the cathode electrode and the like are made of a normal metal-based material, the surface of the metal-based material has a hydroxyl group derived from adsorbed moisture, Hydroxyl groups derived from dangling bonds of Si—O bonds and adsorbed moisture are present on the surface, and are usually in a state of high hydrophilicity. Therefore, it is particularly effective to use a sphere having a hydrophobic surface treatment layer. As a constituent material of the hydrophobic surface treatment layer, a fluorine-based resin, for example, polytetrafluoroethylene can be used. When the sphere has a hydrophobic surface treatment layer, the inside of the hydrophobic surface treatment layer is referred to as a core material, and the core material is made of a polymer material other than glass, ceramics, and fluororesin. Any of these may be used.

The organic material constituting the sphere is not particularly limited, but a general-purpose polymer material is preferable. However, in the case of a polymer material having an extremely high degree of polymerization or an extremely large content of multiple bonds, the combustion temperature becomes too high, and the cathode electrode may be adversely affected when the sphere is removed by combustion. Therefore, it is preferable to select a polymer material that can be burned or carbonized at a temperature at which there is no risk of adversely affecting these materials. In particular, when the insulating layer is formed using a material that needs to be fired in a later step, such as a glass paste, a polymer material that can be burned or carbonized at the firing temperature of the glass paste from the viewpoint of reducing the number of steps as much as possible. It is preferable to select Since the typical firing temperature of the glass paste is about 530 ° C., it is preferable that the burning temperature of such a polymer material is about 350 to 500 ° C. Representative polymer materials include styrene, urethane, acrylic, vinyl, divinylbenzene, melamine, formaldehyde, and polymethylene homopolymers and copolymers. Alternatively, a fixed-type sphere having an adhesive force may be used as the sphere in order to secure a reliable arrangement on the support. As the fixed type sphere, a sphere made of an acrylic resin can be exemplified.

Alternatively, for example, a heat-expandable microsphere encapsulated with a vinylidene chloride-acrylonitrile copolymer as an outer shell, isobutane as a foam material, and encapsulated can be used as a sphere. In the crater-type field emission device-1, when the heat-expandable microspheres are heated using the heat-expandable microspheres, the polymer of the outer shell is softened, and the contained isobutane is gasified and expanded. A hollow body of a true sphere having a diameter of about four times that before the expansion is formed. As a result, in the crater type field emission device-1, a raised portion that emits electrons and a concave portion that is surrounded by the raised portion and reflects a part of the shape of a sphere can be formed in the cathode electrode. In this specification, the expansion of the heat-expandable microsphere due to heating is also included in the concept of the removal of the sphere. Thereafter, the thermal expansion type microspheres may be removed using an appropriate solvent.

In the crater type field emission device-1,
After disposing a plurality of spheres on the support, a cathode electrode covering the spheres may be formed. In this case, or alternatively, in a crater-type field emission device-3 or a crater-type field emission device-4 described later, as a method of arranging a plurality of spheres on a support, a dry method of spraying the spheres on the support is used. Law. For example, in the field of manufacturing a liquid crystal display device, a technique of spraying spacers for maintaining a constant panel interval can be applied to the spraying of spheres. Specifically, a so-called spray gun that sprays a sphere from a nozzle with compressed gas can be used. When the sphere is ejected from the nozzle, the sphere may be dispersed in a volatile solvent. Alternatively, the spheres can be sprinkled using an apparatus or method commonly used in the field of electrostatic powder coating. For example, a sphere negatively charged by an electrostatic powder spray gun utilizing corona discharge can be sprayed toward a grounded support. Since the sphere used is very small as described later, when the sphere is sprayed on the support, it adheres to the surface of the support by, for example, electrostatic force, and does not easily fall off the support in the subsequent steps. After arranging a plurality of spheres on the support, if the spheres are pressurized, overlapping of the plurality of spheres on the support can be eliminated, and the spheres can be densely arranged in a single layer on the support. it can.

Alternatively, like a crater-type field emission device-2 to be described later, a composition layer composed of a composition obtained by dispersing a sphere and a cathode electrode material in a dispersion medium is formed on a support. After arranging a plurality of spheres on a support and covering the spheres with a cathode electrode made of a cathode electrode material,
The dispersion medium can also be removed. The composition may be in the form of a slurry or a paste, and the composition and viscosity of the dispersion medium may be appropriately selected according to the desired properties. As a method for forming the composition layer on the support, a screen printing method is suitable. Typically, the cathode electrode material is preferably fine particles whose sedimentation speed in the dispersion medium is lower than that of a sphere. Examples of a material constituting such fine particles include carbon, barium, strontium, and iron. After removing the dispersion medium, the cathode electrode is fired if necessary. Examples of the method for forming the composition layer on the support include a spraying method, a dropping method, a spin coating method, and a screen printing method.
It should be noted that the sphere is arranged and the sphere is covered with a cathode electrode made of a cathode electrode material. Depending on the method of forming the composition layer, it is necessary to pattern the cathode electrode.

Alternatively, in a crater-type field emission element-3 or crater-type field emission element-4 described later, a composition layer composed of a composition obtained by dispersing spheres in a dispersion medium is formed on a support. Thus, after disposing the plurality of spheres on the support, the dispersion medium can be removed. As a property of the composition, a slurry or a paste is possible,
The composition and viscosity of the dispersion medium may be appropriately selected according to the desired properties. Typically, an organic solvent such as isopropyl alcohol is used as a dispersion medium, and the dispersion medium can be removed by evaporation. Examples of the method for forming the composition layer on the support include a spraying method, a dropping method, a spin coating method, and a screen printing method.

The gate electrode and the cathode electrode extend in directions different from each other (for example, the angle formed by the projected image of the striped gate electrode and the projected image of the striped cathode electrode is 90 degrees). It is patterned in a stripe shape, and electrons are emitted from the ridge located in the electron emission region. Therefore, the raised portion only needs to be present only in the electron emission region in terms of function. However, even if the protrusions and recesses exist in a region other than the electron emission region, such protrusions and recesses do not perform any function of emitting electrons while being covered with the insulating layer. Therefore, no problem occurs even if the sphere is arranged on the entire surface.

On the other hand, when the portions of the conductive material layer for the cathode electrode covering the sphere, the insulating layer, and the layer constituting the gate electrode are removed, the positions of the individual spheres and the positions of the openings are changed. An opening is also formed in a region other than the electron emission region so as to correspond one-to-one. Hereinafter, an opening formed in a region other than the electron emission region is referred to as an “ineffective opening” and is distinguished from an original opening that contributes to electron emission. By the way, even if an ineffective opening is formed in a region other than the electron emission region, the ineffective opening does not function as a field emission device at all, and has no adverse effect on the operation of the field emission device formed in the electron emission region. Absent. This is because the gate electrode is not formed at the upper end of the invalid opening even if the protrusion and the concave portion are exposed at the bottom of the invalid opening, or the gate electrode is formed at the upper end of the invalid opening. Even if it is formed, the raised portion and the concave portion are not exposed at the bottom, or the raised portion and the concave portion are not exposed at the bottom of the invalid opening, and the gate electrode is not formed at the upper end. This is simply because the surface of the support is exposed. Therefore, no problem occurs even if the sphere is arranged on the entire surface. The hole formed on the boundary between the electron emission region and the other region is included in the opening.

The diameter of the sphere should constitute a desired diameter of the opening, a diameter of the recess, a display screen size of the display device using the field emission element, the number of pixels, the size of the electron emission region, and one pixel. The selection can be made according to the number of field emission devices, but is preferably selected in the range of 0.1 to 10 μm. For example, a sphere that is commercially available as a spacer for a liquid crystal display device has a favorable particle size distribution of 1 to 3%, and it is preferable to use this. Ideally, the shape of the sphere is a true sphere, but it need not necessarily be a true sphere. It is preferable to arrange spheres on the support at a density of about 100 to 5000 spheres / mm ² . For example, when spheres are arranged on the support at a density of about 1000 / mm ² , for example, the size of the electron emission region is assumed to be 0.5 mm × 0.2 mm
In this case, about 100 spheres exist in the electron emission region, and about 100 ridges are formed.
If such a number of protrusions are formed in one electron emission region, the variation in the diameter of the concave portion due to the variation in the particle size distribution and the sphericity of the sphere is almost averaged, and in practice,
The emission electron current density and luminance per pixel (or one sub-pixel) are substantially uniform.

In the crater type field emission device-1 or crater type field emission device-2 to crater type field emission device-4 which will be described later, a part of the shape of the sphere is reflected in the shape of the concave portion forming the electron emission portion. You. The profile of the tip of the raised portion may have irregular irregularities or may be smooth. In particular, in the crater type field emission device-1 and the crater type field emission device-2, this profile Since the tip is formed by breaking the cathode electrode, the tip of the raised portion is likely to have an irregular shape. When the tip is sharpened to the ridge due to the breakage, the tip can function as a highly efficient electron-emitting portion, which is advantageous. In the crater-type field emission device-1 to the crater-type field emission device-4, each of the raised portions surrounding the concave portion has a substantially annular shape. Present.

The arrangement of the ridges on the support may be regular or random, depending on the arrangement of the spheres. When the above-mentioned dry method or wet method is adopted,
The arrangement of the ridges on the support is random. still,
The concave portion may be surrounded by a raised portion continuous along the circumferential direction of the concave portion, or in some cases, the concave portion may be surrounded by a discontinuous raised portion along the circumferential direction of the concave portion.

In the crater type field emission device-1 to crater type field emission device-4, after the insulating layer is formed, an opening is formed in the insulating layer. After obtaining the portion, a protective layer may be formed, and after forming the opening, the protective layer may be removed. Chromium can be exemplified as a material constituting the protective layer.

Hereinafter, a method of manufacturing the crater type field emission device-1 will be described with reference to FIGS.
(A), (A) of FIG. 17, and (A) of FIG. 18 are schematic partial end views, and (A) and (B) of FIG. 19 are schematic partial cross-sectional views. 16 (B), FIG. 17 (B) and FIG. 18 (B) are FIGS. 16 (A) and 17 (A).
FIG. 19 is a partial perspective view schematically showing a range wider than (A) of FIG. 18.

[Step-H1] First, the cathode electrode 111 covering the plurality of spheres 80 is formed on the support.
Specifically, first, the sphere 80 is arranged on the entire surface of the support 10 made of, for example, glass. The sphere 80 is made of, for example, a polymethylene-based polymer material and has an average diameter of about 5 μm.
m, particle size distribution is less than 1%. Approximately 1000 spheres / mm ² were placed on the support 10 using a spray gun.
At random. Spraying using a spray gun may be either a method of spraying a sphere mixed with a volatile solvent or spraying it from a nozzle in a powder state. The placed sphere 80 is supported by the support 10 by electrostatic force.
Is held on. This state is shown in FIGS. 16A and 16B.

[Step-H2] Next, the cathode electrode 111 is formed on the sphere 80 and the support 10. FIGS. 17A and 17B show a state in which the cathode electrode 111 is formed. The cathode electrode 111 can be formed, for example, by screen-printing a carbon paste in a stripe shape. At this time, since the sphere 80 is disposed on the entire surface of the support 10, FIG.
As shown in FIG. 7 (B), there are some which are not covered with the cathode electrode 111. Next, the cathode electrode 111
To remove water and solvent contained in the cathode electrode 1
In order to flatten the electrode 11, the cathode electrode 111 is dried at, for example, 150 ° C. At this temperature, the sphere 80 undergoes no state change and / or chemical change. Instead of the screen printing using the carbon paste as described above, a cathode electrode conductive material layer constituting the cathode electrode 111 is formed on the entire surface, and the cathode electrode conductive material layer is formed by a usual lithography technique and dry etching. Patterned cathode electrode 1 using technology
11 can also be formed. When a lithography technique is applied, a resist material layer is usually formed by a spin coating method.
If the number of rotations of 0 is about 500 rpm and the rotation time is about several seconds, the sphere 80 can be held on the support 10 without falling off or displacing.

[Step-H3] Next, by removing the sphere 80, the cathode electrode 111 coated on the sphere 80 is removed.
Are removed, and a plurality of raised portions 1 emitting electrons are removed.
11A and a sphere 80 surrounded by each raised portion 111A.
And a concave portion 111B reflecting a part of the shape of the cathode electrode 111 are formed. This state is shown in FIG.
And (B). Specifically, the sphere 80 is burned by heating at about 530 ° C., also serving as firing of the cathode electrode 111. With the burning of the sphere 80, the sphere 80
The pressure in the enclosed space in which the
When the portion of the cathode electrode 111 covering 0 exceeds a certain withstand voltage limit, it is ruptured and removed. As a result, a raised portion 111A and a concave portion 111B are formed in a part of the cathode electrode 111 formed on the support 10. If a part of the sphere remains as a residue after the sphere is removed, the residue may be removed using an appropriate cleaning solution, depending on the material constituting the sphere to be used.

[Step-H4] Thereafter, the cathode electrode 11
An insulating layer 12 is formed on the substrate 1 and the support 10. Specifically, for example, a glass paste is screen-printed on the entire surface to a thickness of about 5 μm. Next, the insulating layer 12 is dried at, for example, 150 ° C. in order to remove moisture and a solvent contained in the insulating layer 12 and to planarize the insulating layer 12. Instead of screen printing using a glass paste as described above, an SiO ₂ film may be formed by, for example, a plasma CVD method.

[Step-H5] Next, a stripe-shaped gate electrode 13 is formed on the insulating layer 12 (see FIG. 19A). The direction in which the projected image of the striped gate electrode 13 extends forms an angle of 90 degrees with the direction in which the projected image of the striped cathode electrode 111 extends.

[Step-H6] Thereafter, in the electron emission region where the projected image of the gate electrode 13 and the projected image of the cathode electrode 111 overlap, the gate electrode 13 and the insulating layer are formed based on the same method as in [Step-A2]. An opening 14 is formed in the opening 12, thereby exposing a plurality of raised portions 111A and recesses 111B at the bottom of the opening 14 (hole). Note that it is preferable to perform the etching under the condition that a sufficiently high etching selectivity with respect to the cathode electrode 111 can be secured. Alternatively, it is preferable to form a protective layer made of, for example, chromium after forming the protruding portion 111A and remove the protective layer after forming the opening. Thus, the field emission device shown in FIG. 19B can be obtained.

As a modified example of the method for manufacturing the crater type field emission device-1, [Step-H2], [Step-H]
4] to [Step-H6], and then [Step-H
3] may be performed. In this case, the burning of the sphere and the firing of the material forming the gate electrode 13 and the insulating layer 12 may be performed simultaneously.

Alternatively, after [Step-H2], [Step-H4] is performed, and in the same step as [Step-H5], a striped gate electrode having no opening is formed. After forming a layer to be formed on the insulating layer, [Step-H
3]. As a result, the cathode electrode 111 covering the sphere 80, the insulating layer 12, and the respective parts of the layers constituting the gate electrode 13 are removed, whereby the opening 14 penetrating the gate electrode 13 and the insulating layer 12 is formed. At the same time, a raised portion 111A for emitting electrons and a raised portion 111A
, And a concave portion 111B reflecting a part of the shape of the sphere 80, can be formed on the cathode electrode 111 located at the bottom of the opening 14.
That is, the pressure of the closed space in which the sphere 80 is confined increases with the burning of the sphere 80, and the cathode electrode 111, the insulating layer 12, and the layer constituting the gate electrode 13 in the portion covering the sphere have a certain pressure resistance. The rupture occurs when the limit is exceeded, the opening 14 is formed at the same time as the protrusion 111A and the recess 111B, and the sphere 80 is removed. The opening 14 is
The sphere 8 penetrating through the gate electrode 13 and the insulating layer 12
0 reflects a part of the shape. At the bottom of the opening 14, a raised portion 111A that emits electrons and a concave portion 111B that is surrounded by the raised portion 111A and reflects a part of the shape of the sphere 80 remain.

[Crater-Type Field Emission Device-2] A method of manufacturing the crater-type field emission device-2 will be described with reference to FIG. 20. The step of disposing a plurality of spheres 80 on the support 10 is as follows. And a cathode electrode material dispersed in a dispersion medium, a composition layer 81 made of a composition is formed on the support 10, and a plurality of spheres 80 are arranged on the support 10 to form a cathode electrode material. After the sphere is covered with the cathode electrode 111 composed of a crater-type field emission device-1.
Is different from the manufacturing method.

[Step-J1] First, a plurality of spheres 80 are arranged on the support 10. Specifically, a composition layer 81 made of a composition obtained by dispersing a sphere 80 and a cathode electrode material 81B in a dispersion medium 81A is formed on the support 10. That is, for example, isopropyl alcohol is added to the dispersion medium 8.
1A, a sphere 80 made of a polymethylene polymer material having an average diameter of about 5 μm;
A composition formed by dispersing carbon particles of μm as a cathode electrode material 81B in a dispersion medium 81A is screen-printed in stripes on the support 10 to form a composition layer 81. FIG. 20A shows a state immediately after the formation of the composition layer 81.

[Step-J2] In the composition layer 81 held by the support 10, the sphere 80 will soon be settled down and disposed on the support 10, and the sphere 80 will extend from the sphere 80 onto the support 10. The cathode electrode material 81B is settled, and the cathode electrode 111 made of the cathode electrode material 81B is formed. Thereby, the plurality of spheres 80 can be arranged on the support 10 and the spheres 80 can be covered with the cathode electrode 111 made of the cathode electrode material. This state is shown in FIG.
(B) of FIG.

[Step-J3] Thereafter, the dispersion medium 81A is removed, for example, by evaporation. This state is shown in FIG.

[Step-J4] Next, the same steps as [Step-H3] to [Step-H6] of the crater-type field emission device-1, or a modification of the method of manufacturing the crater-type field emission device-1 will be described. By performing this, a field emission device similar to that shown in FIG. 19B can be completed.

[Crater-type field emission device-3] In the method of manufacturing the crater-type field emission device-3, the step of forming a striped cathode electrode on the support is more specifically performed on the support. Arranging a plurality of spheres;
It has a plurality of ridges for emitting electrons, and a recess surrounded by each ridge and reflecting a part of the shape of the sphere, and each ridge supports a cathode electrode formed around the sphere. It comprises the steps of providing on the body and removing the sphere. The arrangement of the plurality of spheres on the support is performed by scattering the spheres. The sphere has a hydrophobic surface treatment layer. Less than,
A method for manufacturing such a field emission device will be described with reference to FIG.

[Step-K1] First, a plurality of spheres 180 are arranged on the support. Specifically, a plurality of spheres 180 are arranged on the entire surface of the support 10 made of glass.
The sphere 180 is formed by coating a core material 180A made of, for example, a divinylbenzene polymer material with a surface treatment layer 180B made of a polytetrafluoroethylene resin.
The average diameter is about 5 μm, and the particle size distribution is less than 1%. Sphere 18
0 on the support 10 using a spray gun.
Randomly arranged at a density of 000 pieces / mm ² . The placed sphere 180 is adsorbed on the support 10 by electrostatic force. FIG. 21 shows a state in which the processes up to this point have been completed.
(A).

[Step-K2] Next, each step has a plurality of raised portions 111A for emitting electrons, and a concave portion 111B surrounded by each raised portion 111A and reflecting a part of the shape of the sphere 180. A cathode electrode 111 having a raised portion 111 </ b> A formed around a sphere 180 is provided on a support 10. Specifically, in the same manner as described for the crater-type field emission device-1, for example, a carbon paste is screen-printed in a stripe shape. The carbon paste screen-printed on the sphere 180 is immediately flipped and dropped due to the
And a protrusion 111A is formed. The tip 111C of the raised portion 111A is not as sharp as in the case of the crater type field emission device-1. The portion of the cathode electrode 111 that has entered between the sphere 180 and the support 10 is
The recess 111B is formed. In FIG. 21B, although a gap is shown between the cathode electrode 111 and the sphere 180, the cathode electrode 111 and the sphere 180 may be in contact with each other. Then, the cathode electrode 111
Is dried at 150 ° C., for example. FIG. 21B shows a state in which the processes up to this point have been completed.

[Step-K3] Next, the spherical body 180 is removed from the support 10 by applying an external force to the spherical body 180. As a specific removing method, cleaning and blowing of compressed gas can be mentioned. FIG. 21C shows a state in which the processes up to this point have been completed. The sphere can be removed based on the state change and / or chemical change of the sphere, more specifically, for example, by burning.

[Step-K4] After that, [Step-H4] to [Step-H6] of the crater type field emission device-1 are executed, thereby obtaining a field emission device substantially similar to that shown in FIG. Can be obtained.

As a modified example of the method for manufacturing the crater type field emission device-3, [Step-H4] to [Step-H4] in the crater type field emission device-1 after [Step-K2].
6], and then [Step-K3].

[Crater-Type Field Emission Device-4] In the method of manufacturing the crater-type field emission device-4, the step of forming a striped cathode electrode on the support is more specifically performed on the support. Arranging a sphere, a plurality of ridges emitting electrons, and surrounded by each ridge,
Providing a concave portion reflecting a part of the shape of the sphere, wherein each raised portion has a cathode electrode formed around the sphere on the support. When the insulating layer is provided over the entire surface, an insulating layer having an opening formed above the sphere is provided on the cathode electrode and the support. The removal of the sphere is performed after the formation of the opening. In the method for manufacturing the crater type field emission device-4, the plurality of spheres are arranged on the support by scattering the spheres. The sphere has a hydrophobic surface treatment layer.
Hereinafter, a method of manufacturing the crater type field emission device-4 will be described with reference to FIG.
2 and FIG.

[Step-L1] First, a plurality of spheres 180 are arranged on the support. Specifically, the same step as [Step-K1] in the manufacturing process of the crater type field emission device-3 is executed.

[Step-L2] Thereafter, each of the protrusions 111A has a plurality of protrusions 111A that emit electrons, and a recess 111B that is surrounded by the protrusions 111A and reflects a part of the shape of the sphere 180. The cathode electrode 111 in which the portion 111A is formed around the sphere 180 is provided on the support 10. Specifically, the same step as [Step-K2] in the manufacturing process of the crater type field emission device-3 is executed.

[Step-L3] Next, the insulating layer 12 having the opening 14A formed above the sphere is placed on the cathode electrode 111
And on the support 10. Specifically, for example, a glass paste is screen-printed on the entire surface to a thickness of about 5 μm. Since the surface of the sphere 180 is made hydrophobic by the surface treatment layer 180B, the glass paste screen-printed on the sphere 180 is immediately flipped and dropped, and the surface of the sphere 180 of the insulating layer 12 is dropped by its own surface tension. The upper part shrinks. As a result, the top of the sphere 180 is exposed in the opening 14A without being covered by the insulating layer 12. This state is shown in FIG. In the illustrated example, the opening 1
Although the diameter of the upper end of 4A is larger than the diameter of the sphere 180, when the interfacial tension of the surface treatment layer 180B is smaller than the interfacial tension of the glass paste, the diameter of the opening 14A tends to be smaller. Conversely, when the interfacial tension of the surface treatment layer 180B is significantly higher than the interfacial tension of the glass paste, the diameter of the opening 14A tends to increase.
Thereafter, the insulating layer 12 is dried at, for example, 150 ° C.

[Step-L4] Next, the gate electrode 13 having the opening 14B communicating with the opening 14A is formed on the insulating layer 12
Form on top. Specifically, for example, the paste is screen-printed in a stripe shape. Since the surface of the sphere 180 is made hydrophobic by the surface treatment layer 180B, the paste printed on the sphere 180 is immediately repelled, shrinks due to its own surface tension, and only on the surface of the insulating layer 12 It will be in a state of attachment. At this time, the gate electrode 1
3 may be formed so as to slightly extend from the opening end of the insulating layer 12 into the opening 14A as shown in the figure. Thereafter, the gate electrode 13 is dried at, for example, 150 ° C. FIG. 22B shows a state in which the steps up to this point have been completed. Note that the surface tension of the surface treatment layer 180B is
If the interfacial tension of the paste is smaller, the opening 14
The diameter of A tends to be small. Conversely, surface treatment layer 1
When the interfacial tension at 80B is significantly higher than the interfacial tension of the paste, the diameter of the opening 14A tends to increase.

[Step-L5] Next, the openings 14B, 14
The sphere 180 exposed at the bottom of A is removed. Specifically, it also serves as firing of the cathode electrode 111 and the insulating layer 12,
Typical firing temperature of glass paste is about 530 ° C
The sphere 180 is burned by heating at.
At this time, unlike the crater type field emission device-1, the openings 14A and 14B are formed in the insulating layer 12 and the gate electrode 13 from the beginning, so that the cathode electrode 111, the insulating layer 12, and a part of the gate electrode 13 are formed. Are not scattered, and the sphere 180 is quickly removed. The opening 14
When the diameters of the upper ends of the A and 14B are larger than the diameter of the sphere 180, the sphere 180 can be removed without burning the sphere 180 by, for example, an external force such as washing or blowing compressed gas. FIG. 23A shows a state in which the steps up to this point have been completed.

[Step-L6] After that, a portion of the insulating layer 12 corresponding to the side wall surface of the opening 14A is isotropically etched, whereby the field emission device shown in FIG. 23B can be completed. . Here, the end of the gate electrode 13 faces downward, which is preferable in order to increase the electric field intensity in the opening 14.

[Edge Type Field Emission Device] FIG. 24A is a schematic partial sectional view of an edge type field emission device.
The edge type field emission device includes a stripe-shaped cathode electrode 211 formed on a support 10, an insulating layer 12 formed on the support 10 and the cathode electrode 211, and a stripe formed on the insulating layer 12. Gate electrode 13
And an opening 14 is provided in the gate electrode 13 and the insulating layer 12. The edge portion 211A of the cathode electrode 211 is exposed at the bottom of the opening 14.
By applying a voltage to the cathode electrode 211 and the gate electrode 13, an edge portion 211 of the cathode electrode 211 is applied.
A emits electrons.

As shown in FIG. 24B, the recess 1 is formed in the support 10 below the cathode electrode 211 in the opening 14.
0A may be formed. Alternatively, as shown in a schematic partial cross-sectional view of FIG. 24C, a first gate electrode 13A formed on the support 10 and a first gate electrode 13A formed on the support 10 and the first gate electrode 13A are formed. Interlayer insulating layer 1 formed
2A, a cathode electrode 211 formed on the interlayer insulating layer 12A, an insulating layer 12B formed on the interlayer insulating layer 12A and the cathode electrode 211, and a second gate electrode 13B formed on the insulating layer 12B. You can also.
An opening 14 is provided in the second gate electrode 13B, the insulating layer 12B, the cathode electrode 211, and the interlayer insulating layer 12A.
Eleven edge portions 211A are exposed. By applying a voltage to the cathode electrode 211, the first gate electrode 13A, and the second gate electrode 13B, electrons are emitted from the edge portion 211A of the cathode electrode 211 corresponding to the electron emission portion.

For example, a method of manufacturing the edge type field emission device shown in FIG. 24C will be described below with reference to FIG. 25 which is a schematic partial end view of a support or the like.

[Step-M1] First, a tungsten film having a thickness of about 0.2 μm is formed on a support 10 made of, for example, glass by a sputtering method, and is subjected to a photolithography technique and a dry etching technique according to a usual procedure. This tungsten film is patterned to form a first gate electrode 13A. Next, a 0.3 μm thick interlayer insulating layer 12A made of SiO ₂ is formed on the entire surface, and then a striped cathode electrode 211 made of tungsten is formed on the interlayer insulating layer 12A (FIG. 25A )reference).

[Step-M2] Thereafter, for example, S
An insulating layer 12B made of iO ₂ and having a thickness of 0.7 μm is formed, and then a second gate electrode 13B in a stripe shape is formed on the insulating layer 12B (see FIG. 25B).

[Step-M3] Next, based on the same method as in [Step-A2], the second gate electrode 13B is, for example, R
An opening is formed by anisotropic etching by the IE method. Next, the insulating layer 12B exposed on the bottom surface of the opening is isotropically etched to form a hole. The insulating layer 12B is made of S
Since it is formed using iO ₂ , wet etching using a buffered hydrofluoric acid aqueous solution is performed. The wall surface of the hole formed in the insulating layer 12B recedes from the opening end face of the opening formed in the second gate electrode 13B, and the amount of retreat can be controlled by the length of the etching time. . Here, wet etching is performed until the lower end of the hole formed in the insulating layer 12B recedes from the opening end surface of the opening formed in the second gate electrode 13B.

Next, the cathode electrode 211 exposed on the bottom of the hole is dry-etched under the condition that ions are used as main etching species. In dry etching using ions as a main etching species, charged particles can be accelerated by applying a bias voltage to an object to be etched or by using an interaction between a plasma and a magnetic field. As the etching proceeds, the processed surface of the object to be etched becomes a vertical wall. However, in this process, the main etching species in the plasma also have some incident components having an angle other than perpendicular, and the oblique incident components also occur due to scattering at the end of the opening, so that the cathode is In the exposed surface of the electrode 211, the main etching species is also incident with a certain probability to a region where the ions should not reach because of being normally blocked by the opening. At this time,
The main etching species having a smaller incident angle with respect to the normal line of the support 10 has a higher incidence probability, and the main etching species having a larger incident angle has a lower incidence probability.

Accordingly, although the position of the upper end of the hole formed in the cathode electrode 211 is almost aligned with the lower end of the hole formed in the insulating layer 12B,
The position of the lower end of the hole formed in the hole protrudes from the upper end. That is, the thickness of the edge portion 211A of the cathode electrode 211 becomes thinner toward the front end portion in the protruding direction, and the edge portion 211A is sharpened. For example, by using SF ₆ as an etching gas, favorable processing of the cathode electrode 211 can be performed.

Next, the interlayer insulating layer 12A exposed at the bottom of the hole formed in the cathode electrode 211 is isotropically etched to form a hole in the interlayer insulating layer 12A.
To complete. Here, wet etching using a buffered hydrofluoric acid aqueous solution is performed. The wall surface of the hole formed in interlayer insulating layer 12A is recessed from the lower end of the hole formed in cathode electrode 211. The amount of retreat at this time can be controlled by the length of the etching time. When the first resist layer is removed after the opening 14 is completed, FIG.
Can be obtained.

[Modification of Manufacturing Method of Spindt-Type Field Emission Device-1] A modification of the manufacturing method of Spindt-type field emission device described in [Spindt-type field emission device] Although described with reference to FIGS. 26 to 29 which are partial end views, this Spindt-type field emission device is basically manufactured based on the following steps. (A) Stripe-shaped cathode electrode 11 on support 10
(B) forming an insulating layer 12 on the support 10 including the cathode electrode 11 (c) forming a striped gate electrode 13 on the insulating layer 12 (d) forming a cathode electrode on the bottom Opening 14 with exposed 11
(E) a step of forming a conductive material layer 91 for forming an electron-emitting portion on the entire surface including the inside of the opening 14 (f) a step of forming a central part of the opening 14 Step of forming a mask material layer 92 on the conductive material layer 91 so as to shield the region of the conductive material layer 91. (g) The etching rate of the conductive material layer 91 in the direction perpendicular to the support 10 The conductive material layer 91 and the mask material layer 92 are etched under anisotropic etching conditions in which the etching rate in the direction perpendicular to the support 92 is higher than that of the conductive material layer 9.
1, the electron emitting portion 15 having a conical tip.
Step of Forming E on Cathode Electrode 11 Exposed in Opening 14

[Step-N1] First, a cathode electrode 11 made of chromium (Cr) is provided on a support 10 having a SiO ₂ layer having a thickness of about 0.6 μm formed on a glass substrate, for example. Specifically, a cathode conductive material layer made of chromium is deposited on the support 10 by, for example, a sputtering method or a CVD method, and the cathode conductive material layer is patterned to form a plurality of cathode electrodes 11. Can be formed. The width of the cathode electrode 11 is, for example, 50 μm, and the space between the cathode electrodes is, for example, 3 μm.
0 μm. Thereafter, an insulating layer 12 made of SiO ₂ is formed on the support 10 including the cathode electrode 11 by a plasma CVD method using TEOS (tetraethoxysilane) as a source gas. The thickness of the insulating layer 12 is about 1 μm.
m. Next, a stripe-shaped gate electrode 13 extending parallel to a direction orthogonal to the cathode electrode 11 is formed on the entire surface of the insulating layer 12.

Next, the cathode electrode 11 and the gate electrode 13
In the electron emission region which is an overlap region with the above, that is, in one pixel region, an opening 14 penetrating the gate electrode 13 and the insulating layer 12 is formed based on the same method as in [Step-A2] (FIG. 26). (A)). The planar shape of the opening 14 is
For example, it is a circle having a diameter of 0.3 μm. The opening 14 is
Usually, several hundred to one thousand pieces are formed in one pixel area.

[Step-N2] Next, an adhesion layer 90 is formed on the entire surface by a sputtering method (see FIG. 26B). The adhesion layer 90 is formed between the gate electrode 13 and the opening 14.
This is a layer provided to increase the adhesion between the insulating layer 12 exposed on the side wall surface of the substrate and the conductive material layer 91 which is entirely formed in the next step. Assuming that the conductive material layer 91 is formed of tungsten, the adhesion layer 90 made of tungsten is formed to a thickness of 0.07 μm by DC sputtering.
m.

[Step-N3] Next, a conductive material layer 91 for forming an electron emission portion made of tungsten having a thickness of about 0.6 μm is formed on the entire surface including the inside of the opening portion 14 by a hydrogen-reduced low-pressure CVD method. FIG. 27A). On the surface of the conductive material layer 91 on which the film is formed, a concave portion 91A reflecting a step between the upper end surface and the bottom surface of the opening 14 is formed.

[Step-N4] Next, a region of the conductive material layer 91 located at the center of the opening 14 (specifically, the concave 91
A mask material layer 92 is formed so as to shield A). Specifically, first, the thickness is 0.35 μm by a pin coating method.
The resist material is used as a mask material layer 92 to form the conductive material layer 9.
1 (see FIG. 27B). The mask material layer 92 absorbs the concave portions 91A of the conductive material layer 91 and has a substantially flat surface. Next, the mask material layer 92 is etched by RIE using an oxygen-based gas. This etching is completed when the flat surface of the conductive material layer 91 is exposed. As a result, the mask material layer 92 remains so as to bury the recess 91A of the conductive material layer 91 flat (see FIG. 28A).

[Step-N5] Next, the conductive material layer 91, the mask material layer 92, and the adhesion layer 90 are etched to form a conical electron emission portion 15E (see FIG. 28B). The etching of these layers is performed under anisotropic etching conditions in which the etching rate of the conductive material layer 91 is higher than the etching rate of the mask material layer 92. The etching conditions are illustrated in Table 2 below.

[Table 2] [Etching conditions for conductive material layer 91 etc.] SF ₆ flow rate: 150 SCCM O ₂ flow rate: 30 SCCM Ar flow rate: 90 SCCM Pressure: 35 Pa RF power: 0.7 kW (13.56 MHz)

[Step-N6] Thereafter, when the side wall surface of the opening 14 provided in the insulating layer 12 is retreated inside the opening 14 under isotropic etching conditions, the field emission device shown in FIG. Be completed. Isotropic etching is
It can be performed by dry etching using a radical as a main etching species, such as chemical dry etching, or wet etching using an etchant. As an etching solution, for example, a mixed solution of 1: 100 (volume ratio) of a 49% hydrofluoric acid aqueous solution and pure water can be used.

Here, the mechanism for forming the electron-emitting portion 15E in [Step-N5] will be described with reference to FIG. FIG. 30A is a schematic diagram showing how the surface profile of the object to be etched changes at regular time intervals with the progress of etching, and FIG. 5 is a graph showing a relationship between the center of an opening 14 and the thickness of an object to be etched. The thickness of h _p of the mask material layer in the center of the opening 14, the height of the electron-emitting portion 15E at the center of the opening 14 h _e
And

Under the etching conditions shown in Table 2, the etching rate of the conductive material layer 91 is naturally higher than the etching rate of the mask material layer 92 made of the resist material.
In a region where the mask material layer 92 does not exist, the conductive material layer 9
1 immediately starts to be etched, and the surface of the object to be etched quickly descends. On the other hand, in the region where the mask material layer 92 exists, the etching of the conductive material layer 91 thereunder does not start unless the mask material layer 92 is first removed. rate of decrease in the thickness of the object to be etched is slow (h _p decreasing segment), the first time when the mask material layer 92 is lost,
Rate of decrease in the thickness of the object to be etched is similar to the nonexistent areas of the mask material layer 92 faster (h _e decreasing segment). h _p
The start time of the decreasing section is the latest at the center of the opening 14 where the thickness of the mask material layer 92 is the largest, and
Of the opening 14 having a small thickness. Thus, a conical electron emitting portion 15E is formed.

The ratio of the etching rate of the conductive material layer 91 to the etching rate of the mask material layer 92 made of the resist material will be referred to as “resist selectivity”.
The fact that the resist selectivity is an important factor in determining the height and shape of the electron-emitting portion 15E will be described with reference to FIG. FIG. 31A shows a case where the resist selectivity is relatively small, FIG. 31C shows a case where the resist selectivity is relatively large, and FIG. In this case, the shape of the electron-emitting portion 15E is shown. The larger the selectivity with respect to the resist, the more the mask material layer 92
Since the film thickness of the conductive material layer 91 is more severe than that of the electron emission portion 15, it can be seen that the electron emitting portion 15E is higher and sharper. The resist selectivity decreases as the ratio of the O ₂ flow rate to the SF ₆ flow rate increases. Also, when using an etching apparatus that can change the incident energy of ions by using a substrate bias, it is possible to increase the RF bias power or reduce the frequency of the AC power supply for bias application to select the resist. The ratio can be reduced.
The value of the resist selectivity is selected to be 1.5 or more, preferably 2 or more, and more preferably 3 or more.

In the above-described etching, it is naturally necessary to ensure a high selectivity with respect to the gate electrode 13 and the cathode electrode 11, but there is no problem at all under the conditions shown in Table 2. This is because the material constituting the gate electrode 13 and the cathode electrode 11 is hardly etched by the fluorine-based etching species, and an etching selectivity of about 10 or more can be obtained under the above conditions.

[Modification-2 of manufacturing method of Spindt-type field emission device] [Modification of manufacturing method of Spindt-type field emission device-
The manufacturing method of [2] is a modification of the manufacturing method of [Modification-1 of Manufacturing Method of Spindt Field Emission Element]. In this manufacturing method, the region of the conductive material layer shielded by the mask material layer can be narrower than in the manufacturing method in [Modification-1 of Spindt-type field emission device manufacturing method]. That is, in the method for manufacturing a Spindt-type field emission device according to [Modification 2 of Spindt-type field emission device manufacturing method], the columnar portion and the columnar portion are reflected by reflecting the step between the upper end surface and the bottom surface of the opening. A substantially funnel-shaped concave portion including an enlarged portion communicating with the upper end of the portion is formed on the surface of the conductive material layer. In step (f), after forming a mask material layer over the entire surface of the conductive material layer, the mask material layer By removing the conductive material layer in a plane parallel to the surface of the support, the mask material layer is left on the columnar portion.

The method for manufacturing a Spindt-type field emission device in [Modification-2 of method for manufacturing Spindt-type field emission device] will now be described with reference to FIGS.
This will be described with reference to FIG.

[Step-P1] First, the cathode electrode 11 is formed on the support. The cathode electrode 11 is formed, for example, by a DC sputtering method using a TiN layer (0.1 μm thick).
m), a Ti layer (5 nm thick), and an Al-Cu layer (0.1 mm thick).
4 μm), a Ti layer (5 nm thick), a TiN layer (0.3 mm thick).
02 μm) and a Ti layer (0.02 μm) in this order to form a laminated film, and then the laminated film can be formed by patterning. In the figure, the cathode electrode 1
1 was represented as a single layer. Next, the support 10 and the cathode 1
1, an insulating layer 12 having a thickness of 0.7 μm is
Plasma C using (tetraethoxysilane) as a source gas
It is formed based on the VD method. Next, the gate electrode 13 is formed on the insulating layer 12.

Further, an etching stopper layer 93 made of, for example, SiO ₂ and having a thickness of 0.2 μm is formed on the entire surface. The etching stop layer 93 is not an indispensable member for the function of the field emission device, and plays a role of protecting the gate electrode 13 when the conductive material layer 91 is etched in a later step. still,
The gate electrode 1 for the etching conditions of the conductive material layer 91
If 3 can have a sufficiently high etching resistance, the etching stop layer 93 may be omitted. Then, R
Etching stop layer 93, gate electrode 1 by IE method
3. An opening 14 penetrating the insulating layer 12 and exposing the cathode electrode 11 at the bottom is formed based on the same method as in [Step-A2]. Thus, the state shown in FIG. 32A is obtained.

[Step-P2] Next, an adhesion layer 90 made of, for example, tungsten having a thickness of 0.03 μm is formed on the entire surface including the inside of the opening 14. Next, a conductive material layer 91 for forming an electron-emitting portion is formed on the entire surface including the inside of the opening 14 (see FIG. 32B). However, the conductive material layer 91 in [Modification-2 of manufacturing method of Spindt-type field emission device]
Is [Modification-1 of manufacturing method of Spindt-type field emission device]
The thickness of the conductive material layer 91 is selected so that a concave portion 91A deeper than the concave portion 91A described in the manufacturing method described above is formed on the surface. That is, by appropriately setting the thickness of the conductive material layer 91, the columnar portion 91 </ b> B and the enlarged portion communicating with the upper end of the columnar portion 91 </ b> B are reflected by reflecting the step between the upper end surface and the bottom surface of the opening portion 14. A substantially funnel-shaped concave portion 91 </ b> A made of the conductive material layer 91 </ b> C can be formed on the surface of the conductive material layer 91.

[Step-P3] Next, the entire surface of the conductive material layer 91 is formed to a thickness of about 0.5 μm by, for example, electroless plating.
A mask material layer 92 made of copper (Cu) is formed (see FIG. 33A). The electroless plating conditions are illustrated in Table 3 below.

[0200] [Table 3] Plating liquid: copper sulfate _{(CuSO 4 · 5H 2 O)} 7g / liter Formalin (37% HCHO) 20ml / l sodium hydroxide (NaOH) 10 g / l sodium potassium tartrate 20 g / l plating bath temperature ： 50 ℃

[Step-P4] Thereafter, the mask material layer 92 is formed.
By removing the and the conductive material layer 91 in a plane parallel to the surface of the support 10, the mask material layer 92 is left on the columnar portion 91B (see FIG. 33B). This removal can be performed by, for example, a chemical mechanical polishing method (CMP method).

[Step-P5] Next, the conductive material layer 91 and the mask material layer 90 are anisotropically etched under the condition that the etching rate of the conductive material layer 91 and the adhesion layer 90 is higher than that of the mask material layer 92. 92 and the adhesion layer 90 are etched. As a result, an electron-emitting portion 15E having a conical shape is formed in the opening 14 (see FIG. 34A). The mask material layer 9 is provided at the tip of the electron emitting portion 15E.
When 2 remains, the mask material layer 92 can be removed by wet etching using a diluted hydrofluoric acid aqueous solution.

[Step-P6] Next, when the side wall surface of the opening 14 provided in the insulating layer 12 is retreated inside the opening 14 under isotropic etching conditions, FIG.
Is completed. The isotropic etching may be the same as that described in the manufacturing method of [Modification-1 of Manufacturing Method of Spindt-Type Field Emission Element].

By the way, in the electron emitting portion 15E formed by the manufacturing method of [Spindt-type field emission device manufacturing method-2], the manufacturing method of [Spindt-type field emission device manufacturing method-1] is used. Electron emitting portion 15 formed of
A sharper conical shape is achieved as compared to E. This is due to the difference between the shape of the mask material layer 92 and the ratio of the etching rate of the conductive material layer 91 to the etching rate of the mask material layer 92. This difference will be described with reference to FIG. FIG. 35 is a diagram showing how the surface profile of the object to be etched changes at predetermined time intervals. FIG. 35A shows a case where a mask material layer 92 made of copper is used. B) shows the case where a mask material layer 92 made of a resist material is used, respectively.
For the sake of simplicity, it is assumed that the etching rate of the conductive material layer 91 is equal to the etching rate of the adhesion layer 90, and the illustration of the adhesion layer 90 is omitted in FIG.

When the mask material layer 92 made of copper is used (see FIG. 35A), the etching rate of the mask material layer 92 is sufficiently lower than the etching rate of the conductive material layer 91. The mask material layer 92 does not disappear therein, and therefore, the electron emitting portion 1 having a sharp tip portion.
5E can be formed. On the other hand, when the mask material layer 92 made of a resist material is used (see FIG. 35B), the etching rate of the mask material layer 92 is not so slow as compared with the etching rate of the conductive material layer 91. In addition, the mask material layer 92 tends to disappear during the etching, so that the conical shape of the electron-emitting portion 15E after the disappearance of the mask material layer tends to be blunted.

Further, the mask material layer 9 remaining in the columnar portion 91B
2 has the merit that the shape of the electron-emitting portion 15E hardly changes even if the depth of the columnar portion 91B slightly changes.
In other words, the depth of the columnar portion 91B can change due to variations in the thickness of the conductive material layer 91 and the step coverage.
Since the width of the columnar portion 91B is substantially constant irrespective of the depth, the width of the mask material layer 92 is also substantially constant, and there is no great difference in the shape of the finally formed electron emitting portion 15E. On the other hand, in the mask material layer 92 remaining in the concave portion 91A, the width of the mask material layer also changes depending on whether the concave portion 91A is shallow or deep, so that the concave portion 91A is shallow and the thickness of the mask material layer 92 is small. As the thickness becomes thinner, the conical shape of the electron-emitting portion 15E starts to blunt earlier. The electron emission efficiency of the field emission device is determined by the potential difference between the gate electrode and the cathode electrode, the distance between the gate electrode and the cathode electrode, the work function of the constituent materials of the electron emission portion, and the tip of the electron emission portion. It also changes depending on the shape. Therefore, it is preferable to select the shape of the mask material layer and the etching rate as described above as necessary.

[Modification of Manufacturing Method of Spindt-Type Field Emission Device-3] [Modification of Manufacturing Method of Spindt-Type Field Emission Device]
The manufacturing method of [3] is a modification of the method of manufacturing a Spindt-type field emission device of [Modification-2 of manufacturing method of Spindt-type field emission device]. In the manufacturing method of [Modification-3 of manufacturing method of Spindt-type field emission device], in step (e),
By reflecting a step between the upper end surface and the bottom surface of the opening, a substantially funnel-shaped concave portion including a columnar portion and an enlarged portion communicating with the upper end of the columnar portion is generated on the surface of the conductive material layer, In f), after forming a mask material layer on the entire surface of the conductive material layer, the mask material layer on the conductive material layer and in the enlarged portion is removed, so that the mask material layer remains on the columnar portion. Hereinafter, the manufacturing method of the Spindt-type field emission device in [Modification-3 of manufacturing method of Spindt-type field emission device] will be described with reference to FIGS. 36 and 37 which are schematic partial end views of a support and the like. I do.

[Step-Q1] First, the steps up to the formation of the mask material layer 92 shown in FIG.
1] to [Step-P3], and then the conductive material layer 9
By removing only the mask material layer 92 above 1 and in the enlarged portion 91C, the mask material layer 92 is left in the columnar portion 91B (see FIG. 36A). At this time, for example, by performing wet etching using a diluted hydrofluoric acid aqueous solution, only the mask material layer 92 made of copper can be selectively removed without removing the conductive material layer 91 made of tungsten. Mask material layer 9 remaining in columnar portion 91B
The height of 2 depends on the etching time, but this etching time does not need to be so strict as long as the portion of the mask material layer 92 embedded in the enlarged portion 91C is sufficiently removed. This is because the discussion on the height of the mask material layer 92 is substantially the same as the discussion on the shallow depth of the columnar portion 91B described above with reference to FIG. This is because the shape of the formed electron-emitting portion 15E is not significantly affected.

[Step-Q2] Next, etching of the conductive material layer 91, the mask material layer 92, and the adhesion layer 90 is performed in the same manner as in the manufacturing method of [Modification 2 of Manufacturing Method of Spindt Field Emission Element]. Electron emitting portion 1 as shown in FIG.
Form 5E. This electron emitting portion 15E may have a conical shape as a whole as shown in FIG. 34 (A), but FIG. 36 (B) shows only a tip portion having a conical shape. Modified examples are shown. Such a shape corresponds to the columnar portion 91.
This may occur when the height of the mask material layer 92 embedded in B is low or the etching rate of the mask material layer 92 is relatively high, but this does not hinder the function as the electron emission portion 15E.

[Step-Q3] Thereafter, the side wall surface of the opening 14 provided in the insulating layer 12 inside the opening 14 is retreated under isotropic etching conditions to complete the field emission device shown in FIG. Is done. For isotropic etching, see [Modification of manufacturing method of Spindt-type field emission device-
1].

[Modification of Manufacturing Method of Spindt-Type Field Emission Element-4] [Modification of Manufacturing Method of Spindt-Type Field Emission Element]
The manufacturing method of [4] is a modification of the manufacturing method of [Spindt-type field emission device manufacturing method-1]. FIG. 38 is a schematic partial end view of [Modification-4 of manufacturing method of Spindt-type field emission device]. [Modification-4 of manufacturing method of Spindt-type field emission device] is different from [Modification-1 of manufacturing method of Spindt-type field emission device] in that the electron-emitting portion has a base 94.
And a conical electron-emitting portion 15E stacked on the base 94. Here, the base 94 and the electron emitting portion 15E are made of different conductive materials.
Specifically, the base portion 94 is a member for adjusting the distance between the electron emitting portion 15E and the opening end of the gate electrode 13, has a function as a resistor layer, and contains impurities. And a polysilicon layer. The electron emitting portion 15E is made of tungsten and has a conical shape,
More specifically, it has a conical shape. Note that an adhesion layer 90 made of TiN is formed between the base 94 and the electron-emitting portion 15E. Note that the adhesion layer 90 is not a component essential for the function of the electron emission portion, but is formed for manufacturing reasons. The insulating layer 12 is formed just below the gate electrode 13 from the base 9.
4 through the upper end of the opening 14.
Are formed.

Hereinafter, the manufacturing method of [Modification-4 of manufacturing method of Spindt-type field emission device] will be described with reference to FIGS. 39 to 41 which are schematic partial end views of a support and the like.

[Step-R1] First, the steps up to the formation of the opening 14 are described in [Modification of Manufacturing Method of Spindt-Type Field Emission Element-
1] in the same manner as in [Step-N1] of the production method. Subsequently, a conductive material layer 94A for forming a base is formed on the entire surface including the inside of the opening 14. The conductive material layer 94A also functions as a resistor layer, is composed of a polysilicon layer, and has a plasma C
It can be formed by a VD method. Then, on the whole surface,
Flattening layer 95 made of resist material by spin coating
Is formed so that the surface is substantially flat (see FIG. 39A). Next, both layers are etched under the condition that the etching rates of the planarizing layer 95 and the conductive material layer 94A are both substantially equal, and the bottom of the opening 14 is buried with the base 94 having a flat upper surface (see FIG. 39B). ). Etching can be performed by an RIE method using an etching gas containing a chlorine-based gas and an oxygen-based gas. Since the etching is performed after the surface of the conductive material layer 94A is once flattened by the flattening layer 95, the upper surface of the base 94 becomes flat.

[Step-R2] Next, an adhesion layer 90 is formed on the entire surface including the remaining portion of the opening 14, and a conductive material layer 91 for forming an electron emission portion is further formed on the entire surface including the remaining portion of the opening 14. A film is formed, and the remaining portion of the opening 14 is filled with a conductive material layer 91 (see FIG. 40A). The adhesion layer 90 is a 0.07 μm-thick TiN layer formed by a sputtering method, and the conductive material layer 91 is a 0.6 μm-thick tungsten layer formed by a low-pressure CVD method. Conductive material layer 91
A concave portion 91 </ b> A is formed on the surface of the light-reflective surface reflecting the step between the upper end surface and the bottom surface of the opening 14.

[Step-R3] Next, a mask material layer 92 made of a resist material is formed on the entire surface of the conductive material layer 91 by spin coating so that the surface is substantially flat (FIG. 4).
0 (B)). The mask material layer 92 includes the conductive material layer 9.
The first surface has a flat surface by absorbing the concave portion 91A. Next, the mask material layer 92 is formed by RI using an oxygen-based gas.
Etching is performed by the E method (see FIG. 41A). This etching ends when the flat surface of the conductive material layer 91 is exposed. Thereby, the concave portion 91 of the conductive material layer 91 is formed.
A, the mask material layer 92 is left flat, and the mask material layer 9 is removed.
2 is formed so as to shield the region of the conductive material layer 91 located at the center of the opening 14.

[Step-R4] Next, [Step-N] of the manufacturing method of [Modification-1 of manufacturing method of Spindt-type field emission device].
5], the conductive material layer 91 and the mask material layer 92
When the contact layer 90 and the adhesion layer 90 are both etched, the electron emission section 15E and the adhesion layer 90 having a conical shape corresponding to the magnitude of the resist selectivity are formed based on the mechanism described above, and the electron emission section is completed (FIG. 41 (B)). afterwards,
When the side wall surface of the opening 14 provided in the insulating layer 12 inside the opening 14 is retreated, the field emission device shown in FIG. 38 can be obtained.

[Modification-5 of manufacturing method of Spindt-type field emission device] [Modification of manufacturing method of Spindt-type field emission device]
The manufacturing method of [5] is a modification of the manufacturing method of [Modification-2 of manufacturing method of Spindt-type field emission device]. FIG. 43B is a schematic partial end view of [Modification-5 of Manufacturing Method of Spindt Field Emission Element]. [Modification-5 of manufacturing method of Spindt-type field emission device] is different from [Modification-2 of manufacturing method of Spindt-type field emission device] in that the electron-emitting portion is
As in [Modification-4 of Manufacturing Method of Spindt-Type Field Emission Element], the present embodiment is configured to include a base 94 and a conical electron emission portion 15E stacked on the base 94. here,
The base 94 and the electron-emitting portion 15E are made of different conductive materials. Specifically, the base 94 includes the electron emitting section 1
It is a member for adjusting the distance between 5E and the opening end of the gate electrode 13, has a function as a resistor layer, and is made of a polysilicon layer containing impurities. The electron emission portion 15E is made of tungsten, and has a conical shape, more specifically, a conical shape. still,
An adhesion layer 90 made of TiN is formed between the base 94 and the electron emission section 15E. Note that the adhesion layer 90 is not a component essential for the function of the electron emission portion, but is formed for manufacturing reasons. The opening 14 is formed by digging the insulating layer 12 from immediately below the gate electrode 13 to the upper end of the base 94.

Hereinafter, the manufacturing method of [Modification-5 of manufacturing method of Spindt-type field emission device] will be described with reference to FIGS. 42 and 43 which are schematic partial end views of a support and the like.

[Step-S1] First, the steps up to the formation of the opening 14 are described in [Modification of Manufacturing Method of Spindt-Type Field Emission Element-
1] in the same manner as in [Step-N1] of the production method. next,
By forming a conductive material layer for forming a base on the entire surface including the inside of the opening 14 and etching the conductive material layer, the base 94 burying the bottom of the opening 14 can be formed. Although the illustrated base 94 has a flattened surface, the surface may be concave. The base 94 having the flattened surface can be formed by the same process as [Step-R1] of the manufacturing method of [Modification-4 of Manufacturing Method of Spindt-Type Field Emission Element]. Further, the opening 1
An adhesive layer 90 and a conductive material layer 91 for forming an electron emitting portion are sequentially formed on the entire surface including the remaining portion of No. 4. At this time, the columnar portion 91B reflecting the step between the upper end surface and the bottom surface of the remaining portion of the opening 14 and the enlarged portion 9 communicating with the upper end of the columnar portion 91B.
1C is formed into a substantially funnel-shaped concave portion 91A.
The thickness of the conductive material layer 91 is selected so as to be generated on the surface of the conductive material layer 91. Next, a mask material layer 92 is formed over the conductive material layer 91. This mask material layer 92 is formed using, for example, copper. FIG. 42A shows a state in which the processes up to this point have been completed.

[Step-S2] Next, the mask material layer 92 and the conductive material layer 91 are removed in a plane parallel to the surface of the support 10 to leave the mask material layer 92 in the columnar portion 91B. (See FIG. 42 (B)). This removal is performed by a chemical mechanical polishing method (CMP method) as in [Step-P4].
Can be performed.

[Step-S3] Next, when the conductive material layer 91, the mask material layer 92, and the adhesive layer 90 are etched, the electron emission having a conical shape corresponding to the magnitude of the resist selectivity based on the mechanism described above. A portion 15E is formed. These layers can be etched in the same manner as in [Step-P5] of the manufacturing method of [Modification-2 of Manufacturing Method of Spindt-Type Field Emission Element]. An electron emission portion is formed by the electron emission portion 15E and the base 94, and the adhesion layer 90 remaining between the electron emission portion 15E and the base 94. The electron emitting portion may have a conical shape as a whole, but FIG. 43A shows a state in which a part of the base 94 remains so as to bury the bottom of the opening 14. . Such a shape is
This may occur when the height of the mask material layer 92 buried in the columnar portion 91B is low or the etching rate of the mask material layer 92 is relatively high, but this does not hinder the function as the electron emission portion.

[Step-S4] Then, when the side wall surface of the insulating layer 12 is recessed inside the opening 14 under isotropic etching conditions, the field emission device shown in FIG. 43B is completed. . The isotropic etching conditions may be the same as those described in the manufacturing method of [Modification-1 of Manufacturing Method of Spindt Field Emission Element].

[Modification of Manufacturing Method of Spindt-Type Field Emission Device-6] [Modification of Manufacturing Method of Spindt-Type Field Emission Device]
The manufacturing method of [6] is a modification of the manufacturing method of Spindt-type field emission device of [Modification-3 of manufacturing method of Spindt-type field emission device]. [Modification-6 of manufacturing method of Spindt-type field emission device] is a modification of manufacturing method of Spindt-type field emission device-
3] is that the electron-emitting portion has a base 94 and a base 94 in the same manner as in [Modification-4 of manufacturing method of Spindt-type field emission device].
And a conical electron emitting portion 15E stacked on the base 94. Hereinafter, a Spindt-type field emission device will be described.
6] will be described with reference to FIG. 44 which is a schematic partial end view of a support and the like.

[Step-T1] The process up to the formation of the mask material layer 92 is described as [Modification-5 of Manufacturing Method of Spindt-Type Field Emission Element].
In the same manner as in [Step-S1] of the manufacturing method. After that, only the mask material layer 92 on the conductive material layer 91 and in the enlarged portion 91C is removed to leave the mask material layer 92 on the columnar portion 91B (see FIG. 44). For example, by performing wet etching using a diluted hydrofluoric acid aqueous solution, only the mask material layer 92 made of copper can be selectively removed without removing the conductive material layer 91 made of tungsten. Thereafter, etching of the conductive material layer 91 and the mask material layer 92,
All processes such as isotropic etching of the insulating layer 12 are described in [Modification-5 of manufacturing method of Spindt-type field emission device].
Can be carried out in the same manner as in the production method.

The present invention has been described based on the embodiments of the present invention, but the present invention is not limited to these embodiments. The structures, configurations, and manufacturing methods of the anode panel, the cathode panel, and the display device described in the embodiment of the invention are merely examples, and can be appropriately changed.

Further, various materials used in the manufacture of the field emission device are also examples, and can be appropriately changed. In the field emission device, a configuration in which one electron emission portion corresponds to one opening portion has been described. However, depending on the structure of the field emission device, a configuration in which one opening portion corresponds to a plurality of electron emission portions. Alternatively, a mode in which one electron-emitting portion corresponds to a plurality of openings may be adopted.

A structure in which a focusing electrode is formed above the gate electrode may be employed. Here, the converging electrode is an electrode for converging the trajectory of the emitted electrons emitted from the opening toward the anode electrode, thereby improving the luminance and preventing color turbidity between adjacent pixels. Particularly effective when a potential difference between the electrode and the cathode electrode is on the order of several kilovolts and the distance between the cathode panel and the anode panel is relatively long, so-called high voltage type flat display device is assumed. Member. A relative negative voltage is applied to the focusing electrode from a focusing power supply. The focusing electrode does not necessarily need to be provided for each field emission element,
For example, a common convergence effect can be exerted on a plurality of field emission devices by extending the field emission devices along a predetermined arrangement direction.

In the display device, when the cathode panel CP and the anode panel AP are joined at the periphery,
The bonding may be performed using an adhesive layer, or may be performed using a frame body made of an insulating rigid material such as glass or ceramic and the adhesive layer in combination. When the frame body and the adhesive layer are used together, by appropriately selecting the height of the frame body, the facing distance between the cathode panel CP and the anode panel AP is increased as compared with the case where only the adhesive layer is used. It can be set longer. In addition, as a constituent material of the adhesive layer,
Frit glass is common, but has a melting point of 120-40.
A so-called low melting point metal material of about 0 ° C. may be used. As such a low melting point metal material, In (indium: melting point 1)
57 ° C); indium-gold based low melting point alloy; Sn ₈₀ A
g ₂₀ (mp 220-370 ° C), Sn ₉₅ Cu ₅ (melting point 227 to 370 ° C) such as tin (Sn) based high-temperature solder; P
b _97.5 Ag _2.5 (melting point 304 ° C), Pb _94.5 Ag
_5.5 (melting point 304-365 ° C), Pb _97.5 Ag _1.5 Sn
_1.0 (melting point: 309 ° C) lead (Pb) based high temperature solder;
Zinc (Zn) -based high-temperature solder such as Zn ₉₅ Al ₅ (melting point 380 ° C.); Sn ₅ Pb ₉₅ (melting point 300-314 ° C.);
Examples include tin-lead-based standard solders such as Sn ₂ Pb ₉₈ (melting point 316-322 ° C.); brazing materials such as Au ₈₈ Ga ₁₂ (melting point 381 ° C.) (all the above suffixes represent atomic%). Can be.

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

In the case of performing exhaust after bonding, the exhaust can be performed through a chip tube previously connected to the cathode panel CP and / or the anode panel AP. The tip tube is typically configured using a glass tube, and is formed around the through hole provided in the ineffective area of the cathode panel CP and / or the anode panel AP by using frit glass or the above-described low melting point metal material. After being joined and the space reaching a predetermined degree of vacuum, it is sealed off by heat fusion. In addition, if the entire display device is once heated and then cooled before the sealing is performed, the residual gas can be released into the space, and the residual gas can be removed to the outside of the space by exhaustion. is there.

In the display device, depending on the configuration of the field emission device (for example, when the electron emission portion is formed of a carbon thin film), the electron emission is simply provided on the cathode electrode without providing an insulating layer or a gate electrode. It is also possible to adopt a structure provided with a portion. In such a structure, the control of the voltage applied to the cathode electrode is performed in units of one pixel (one subpixel). The planar shape of the cathode electrode is substantially rectangular, and each cathode electrode is connected to a control circuit via a wiring and a switching element composed of, for example, a transistor. When a voltage equal to or higher than the threshold voltage is applied to each cathode electrode, electrons are emitted from the electron emitting portion based on an electric field formed by the anode electrode and quantum tunnel effect, and the electrons are attracted to the anode electrode, and the phosphor Hit the layers. Brightness is controlled by a voltage applied to the cathode electrode.

The gate electrode is formed of a band-shaped or sheet-shaped metal foil having an opening formed thereon. A gate electrode support is formed on a support, and the metal foil is in contact with the top surface of the gate electrode support. The metal foil may be stretched so that the opening is positioned above the electron-emitting portion. In this case, one electron emitting portion may be formed below a plurality of openings formed in the metal foil, or one electron emitting portion may be formed below one opening formed in the metal foil. May be formed.

The electron emission region can be constituted by a field emission element commonly called a surface conduction type field emission element. This surface conduction type field emission device is composed of, for example, tin oxide (SnO ₂ ), gold (Au), indium oxide (In ₂ O ₃ ) / tin oxide (SnO ₂ ), carbon, palladium oxide ( A pair of electrodes made of a conductive material such as PdO) and having a small area and arranged at a predetermined interval (gap) are formed in a matrix. A carbon thin film is formed on each electrode. Then, a row-direction wiring is connected to one electrode of the pair of electrodes, and a column-direction wiring is connected to the other electrode of the pair of electrodes. By applying a voltage to the pair of electrodes,
An electric field is applied to the carbon thin films facing each other across the gap, and electrons are emitted from the carbon thin films. By causing such electrons to collide with the phosphor layer on the anode panel, the phosphor layer is excited and emits light, and a desired image can be obtained.

[0234]

According to the present invention, a phosphor-forming layer composed of a resin and phosphor particles is formed between partition walls, and the resin is removed by a heat treatment in a later step, so that a smooth surface is formed on the phosphor layer. The anode electrode can be easily formed,
The brightness of the cold cathode field emission display can be improved. Furthermore, unlike the conventional method, there is no need to form an intermediate film, so that the manufacturing process of an anode panel or a cold cathode field emission display for a cold cathode field emission display is simplified and the manufacturing cost is reduced. Can be.

If the phosphor forming layer is formed by a printing method, the step of exposing and developing the phosphor forming layer is not required, and the anode panel or the cold cathode field electron for a cold cathode field emission display device is not required. The manufacturing process of the emission display device can be greatly simplified, and the manufacturing cost can be further reduced. Moreover, the photosensitivity is not required for the raw material of the phosphor forming layer, and the range of selection of the raw material of the phosphor forming layer is widened.

[Brief description of the drawings]

FIG. 1 is a schematic partial cross-sectional view of a substrate and the like for explaining a method of manufacturing a cold cathode field emission display or an anode panel for a cold cathode field emission display according to an embodiment of the invention.

FIG. 2 is a partial plan view of a substrate or the like for describing a method of manufacturing a cold cathode field emission display or an anode panel for a cold cathode field emission display according to an embodiment of the present invention.

FIG. 3 is a schematic partial end view of a cold cathode field emission display.

FIG. 4 is a schematic partial perspective view of a cathode panel constituting a cold cathode field emission display.

FIG. 5 is a schematic partial end view of a support and the like for describing a method for manufacturing a Spindt-type cold cathode field emission device.

FIG. 6 is a schematic partial end view of a support and the like for explaining a method of manufacturing the Spindt-type cold cathode field emission device following FIG. 5;

FIG. 7 is a schematic partial end view of a support and the like for describing a method of manufacturing a crown-type cold cathode field emission device.

FIG. 8 is a schematic partial end view of a support and the like for explaining the method of manufacturing the crown-type cold cathode field emission device following FIG.

FIG. 9 is a schematic partial cross-sectional view of a support and the like for describing a method of manufacturing the flat cold cathode field emission device-1.

FIG. 10 is a schematic partial cross-sectional view of a support and the like for explaining a method of manufacturing the flat type cold cathode field emission device-2.

FIG. 11 is a schematic partial end view of a support and the like for explaining a method of manufacturing the flat type cold cathode field emission device-3.

FIG. 12 is a schematic partial end view of a support and the like for describing a method of manufacturing the flat type cold cathode field emission device-3, following FIG. 12;

FIG. 13 is a schematic partial cross-sectional view of a support and the like for describing a method of manufacturing the flat cold cathode field emission device-1.

FIG. 14 is a schematic partial cross-sectional view of a flat cold cathode field emission device-2.

FIG. 15 is a schematic partial cross-sectional view of a flat cold cathode field emission device-2.

FIG. 16 is a schematic partial end view and a partial perspective view of a support and the like for describing a method of manufacturing the crater-type cold cathode field emission device-1.

17 is a schematic partial end view and a partial perspective view of a support and the like for describing a method for manufacturing the crater-type cold cathode field emission device-1 following FIG.

18 is a schematic partial end view and a partial perspective view of a support and the like for describing a method of manufacturing the crater-type cold cathode field emission device-1 following FIG. 18;

FIG. 19 is a schematic partial cross-sectional view of a support and the like for describing a method for manufacturing the crater-type cold cathode field emission device-1 following FIG. 19;

FIG. 20 is a schematic partial cross-sectional view of a support and the like for explaining a method of manufacturing the crater-type cold cathode field emission device-2.

FIG. 21 is a schematic partial end view of a support and the like for explaining a method of manufacturing the crater-type cold cathode field emission device-3.

FIG. 22 is a schematic partial end view of a support and the like for explaining a method of manufacturing the crater-type cold cathode field emission device-4.

FIG. 23 is a schematic partial end view of the support and the like for explaining the method for manufacturing the crater-type cold cathode field emission device-4, following FIG. 22;

FIG. 24 is a schematic partial sectional view of an edge-type cold cathode field emission device.

FIG. 25 is a schematic partial end view of a support and the like for explaining a method of manufacturing an edge-type cold cathode field emission device.

FIG. 26 is a schematic partial end view of a support and the like for describing [Modification-1 of the manufacturing method of Spindt-type cold cathode field emission device].

FIG. 27 is a schematic partial end view of a support and the like for explaining [Modification-1 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 26;

FIG. 28 is a schematic partial end view of the support and the like for explaining [Modification-1 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 27;

FIG. 29 is a schematic partial end view of the support and the like for explaining [Modification-1 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 28;

FIG. 30 is a view for explaining a mechanism for forming a conical electron emitting portion.

FIG. 31 is a diagram schematically showing a relationship between a resist selectivity and the height and shape of an electron-emitting portion.

FIG. 32 is a schematic partial end view of a support and the like for explaining [Modification-2 of the method for manufacturing a Spindt-type cold cathode field emission device].

FIG. 33 is a schematic partial end view of the support and the like for explaining [Modification-2 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 32;

FIG. 34 is a schematic partial end view of a support and the like for illustrating [Modification-2 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 33;

FIG. 35 is a diagram showing how the surface profile of the object to be etched changes at regular intervals.

FIG. 36 is a schematic partial end view of a support or the like for describing [Modification-3 of the Spindt-type cold cathode field emission device manufacturing method].

FIG. 37 is a schematic partial end view of the support and the like for illustrating [Modification-3 of the Spindt-type cold cathode field emission device manufacturing method] following FIG. 36;

FIG. 38 is a schematic partial end view of a Spindt-type cold cathode field emission device obtained by [Modification-4 of manufacturing method of Spindt-type cold cathode field emission device].

FIG. 39 is a schematic partial end view of a support and the like for explaining [Modification-4 of the method for manufacturing a Spindt-type cold cathode field emission device].

FIG. 40 is a schematic partial end view of the support and the like for explaining [Modification-4 of method for manufacturing Spindt-type cold cathode field emission device] following FIG. 39;

FIG. 41 is a schematic partial end view of the support and the like for explaining [Modification-4 of the method for manufacturing a Spindt-type cold cathode field emission device] following FIG. 40;

FIG. 42 is a schematic partial end view of a support and the like for explaining [Modification-5 of the Spindt-type cold cathode field emission device manufacturing method].

FIG. 43 is a schematic partial end view of the support and the like for explaining [Modification-5 of the manufacturing method of Spindt-type cold cathode field emission device] following FIG. 42;

FIG. 44 is a schematic partial end view of a support and the like for describing [Modification-6 of the Spindt-type cold cathode field emission device manufacturing method].

FIG. 45 is a schematic partial cross-sectional view of a substrate or the like for explaining a conventional method of manufacturing a cold cathode field emission display or an anode panel for a cold cathode field emission display.

FIG. 46 is a partial plan view of a substrate or the like for describing a conventional method of manufacturing a cold cathode field emission display or an anode panel for a cold cathode field emission display.

[Explanation of symbols]

CP: cathode panel, AP: anode panel, 10: support, 11, 111, 211 ... cathode electrode, 111A ... ridge, 111B ... recess, 111C ... tip Part, 11A ... minute uneven part,
11B: coating layer, 12, 12A, 12B: insulating layer, 13, 13A, 13B: gate electrode, 14.1
4A, 14B: opening, 15, 15A, 15B, 1
5C, 15D, 15E: electron emission portion, 17: release layer, 18: conductive material layer, 20: substrate, 21 ·
..Partition walls, 22, 22R, 22G, 22B phosphor layer, 22, 22R ', 22G', 22B 'phosphor formation layer, 23 resin layer, 24 intermediate film, 25 ・
..Anode electrode, 30 frame, 40 scanning circuit, 41 control circuit, 42 accelerating power supply, 51
..Release layer, 52 ... conductive composition layer, 60 ... resistor layer, 70 ... carbon thin film selective growth area, 71 ...
Mask layer, 72: metal particles, 73: carbon thin film,
80, 180: sphere, 81: composition layer, 81A
... Dispersion medium, 81B ... Cathode electrode material, 180
A: core material, 180B: surface treatment layer, 90:
Adhesion layer, 91: conductive material layer, 91A: recess, 9
1B: columnar portion, 91C: enlarged portion, 92: mask material layer, 93: etching stop layer, 94:
Base, 94A: conductive material layer, 95: flattening layer

Claims (10)

[Claims] (A) a step of forming a partition on a substrate; (B) a step of forming a phosphor-forming layer made of resin and phosphor particles between the partitions; (C) a step of forming a partition and a phosphor. Forming an anode electrode made of a metal thin film on the layer; and (D) removing the resin constituting the phosphor forming layer by performing a heat treatment, whereby the phosphor layer is formed on the substrate between the partition walls. A method of manufacturing an anode panel for a cold cathode field emission display device. 2. The cold cathode field emission according to claim 1, wherein in the step (B), a phosphor forming layer made of a resin and phosphor particles is formed between the partition walls based on a printing method. A method for manufacturing an anode panel for a display device. 3. The method of manufacturing an anode panel for a cold cathode field emission display according to claim 2, wherein a metal mask having a through hole is used in the printing method. 4. The method according to claim 1, wherein in the step (B), the upper layer is mainly occupied by the resin, and the lower layer is mainly formed by the phosphor particles. Of manufacturing an anode panel for a cold cathode field emission display device. 5. The phosphor layer includes a red light-emitting phosphor layer, a green light-emitting phosphor layer, and a blue light-emitting phosphor layer, and the phosphor for forming the red light-emitting phosphor layer in the step (B). A forming layer, a phosphor forming layer for forming a green light emitting phosphor layer, and a phosphor forming layer for forming a blue light emitting phosphor layer are formed in any order between predetermined partition walls based on a printing method. The method for manufacturing an anode panel for a cold cathode field emission display according to claim 1, wherein: 6. A method for manufacturing a cold cathode field emission display device, comprising joining a cathode panel on which a cold cathode field emission device is formed and an anode panel at their outer peripheral portions, wherein the anode panel is (A) a step of forming a partition on the substrate; (B) a step of forming a phosphor-forming layer comprising a resin and phosphor particles between the partition; and (C) a step of forming a phosphor-forming layer on the partition and the phosphor-forming layer. A step of forming an anode electrode made of a metal thin film; and (D) a step of removing the resin constituting the phosphor-forming layer by performing a heat treatment, thereby obtaining a phosphor layer on the substrate between the partition walls. And a method for manufacturing a cold cathode field emission display device. 7. The cold cathode field emission according to claim 6, wherein in the step (B), a phosphor forming layer made of a resin and phosphor particles is formed between the partition walls based on a printing method. A method for manufacturing a display device. 8. The method of manufacturing a cold cathode field emission display according to claim 7, wherein a metal mask having a through hole is used in the printing method. 9. The method according to claim 6, wherein in the step (B), the upper layer is mainly occupied by the resin, and the lower layer is mainly formed by the phosphor particles. Of manufacturing a cold cathode field emission display device according to the present invention. 10. The phosphor layer includes a red light-emitting phosphor layer, a green light-emitting phosphor layer, and a blue light-emitting phosphor layer, and the phosphor for forming the red light-emitting phosphor layer in the step (B). A forming layer, a phosphor forming layer for forming a green light emitting phosphor layer, and a phosphor forming layer for forming a blue light emitting phosphor layer are formed in any order between predetermined partition walls based on a printing method. 7. The method of manufacturing a cold cathode field emission display according to claim 6, wherein: