JP2002208345A - Manufacturing method of cold cathode field electron emission element and manufacturing method of cold cathode field electron emission display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a cold cathode field electron emission element that can form an electron emission part steadily by a simple method and at the center of the bottom of the opening. SOLUTION: In the manufacturing method of the cold cathode field electron emission element, a cathode electrode 11 and an insulating layer 12 are formed on the support 10, and an opening part 14B is formed on the insulating layer 12, and then a resist material layer 40 is formed on the whole face including the bottom of the opening 14B and the side wall. Then energy rays are irradiated on the resist layer 40 without using the exposure mask, and then by developing the resist material layer 40, the resist material layer 40 is selectively removed from the bottom of the opening 14B. Thereby, after exposing the cathode electrode 11 at the bottom of the opening 14B, an electron emission part is formed on the cathode electrode 11 exposed at the bottom of the opening 14B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a cold cathode field emission device and a method for manufacturing a cold cathode field emission display.

[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, liquid crystal display devices are widely used as display devices for information terminal equipment, but there are still problems in high brightness and large size for application to stationary television receivers. . 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. 23 shows a configuration example of a cold cathode field emission display device (hereinafter, may be referred to as a display device) using a field emission element. The illustrated field emission device has a conical electron emission portion, a so-called Spindt.
This is a type of device called a field emission device. 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, It comprises an opening 114 provided in the electrode 13 and the insulating layer 12, and a conical electron emitting portion 115 formed on the cathode electrode 11 located at the bottom of the opening 114. In general, the cathode electrode 11 and the gate electrode 13 are formed such that the projected images of these two electrodes are formed in a stripe shape in a direction orthogonal to each other, and a region where the projected images of these two electrodes overlap (one pixel). In general, a plurality of field emission elements are arranged in this area. Further, such overlapping areas are usually arranged in a two-dimensional matrix in an effective area (area functioning as an actual display portion) of the cathode panel CP.

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 23 formed thereon. One pixel is composed of a group of field emission elements arranged in an overlapping region of the cathode electrode 11 and the gate electrode 13 on the cathode panel side, and a phosphor layer 22 on the anode panel side facing the group of these field emission elements. It is configured. In the effective area, such pixels are arranged, for example, in the order of several hundred thousand to several million.
Note that a black matrix 21 is formed on the substrate 20 between the phosphor layers 22.

Anode panel AP and cathode panel CP
Are arranged such that the field emission element and the phosphor layer 22 face each other, and are joined at the peripheral portion via the frame 24, whereby a display device can be manufactured. In an invalid area (in the illustrated example, an invalid area of the cathode panel CP) surrounding the effective area and having a peripheral circuit for selecting a pixel, a through hole 25 for evacuation is provided. The through-hole 25 is connected to a chip tube 26 that has been sealed off after evacuation. That is, the anode panel AP
The space surrounded by the cathode panel CP and the frame 24 is a vacuum.

A relative negative voltage is applied to the cathode electrode 11 from the scanning circuit 30, a relative positive voltage is applied to the gate electrode 13 from the control circuit 31, and
Has a higher positive voltage than 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 30 and a video signal is input to the gate electrode 13 from the control circuit 31. Cathode electrode 11 and gate electrode 1
An electron is emitted from the electron-emitting portion 115 based on the quantum tunnel effect by an electric field generated when a voltage is applied between the electron-emitting device 3 and the electron-emitting device 3, and the electron is attracted to the anode electrode 23 and collides with the phosphor layer 22. As a result, the phosphor layer 22 is excited to emit light, and a desired image can be obtained. That is, the operation of this display device basically depends on the gate electrode 13.
And the voltage applied to the electron emission unit 115 through the cathode electrode 11.

In the structure of such a display device, it is effective to sharpen the tip of the electron-emitting portion in order to obtain a large emission electron current at a low driving voltage. It can be said that the electron emission section 115 has excellent performance. However, the formation of the conical electron-emitting portion 115 requires advanced processing technology, and in some cases, tens of millions or more of the electron-emitting portions 115 are formed uniformly over the entire effective area. Are becoming more difficult as the area of the effective region increases.

Therefore, without forming a conical electron emission portion,
A so-called flat type field emission device using a flat electron emission portion exposed at the bottom of the opening has been proposed. The electron emission portion in the flat field emission device is provided on the cathode electrode, and is made of a material having a work function lower than that of the cathode electrode so that a high emission electron current can be achieved even in a flat shape. It is configured.

An outline of a conventional method of manufacturing a flat type field emission device using such a material will be described below with reference to FIGS. 24 and 25 which are schematic partial end views of a support and the like. .

[Step-10] 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 known lithography technique and a reactive ion etching method (RIE method). The striped cathode electrode 11 extends in the left-right direction on the drawing sheet. The cathode electrode 11 is made of, for example, a chromium (Cr) layer having a thickness of about 0.2 μm formed by a sputtering method.

[Step-20] Thereafter, the insulating layer 12 is formed on the entire surface, specifically, on the support 10 and the cathode electrode 11.
To form

[Step-30] Next, after the stripe-shaped gate electrode 13 is formed on the insulating layer 12, a hole 14A of the gate electrode 13 is formed, and the opening 14B communicating with the hole 14A is insulated. Formed on the layer 12, the cathode electrode 11 is exposed at the bottom of the opening 14B (FIG. 24 (A)
reference). The striped gate electrode 13 extends in a direction perpendicular to the plane of the drawing. The hole 14A and the opening 14B may be collectively referred to as the opening 14 hereinafter. The planar shape of the opening 14 is, for example, 1 μm to 30 μm in diameter.
It is a circle of μm. For example, about 1 to 3000 openings 14 may be formed in a region (electron emission region) for one pixel.

[Step-40] Next, the electron-emitting portion 15 is formed on the cathode electrode 11 exposed at the bottom of the opening 14. Specifically, after the resist material layer 40 is formed on the entire surface including the inside of the opening 14 by the spin coating method (see FIG. 24B), the resist is formed based on lithography using an exposure mask. The material layer 40 is exposed (see FIG. 24C). At the bottom of the opening 14, an unexposed portion 40A of the resist material layer is left. After that, the resist material layer 40 is developed. This allows the cathode electrode 11 to be exposed at the center of the bottom of the opening 14 (see FIG. 25A). The resist material layer 40
A portion 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;
Is coated.

[Step-50] Thereafter, on the resist material layer 40 including the surface of the cathode electrode 11 exposed at the bottom of the opening 14, the work function is lower than that of the constituent material of the cathode electrode based on, for example, a sputtering method. An electron emission portion forming layer 41 made of a material is formed (see FIG. 25B). Thereafter, by removing the resist material layer 40, the cathode electrode 11 exposed at the bottom of the opening 14 is formed.
An electron emitting portion 15 composed of the electron emitting portion forming layer 41 can be formed thereon (see FIG. 25C).

[0015]

[Problems to be Solved by the Invention] Usually, [Step-40]
In the step of exposing the resist material layer 40 based on the lithography technique using an exposure mask,
The reference marker provided on the support 10 and the marker of the exposure mask are aligned so that the unexposed portion 40A is formed in the resist material layer 40 located at the center of the bottom of the substrate.

However, in an actual lithography process, a sputtering method or a chemical vapor deposition method (CV
D method), between the exposure mask and the support 10 due to deformation of the support 10 caused by stress when various thin films and layers are formed, expansion and contraction and deformation of the support 10 in various heat treatment steps, and the like. Misalignment is likely to occur. as a result,
The distance between the electron emission portion 15 formed on the cathode electrode 11 exposed at the bottom of the opening 14 and the opening end of the gate electrode 13 varies. When such variations occur, the characteristics of the electron emission from the electron emitter 15 vary, resulting in display unevenness. Such a problem is particularly prominent when the size of the display device is increased.

As a means for realizing a lithography process with less misalignment, a so-called stepper (reduction exposure machine) may be used. However, the stepper is very expensive, and when a display device is enlarged, Exposure takes a long time, and the manufacturing cost of the display device increases.

The object of the present invention is therefore to provide a simple method,
Moreover, a method of manufacturing a cold cathode field emission device capable of reliably forming an electron emission portion at the center of the bottom of the opening, and a cold cathode field emission device to which the method of manufacturing a cold cathode field emission device is applied An object of the present invention is to provide a method for manufacturing an emission display device.

[0019]

To achieve the above object, a method of manufacturing a cold cathode field emission device according to the present invention comprises:
(A) a step of forming a cathode electrode on a support;
(B) a step of forming an insulating layer on the cathode electrode and the support, (C) a step of forming an opening in the insulating layer, and (D)
Forming a resist material layer on the entire surface including the bottom and side walls of the opening, and (E) irradiating the resist material layer with energy rays without using an exposure mask;
Developing the resist material layer to selectively remove the resist material layer from the bottom of the opening, thereby exposing the cathode electrode to the bottom of the opening; and (F) exposing the cathode electrode to the bottom of the opening. Forming an electron-emitting portion on the cathode electrode.

In order to achieve the above object, a method for manufacturing a cold cathode field emission display according to the present invention comprises a plurality of pixels, each pixel comprising a plurality of cold cathode field emission devices and a plurality of cold cathode field emission devices. A cathode panel including a plurality of cold cathode field emission devices formed of an anode electrode and a phosphor layer facing the cathode field emission device, and an anode panel formed with the anode electrode and the phosphor layer are formed of the same. A method of manufacturing a cold cathode field emission display device joined at a peripheral portion, comprising: (A) forming a cathode electrode on a support; (B) forming a cathode electrode; Forming an insulating layer on the support; and (C)
Forming an opening in the insulating layer; (D) forming a resist material layer on the entire surface including the bottom and side walls of the opening; and (E) applying energy to the resist material layer without using an exposure mask. Irradiating a line and then developing the resist material layer to selectively remove the resist material layer from the bottom of the opening, thereby exposing the cathode electrode at the bottom of the opening; (F) Forming at least a step of forming an electron emission portion on the cathode electrode exposed at the bottom of the opening.

In the method for manufacturing a cold cathode field emission device or the method for manufacturing a cold cathode field emission display device of the present invention (hereinafter, these may be collectively simply referred to as the manufacturing method of the present invention). Step (B) and Step (C)
Forming a gate electrode having a hole on the insulating layer, wherein in the step (E), the energy ray is formed at an incident angle other than 0 degree with respect to the normal to the support. Irradiation to the resist material layer can be adopted. In addition, the manufacturing method of the present invention in such an embodiment is referred to as a manufacturing method according to the first embodiment of the present invention for convenience.

In the manufacturing method according to the first aspect of the present invention, when the cathode electrode is exposed at the bottom of the opening in the step (E), the insulating layer and the gate electrode and the opening are removed. A layer of resist material on at least the top of the sidewall of the portion (possibly on all of the sidewall of the opening, or on all of the sidewall of the opening and a portion of the cathode electrode located at the bottom of the opening) Is left.

In the manufacturing method according to the first aspect of the present invention or the manufacturing method according to a third aspect of the present invention described later, the method for forming a gate electrode having a hole on an insulating layer is described below. For example, a physical vapor deposition method (P
After a conductive material layer for a gate electrode is formed based on a VD method or a chemical vapor deposition method (CVD method), a gate electrode that has holes and is patterned in a stripe shape by a lithography technique and an etching technique is formed. Examples of the method include a method of forming a gate electrode that has a hole and is patterned in a stripe shape by a method, a screen printing method, a lift-off method, or the like.

Alternatively, in the manufacturing method of the present invention, a step of forming a conductive material layer for a gate electrode having a hole on the insulating layer between the step (B) and the step (C);
And, after the step (F), the method further comprises a step of patterning the conductive material layer for a gate electrode to form a gate electrode. An embodiment in which the resist material layer is irradiated with energy rays at an incident angle other than 0 degree can be adopted. In addition, the manufacturing method of the present invention in such an embodiment is referred to as a manufacturing method according to the second embodiment of the present invention for convenience.

In the manufacturing method according to the second aspect of the present invention, in the state where the cathode electrode is exposed at the bottom of the opening in the step (E), the gate electrode is formed on the conductive material layer.
And at least over the top of the sidewall of the opening (possibly over all of the sidewall of the opening or over all of the sidewall of the opening and a portion of the cathode electrode located at the bottom of the opening) The resist material layer is left.

In the manufacturing method according to the second aspect of the present invention or the manufacturing method according to a fourth aspect of the present invention described later, a conductive material layer for a gate electrode having a hole is formed on an insulating layer. As a forming method, for example, after forming a conductive material layer for a gate electrode by a PVD method or a CVD method on an insulating layer,
Examples of the method include a method of forming a conductive material layer for a gate electrode having a hole by a lithography technique and an etching technique, and a method of forming a conductive material layer for a gate electrode having a hole by a screen printing method or a lift-off method.

In the manufacturing method according to the first or second aspect of the present invention, the incident angle is such that a portion of the resist material layer located at the center of the bottom of the opening is not irradiated with energy rays. It is preferred that Specifically, for example, the incident angle may be determined based on the aspect ratio of the opening and the thickness of the resist material layer.
Note that the portion of the resist material layer located at the center of the bottom of the opening need not be irradiated with energy rays.For example, the portion of the resist material layer located at the bottom of the opening may not be irradiated with energy rays, or or,
The portion of the resist material layer located at the bottom of the opening and the portion of the resist material layer located below the side wall of the opening may not be irradiated with energy rays.

In the manufacturing method according to the first aspect of the present invention, the method may further include a step of removing the resist material layer after the step (F). Alternatively, between the step (E) and the step (F), the method further comprises a step of forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening, and a step of removing the resist material layer. ,
In the step (F), an electron emitting portion may be formed on the underlayer.

The manufacturing method according to the second aspect of the present invention further comprises a step of removing the resist material layer after the step (F) and before patterning the gate electrode conductive material layer. Configuration. Alternatively, between the step (E) and the step (F), the method further comprises a step of forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening, and a step of removing the resist material layer. In the step (F), an electron emitting portion may be formed on the underlayer.

Alternatively, in the manufacturing method of the present invention, between the step (B) and the step (C), a step of forming a gate electrode having a hole on an insulating layer; ) Between the step (E) and the step (E), further comprising a step of forming a light-shielding film on the resist material layer on the insulating layer and the gate electrode and on the resist material layer on the side wall of the opening. Can be. In addition, the manufacturing method of the present invention in such an embodiment is referred to as a manufacturing method according to the third embodiment of the present invention for convenience.

In the manufacturing method according to the third aspect of the present invention, in the step of forming the light-shielding film, on the insulating layer and the gate electrode, and on at least the upper part of the side wall of the opening (in some cases). May be formed on the entire side wall of the opening, or on the entire side wall of the opening and a part of the cathode electrode located at the bottom of the opening). As a result, in a state where the cathode electrode is exposed at the bottom of the opening in the step (E), the insulating layer and the gate electrode, and at least the upper part of the side wall of the opening (in some cases, the upper part of the side wall of the opening) A layer of resist material is left over all, or over all of the sidewalls of the opening and over a portion of the cathode electrode located at the bottom of the opening.

Alternatively, in the manufacturing method of the present invention, between the step (B) and the step (C), a step of forming a gate electrode conductive material layer having a hole on the insulating layer;
Forming a light-shielding film on the resist material layer on the conductive material layer for the gate electrode and on the resist material layer on the side wall of the opening between the step (D) and the step (E); After the step (F), the conductive material layer for a gate electrode may be patterned to form a gate electrode. In addition, the manufacturing method of the present invention in such an embodiment is referred to as a manufacturing method according to the fourth embodiment of the present invention for convenience.

In the manufacturing method according to the fourth aspect of the present invention, in the step of forming the light-shielding film, on the conductive material layer for the gate electrode and at least on the upper part of the side wall of the opening (case) In some cases, the light-shielding film may be formed over the entire side wall of the opening or over the entire side wall of the opening and a part of the cathode electrode located at the bottom of the opening. As a result, in a state where the cathode electrode is exposed at the bottom of the opening in the step (E), on the conductive material layer for the gate electrode and at least on the upper part of the side wall of the opening (in some cases, the side wall of the opening) , Or over all of the sidewalls of the opening and over a portion of the cathode electrode located at the bottom of the opening).

Alternatively, in the manufacturing method according to the present invention, between the step (D) and the step (E), the resist material layer on the insulating layer and the resist material layer on the side wall of the opening may be formed. Forming a light-shielding film, and the step (F)
After that, the method may further include a step of forming a gate electrode having a hole communicating with the opening provided in the insulating layer over the insulating layer. In addition, the manufacturing method of the present invention in such an embodiment is referred to as a manufacturing method according to the fifth embodiment of the present invention for convenience.

In the manufacturing method according to the fifth aspect of the present invention, the step of forming the light shielding film includes the steps of:
And at least over the top of the sidewall of the opening (possibly over all of the sidewall of the opening or over all of the sidewall of the opening and a portion of the cathode electrode located at the bottom of the opening) What is necessary is just to form a light-shielding film. as a result,
In a state where the cathode electrode is exposed at the bottom of the opening in the step (E), on the insulating layer and on at least the upper part of the side wall of the opening (in some cases, on all of the side walls of the opening, or A layer of resist material is left on all of the sidewalls of the opening and on a portion of the cathode electrode located at the bottom of the opening.

In the manufacturing method according to the fifth aspect of the present invention, as a method of forming a gate electrode having a hole on an insulating layer, for example, an incidence angle other than 0 ° with respect to a normal line of a support is used. After forming a conductive material layer for a gate electrode at a corner by a PVD method, a method of forming a gate electrode patterned into a desired shape by a lithography technique and an etching technique, a screen printing method, a lift-off method, or the like to obtain a desired shape. A method of forming a patterned gate electrode can be exemplified.

In the manufacturing method according to the third to fifth aspects of the present invention, the step of forming the light-shielding film is performed by applying the light-shielding film to the PVD method at an incident angle other than 0 ° with respect to the normal to the support. It is preferable that the method comprises a step of forming a film. Specifically, for example, the incident angle may be determined based on the aspect ratio of the opening and the thickness of the resist material layer. Examples of the PVD method include a vacuum evaporation method and a sputtering method. When the sputtering method is employed, it is desirable to employ a so-called sputtering method using a collimator in order to make the incident angles of the materials constituting the light shielding film uniform.

Further, in the manufacturing method according to the third aspect of the present invention, after the step (F), a step of removing the resist material layer may be further provided. Alternatively, between the step (E) and the step (F), the method further comprises a step of forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening, and a step of removing the resist material layer. In the step (F), an electron emitting portion may be formed on the underlayer.

In the manufacturing method according to the fourth aspect of the present invention, the step of removing the resist material layer after the step (F) and before patterning the gate electrode conductive material layer is performed. Further, a configuration may be provided. Alternatively, between the step (E) and the step (F), the method further comprises a step of forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening, and a step of removing the resist material layer. In the step (F), an electron emitting portion may be formed on the underlayer.

In the manufacturing method according to the fifth aspect of the present invention, the step of removing the resist material layer after the step (F) and before forming the gate electrode on the insulating layer is performed. Further, a configuration may be provided. Alternatively, between the steps (E) and (F), a step of forming an underlayer on the surface of the cathode electrode exposed at the bottom of the opening;
And removing the resist material layer. In the step (F), an electron emission portion may be formed on the underlayer.

In the production method according to the first or second aspect of the present invention, the resist material layer is polymerized or cross-linked by irradiation with an energy beam to become insoluble or hardly soluble in a developing solution. On the other hand, in the manufacturing method according to the third to fifth aspects of the present invention, the positive resist becomes soluble in a developer by decomposing the resist material layer by irradiation with energy rays. It is desirable to be composed of a material. Examples of energy rays include ultraviolet rays having various wavelengths and electron beams.

The material constituting the light-shielding film may be any material that can reliably shield the energy rays, such as chromium (Cr) and titanium (Ti). The thickness of the light-shielding film may be any thickness that can surely shield the energy rays, and for example, may be about 0.2 μm.

The plane shape of the hole and the opening is essentially arbitrary, such as a circle, an ellipse, a rectangle, a rounded rectangle, a polygon, a rounded polygon, etc. Is most preferred.

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

As a structure of a cold cathode field emission device (hereinafter abbreviated as a field emission device), a so-called crown type (crown-shaped electron emission portion) is provided on a cathode electrode located at the bottom of the opening. Field emission device) and a flat type (a field emission device in which a substantially flat electron emission portion is provided on a cathode electrode located at the bottom of an opening).

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 ( Indium tin oxide)
And other transparent conductive materials. 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, irregular, etc.
Although not particularly limited, it is preferable that the exposed portions of the conductive particles have a shape that can be sharp projections. Conductive particles having different sizes and shapes may be mixed and used.

In the flat type field emission device, or alternatively, the electron emission portion is preferably made of a material having a work function Φ smaller than that of the cathode electrode. 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. As a typical material constituting the cathode electrode in the field emission device,
Tungsten (Φ = 4.55 eV), niobium (Φ = 4.55 eV)
02 to 4.87 eV), molybdenum (Φ = 4.53 to)
4.95 eV), aluminum (Φ = 4.28 eV),
Copper (Φ = 4.6 eV), tantalum (Φ = 4.3 eV),
Chromium (Φ = 4.5 eV), silicon (Φ = 4.9 e)
V). The electron emitting portion preferably has a work function Φ smaller than these materials, and its value is preferably approximately 3 eV or less. Such materials include carbon such as graphite (Φ <1e).
V), cesium (Φ = 2.14 eV), LaB ₆ (Φ =
2.66-2.76 eV), BaO (Φ = 1.6-2.
7 eV), SrO (Φ = 1.25-1.6 eV), Y ₂
O ₃ (Φ = 2.0 eV), CaO (Φ = 1.6 to 1.8)
6 eV), BaS (Φ = 2.05 eV), TiN (Φ =
2.92 eV) and 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. Note that the material forming the electron emitting portion does not necessarily need 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 emitting 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 whose secondary electron gain δ is larger than that 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 elements 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 the field emission device, as a material constituting the cathode electrode, tungsten (W), niobium (Nb), tantalum (Ta), molybdenum (Mo), chromium (Cr), aluminum (Al), gold ( Au), metals such as copper (Cu); alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , Mo)
Examples thereof include silicides such as Si ₂ , TiSi ₂ and TaSi ₂ ); semiconductors such as silicon (Si); and ITO (indium tin oxide). 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.

Tungsten (W), niobium (N) may be used as a conductive material forming a gate electrode or a conductive material layer for a gate electrode in a field emission device.
b), metals such as tantalum (Ta), molybdenum (Mo), chromium (Cr), aluminum (Al), and copper (Cu); alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , MoSi ₂ , TiSi
₂ , silicide such as TaSi ₂ ); or silicon (S
Semiconductors such as i), diamond, carbon, and ITO (indium tin oxide) can be exemplified.

In the field emission device, one hole may be provided in the gate electrode and the insulating layer and one electron emission portion may be present in the opening, or a plurality of holes may be provided in the gate electrode. One opening communicating with the hole may be provided in the insulating layer, and a plurality of electron-emitting portions may be present in one opening provided in the insulating layer.

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

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.

As a method of forming the electron emission portion of the field emission device, a coating method, a vapor deposition method, a sputtering method, or a CVD method is used.
And a lift-off method, which is a basic method for forming an electron-emitting portion in the manufacturing method of the present invention.

In the manufacturing method of the present invention, since the resist material layer is irradiated with energy rays without using an exposure mask, the cathode electrode can be exposed at the bottom center of the opening in a self-aligned manner.

[0057]

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

(Embodiment 1) Embodiment 1 relates to the manufacturing method according to the first aspect of the present invention. Hereinafter, the manufacturing method of the first embodiment will be described with reference to FIGS. 4 and 5 which are schematic partial end views of the support and the like. In the first embodiment, a flat type field emission device is manufactured. Here, the electron emission portion is made of tungsten (W) formed by a sputtering method. Embodiment 1
1 are shown in the sequence of [Case 1] in FIG.

[Step-100] First, a striped cathode electrode 11 made of ITO is formed on a support 10 made of, for example, glass. Specifically, a stripe-shaped cathode electrode 11 can be formed by forming an ITO layer on the support 10 by a sputtering method and patterning the ITO layer by a lithography technique and an etching technique. Thereafter, for example, CVD
An insulating layer 12 made of SiO ₂ is formed by a method. The striped cathode electrode 11 extends in the left-right direction of the drawing.

[Step-110] Next, the gate electrode 13 having the hole 14A is formed on the insulating layer. In particular,
For example, after a gate electrode conductive material layer made of aluminum is formed on the insulating layer 12 by a sputtering method, a mask layer is formed on the gate electrode conductive material layer based on a lithography technique, and the mask layer is used as an etching mask. The conductive material layer for the gate electrode is patterned in a stripe shape based on the RIE method. Next, the mask layer is removed, a mask layer is formed again on the entire surface based on the lithography technique, and the mask layer is used as an etching mask for RI.
A hole 14A is formed in the gate electrode conductive material layer by the E method, and an opening 14B is formed in the insulating layer 12 by the RIE method. After that, the mask layer is removed. Thus, the striped gate electrode 13 having the hole 14A, and
The opening 14B can be formed (see FIG. 4A). In the following description, the holes 14A and
The openings 14B communicating with the holes 14A may be simply referred to as the openings 14. The projected image of the gate electrode 13 extending in a stripe shape is orthogonal to the projected image of the cathode electrode 11 extending in a stripe shape. Opening 1
In the formation of No. 4, the higher accuracy is not required as far to the left,
The accuracy may be about μm. Therefore, a normal lithography technique can be used.

[Step-120] Thereafter, a resist material layer 40 is formed on the entire surface including the bottom and the side wall of the opening 14 by a known spin coating method (see FIG. 4B). The resist material layer 40 was composed of a negative resist (ZPN1100 manufactured by Zeon Corporation).

[Step-130] Next, the resist material layer 40 is irradiated with energy rays (specifically, ultraviolet rays) without using an exposure mask. That is, the support 10
The resist material layer 40 is exposed based on a so-called oblique exposure method, in which the resist material layer 40 is irradiated with energy rays (ultraviolet rays) at an incident angle θ that is not 0 ° with respect to the normal line of the support 10 while rotating. (See FIG. 4C). The incident angle θ is set so that the portion 40A of the resist material layer 40 located at the center of the bottom of the opening 14 is not irradiated with energy rays (ultraviolet rays). Specifically, the incident angle θ may be determined in consideration of the aspect ratio of the opening 14 (the ratio of the diameter of the opening to the thickness of the insulating layer) and the thickness of the resist material layer 40. In the illustrated example, the resist material layer 40 on the insulating layer 12 and the gate electrode 13 and on all of the side walls of the opening 14 and a part of the cathode electrode 11 located at the bottom of the opening 14 is exposed.

Next, the resist material layer 40 is developed so that the resist material layer 40
The unexposed portion 40A is selectively removed, and thus the opening 1
The cathode electrode 11 is exposed at the bottom of the substrate 4 (see FIG. 5A). AZ3 manufactured by Clariant Japan KK
The resist material layer 40 was developed using 00MIF as a developing solution.

[Step-140] Then, the electron emitting portion 15 is formed on the surface of the cathode electrode 11 exposed at the bottom of the opening portion 14.
To form Specifically, an electron emission portion forming layer 41 made of tungsten (W) is formed on the entire surface by a sputtering method (see FIG. 5B). An electron emission portion forming layer 41 is deposited on the surface of the cathode electrode 11 exposed at the bottom of the opening 14 and on the resist material layer 40.

[Step-150] Then, acetone or Na
A so-called lift-off method of removing the resist material layer 40 using OH and a resist stripper (eg, AZ Remover 200 manufactured by Clariant Japan KK) is performed. Thereby, the electron emission portion forming layer 41 on the resist material layer 40 is also removed, and the electron emission portion 15 including the electron emission portion formation layer 41 is formed only on the surface of the cathode electrode 11 exposed at the bottom of the opening 14. (See FIG. 5C).
After that, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13.

In [Step-140], for example, the electron-emitting portion 15 made of graphite powder paint may be formed by spin coating. In this case, after [Step-150], it is preferable to perform a heat treatment at 400 ° C. for 30 minutes in order to remove the organic solvent in the electron-emitting portion 15.

[Step-160] Thereafter, a cold cathode field emission display (hereinafter abbreviated as a display) is assembled. Specifically, the phosphor layers 22 (red light emitting phosphor layer 22R, green light emitting phosphor layer 22G, blue light emitting phosphor layer 2
2B) and the anode panel AP and the cathode panel CP are arranged such that the field emission element faces the anode panel AP and the cathode panel CP (more specifically, the substrate 2).
0 and the support 10) are joined at a peripheral portion thereof via a frame 24 having a height of about 1 mm made of ceramics or glass. At the time of joining, the joint portion between the frame 24 and the anode panel AP, and the frame 24 and the cathode panel C
After frit glass is applied to a joint portion with P, the anode panel AP, the cathode panel CP, and the frame 24 are bonded to each other, and the frit glass is dried by pre-baking.
The main baking is performed at 0 ° C. for 10 to 30 minutes. Thereafter, the space surrounded by the anode panel AP, the cathode panel CP, the frame 24, and the frit glass (not shown) is exhausted through the through-hole 25 and the chip tube 26, and the pressure in the space is reduced to about 10 ^-4 Pa. At that point, the tip tube 26 is sealed off by heating and melting. Thus, the anode panel AP
The space surrounded by the cathode panel CP and the frame 24 can be evacuated. Alternatively, for example, the frame 24
The bonding of the anode panel AP and the cathode panel CP may be performed 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. After that, wiring connection with necessary external circuits is performed to complete the display device. FIG. 6 shows a schematic partial end view of the display device thus obtained, and FIG. 7 shows a schematic perspective view of a part of the anode panel AP and the cathode panel CP.
The method of assembling the display device, the structure of the anode panel AP described later, and the operation of the display device can be similarly applied to the cathode panel CP on which various field emission devices described below are formed.

Anode Panel AP Constituting Display Device
Is composed of a substrate 20, a phosphor layer 22 formed on the substrate 20 and having a predetermined pattern, and an anode electrode 23 formed thereon. One pixel includes a group of field emission elements arranged in an overlapping region of the cathode electrode 11 and the gate electrode 13 on the cathode panel side, and a phosphor layer 2 on the anode panel side facing the group of these field emission elements.
And 2. In the effective area, such pixels are arranged, for example, in the order of several hundred thousand to several million. Note that a black matrix 21 is formed on the substrate 20 between the phosphor layers 22.

A relative negative voltage is applied to the cathode electrode 11 from the scanning circuit 30, and a relative positive voltage is applied to the gate electrode 13 from the control circuit 31.
Has a higher positive voltage than 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 30 and a video signal is input to the gate electrode 13 from the control circuit 31. Cathode electrode 11 and gate electrode 1
An electron is emitted from the electron-emitting portion 15 by the 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, and the electron is attracted to the anode electrode 23 and collides with the phosphor layer 22. As a result, the phosphor layer 22 is excited to emit light, and a desired image can be obtained.

An example of a method for manufacturing the anode panel AP is as follows.
Hereinafter, description will be made with reference to FIG. First, a luminescent crystal particle composition is prepared. For this purpose, for example, a dispersant is dispersed in pure water, and the mixture is stirred for 1 minute at 3000 rpm using a homomixer. Next, the luminescent crystal particles are put into pure water in which a dispersant is dispersed, and 50
Stir at 00 rpm for 5 minutes. Then, for example,
Add polyvinyl alcohol and ammonium bichromate, stir well and filter.

In the manufacture of the anode panel AP, a photosensitive film 50 is formed on the entire surface of the substrate 20 made of, for example, glass.
Is formed (applied). Then, the photosensitive film 50 formed on the substrate 20 is exposed by exposure light emitted from an exposure light source (not shown) and passed through an opening 54 provided in the mask 53 to form a photosensitive region 51 ( (See FIG. 22A). Thereafter, the photosensitive film 50 is developed and selectively removed, and the remaining portion of the photosensitive film (photosensitive film after exposure and development) 52 is left on the substrate 20 (see FIG. 22B). Next, a carbon agent (carbon slurry) is applied to the entire surface, dried and baked, and then the remaining portion 52 of the photosensitive film and the carbon agent thereon are removed by a lift-off method. A black matrix 21 made of an agent is formed, and at the same time, the remaining portion 52 of the photosensitive film is removed (see FIG. 22C). Then, on the exposed substrate 20, each of the red, green, and blue phosphor layers 2
2 (see FIG. 22D). Specifically, a luminescent crystal particle composition prepared from each luminescent crystal particle (phosphor particle) is used. For example, a red photosensitive luminescent crystal particle composition (phosphor slurry) is applied to the entire surface. Coating, exposing and developing, then applying a green photosensitive luminescent crystal particle composition (phosphor slurry) over the entire surface, exposing and developing, and further, a blue photosensitive luminescent crystal particle composition (Phosphor slurry) may be applied to the entire surface, exposed and developed.
Then, an anode electrode 23 is formed on the phosphor layer 22 and the black matrix 21 by forming an aluminum thin film having a thickness of about 0.07 μm by a sputtering method. Thus, the anode panel AP can be obtained. Each phosphor layer 22 is formed by a screen printing method or the like.
Can also be formed.

In Embodiment 1, [Step-13]
0], the resist material layer 40 is exposed by an oblique exposure method without using an exposure mask, so that the finally obtained electron-emitting portion 15 is self-aligned with the center of the bottom of the opening 14. As a result, even when the size of the display device is increased, it is possible to form the electron-emitting portion 15 without displacement with respect to the gate electrode 13.

(Embodiment 2) Embodiment 2 is a modification of the manufacturing method of Embodiment 1. In the second embodiment, a crown type field emission device is manufactured. FIG. 9A is a schematic partial end view of a field emission device including a crown-type field emission device, and FIG. 9B is a schematic perspective view with a portion cut away. 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, a hole 14 A and an opening 14 B (opening 14) penetrating the gate electrode 13 and the insulating layer 12, and a cathode electrode 11 located at the bottom of the opening 14. Crown provided above
The electron emission portion 15A is formed.

The manufacturing method according to the second embodiment will be described below with reference to FIGS. 8 to 9 which are schematic partial end views of a support and the like.

[Step-200] First, a striped cathode electrode 11 is placed on a support 10 made of, for example, glass.
To form Note that the cathode electrode 11 extends in the left-right direction of the drawing. Striped cathode electrode 11
Is, for example, after forming an ITO film over the entire surface to a thickness of about 0.2 μm on the support 10 by a sputtering method,
It can be formed by patterning an ITO film. The striped cathode electrode 11 extends in the left-right direction of the drawing. The cathode electrode 11 is
It may be a single material layer, or it may be constituted 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 a 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, the moisture and the solvent contained in the insulating layer 12 are removed and the insulating layer 12 is removed.
In order to make the surface flat, two-stage baking is performed, for example, temporary baking at 100 ° C. for 10 minutes and main baking at 500 ° C. for 20 minutes. Instead of the screen printing using the glass paste as described above, an SiO ₂ film may be formed by, for example, a plasma CVD method.

[Step-210] Next, a stripe-shaped gate electrode 13 is formed on the insulating layer 12 in the same manner as in [Step-110] of the first embodiment. The gate electrode 13 extends in a direction perpendicular to the plane of the drawing. That is, the direction in which the projected image of the gate electrode 13 extends is 90 degrees with the direction in which the projected image of the striped cathode electrode 11 extends.
Next, in the same manner as in [Step-110] of the first embodiment,
The gate electrode 13 and the insulating layer 12 are etched based on the RIE method, and a hole 14A is formed in the gate electrode 13 and the insulating layer 12.
And an opening 14B (opening 14).
The cathode electrode 11 is exposed at the bottom of the substrate. The diameter of the opening 14 is about 2 to 50 μm.

[Step-220] Thereafter, the same steps as [Step-120] to [Step-130] of the first embodiment are executed to expose the cathode electrode 11 at the bottom of the opening 14 (FIG. 8 (A)).

[Step-230] Next, as shown in FIG. 8B, a conductive composition layer 6 made of a composition material is formed on the entire surface.
0 is formed. Composition raw materials used here, for example,
As conductive particles, graphite particles having an average particle size of about 0.1 μm
0% by weight, No. 4 water glass as binder 40% by weight
Including. This composition raw material is, for example, 1400 rpm, 10
Spin coat the entire surface under the condition of seconds. The surface of the conductive composition layer 60 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 60 is performed, for example, in the air at 400 ° C. for 30 minutes.

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 described in 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 to be dispersed in the water glass, affinity with the resist material layer 40, and the aspect ratio of the opening 14 are taken into consideration. Then, it is preferable 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 composition raw material, the electric resistance of the electron-emitting portion 15A to be formed increases, There is a concern 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 emission 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 the carbon-based material particles are used as the conductive particles, the diameter of the carbon-based material particles 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-240] Next, as shown in FIG. 8C, the resist material layer 40 is removed in the same manner as in [Step-150] of the first embodiment. At this time, the removal may be performed while applying ultrasonic vibration. Thereby, the portion of the conductive composition layer 60 on the resist material layer 40 together with the resist material layer 40 is removed, leaving only the portion of the conductive composition layer 60 on the cathode electrode 11 exposed at the bottom of the opening 14. It is. This remaining portion is the electron emitting portion 15A.
Becomes The shape of the electron emitting portion 15A is such that
It is depressed toward the center and becomes a crown. [Step-24]
[0] is shown in FIG. FIG.
9B is a schematic perspective view showing a part of the field emission device, and FIG. 9A is a schematic partial end view along line AA in FIG. 9B. It is. In FIG. 9B, 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. Note that the electron emission portion 15 is so arranged that the conductive particles are reliably exposed on the surface of the electron emission portion 15A.
The binder exposed on the surface of A may be removed by etching.

[Step-250] Next, the electron emitting portion 15A
Is fired. Baking is performed in dry air at 400 ° C., 30
Perform under the condition of 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,
The 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. Whichever 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.

[Step-260] Thereafter, the same steps as [Step-160] of the first embodiment are performed to complete the display device.

(Embodiment 3) Embodiment 3 is also a modification of the manufacturing method of Embodiment 1. Note that, also in the third embodiment, a flat type field emission device is manufactured. Embodiment 3
In, the electron emission portion is composed of a carbon thin film formed based on a CVD method. Further, a carbon thin film selective growth region as a base layer is formed between the electron emitting portion and the cathode electrode.

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).

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 ion incidence probability 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 carbon thin film selective growth region, which is an underlayer, 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. The configuration may be such that That is,
In the manufacturing method according to the third embodiment, a carbon thin film selective growth region as an underlayer is formed on the surface of the cathode electrode exposed at the bottom of the opening before forming the electron-emitting portion. Remove. Then, a carbon thin film corresponding to an electron emission portion is formed on the carbon thin film selective growth region serving as an underlayer. Here, the step of forming the carbon thin film selective growth region is referred to as a carbon thin film selective growth region forming step for convenience. The carbon thin film selective growth region may be formed on the entire surface of the portion of the cathode electrode located at the bottom of the opening, or may be formed partially, and may be formed in the shape of the remaining resist material layer. Dependent.

Here, the carbon thin film selective growth region is preferably a portion of the cathode electrode having metal particles attached to the surface or a portion of the cathode electrode having the 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. 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 triphenylboron.
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,
It is desirable to remove the metal oxide (so-called natural oxide film) on the surface of the metal particles constituting the carbon thin film selective growth region 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.

As a step of forming a carbon thin film selective growth region, a step of forming a layer composed of a solvent and metal particles over the entire surface and then removing the solvent to leave the metal particles can be mentioned. Alternatively, as a carbon thin film selective growth region forming step, after forming metal compound particles containing metal atoms constituting the metal particles on the entire surface, the metal compound particles are decomposed by heating, whereby the metal particles are deposited on the surface. A step of obtaining a carbon thin film selective growth region consisting of the portion of the cathode electrode adhered thereto. In this case, specifically, a method of forming a layer composed of a solvent and metal compound particles on the entire surface and then removing the solvent to leave the metal compound particles can be exemplified. The metal compound particles are made of at least one material selected from the group consisting of halides (e.g., iodides, chlorides, bromides, etc.), oxides, hydroxides, and organometals of the metal constituting the metal particles. Is preferred. In these methods, at an appropriate stage, the resist material layer covering an area other than the area of the cathode electrode where the carbon thin film selective growth area is to be formed is removed.

Alternatively, the carbon thin film selective growth region forming step may be further performed, for example, by an electrolytic plating method in which a region other than the cathode electrode region where the carbon thin film selective growth region is to be formed is covered with a resist material layer. And known methods such as electroless plating, CVD including MOCVD, and PVD. In addition, as a PVD 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 formed. 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.

Hereinafter, the manufacturing method of the third embodiment will be described with reference to FIG. 10 which is a schematic partial end view of a support and the like. The flow of each step of the manufacturing method according to the third embodiment is shown by the sequence of [Case 2] in FIG.

[Step-300] First, a conductive material layer for a cathode electrode is formed on a support 10 made of, for example, glass, and then the conductive material layer for a cathode electrode is patterned based on a well-known lithography technique and RIE method. As a result, the striped cathode electrode 11 is
0. The striped cathode electrode 11
It extends in the horizontal direction of the drawing. Cathode electrode 11
Consists of a chromium (Cr) layer having a thickness of about 0.2 μm formed by, for example, a sputtering method.

[Step-310] Thereafter, the insulating layer 1 is formed on the entire surface, specifically, on the support 10 and the cathode electrode 11.
Form 2 Next, the stripe-shaped gate electrode 13
Is formed on the insulating layer 12 and then the [Step-
110], a hole and an opening (opening 14) are 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. 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, 1 μm or more in diameter.
It is a circular shape of 30 μm. For example, about 1 to 3000 openings 14 may be formed in a region (electron emission region) for one pixel.

[Step-320] Thereafter, the same steps as [Step-120] to [Step-130] of the first embodiment are performed to expose the cathode electrode 11 at the bottom of the opening 14.

[Step-330] Next, the electron emission portion 15B is formed on the cathode electrode 11 exposed at the bottom of the opening 14. Specifically, first, the carbon thin film selective growth region 7 is formed on the surface of the cathode electrode 11 located at the bottom of the opening 14.
0 is formed. Therefore, the exposed cathode electrode 11
Metal particles are adhered on the resist material layer 40 including the surface of the resist material. 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, and the cathode electrode 11 exposed at the bottom of the opening 14 is coated. To form a carbon thin film selective growth region 70 comprising a solvent and metal particles.

[Step-340] Next, the resist material layer 40 is removed in the same manner as in [Step-150] of the first embodiment. After that, the solvent is removed by heating to about 400 ° C., and the metal particles 71 are left on the exposed surface of the cathode electrode 11.
Is completed (see FIG. 10A). The polysiloxane is deposited on the exposed surface of the cathode electrode 11 with the metal particles 7.
1 has a function of fixing (so-called adhesive function).

[Step-350] Thereafter, a carbon thin film 72 having a thickness of about 0.2 μm is formed on the carbon thin film selective growth region 70 to obtain the electron emitting portion 15B. This state is shown in FIG. Table 1 below shows conditions for forming the carbon thin film 72 based on the microwave plasma CVD method. The carbon thin film 72 is selectively formed only on the carbon thin film selective growth region 70, and is not formed on other portions.

[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

[Step-360] Thereafter, the same steps as [Step-160] of the first embodiment are performed to complete the display device.

Embodiment 4 Embodiment 4 is a modification of the manufacturing method described in Embodiment 1, and relates to a manufacturing method according to the second aspect of the present invention. Hereinafter, the manufacturing method of the fourth embodiment will be described with reference to FIGS. 11 to 12 which are schematic partial end views of a support and the like, but the fourth embodiment is similar to the first embodiment. Is manufactured. The flow of each step of the manufacturing method according to the fourth embodiment is shown by the sequence of [Case 3] in FIG.

[Step-400] First, in the same manner as in [Step-100] of the first embodiment, a striped cathode electrode 1 made of ITO is formed on a support 10 made of glass.
Form one. The striped cathode electrode 11
Extend in the left-right direction of the drawing. Thereafter, an insulating layer 12 made of SiO ₂ is formed on the entire surface by, for example, a CVD method.

[Step-410] Next, a gate electrode conductive material layer 13A having a hole 14A is formed on the insulating layer. Specifically, after a gate electrode conductive material layer 13A made of, for example, aluminum is formed on the insulating layer 12 by a sputtering method, a mask layer is formed on the gate electrode conductive material layer 13A based on a lithography technique. Using the mask layer as an etching mask, a hole 14A is formed in the gate electrode conductive material layer 13A, and an opening 14B is formed in the insulating layer 12. After that, the mask layer is removed. Thus, the sheet-shaped conductive material layer 13A for the gate electrode having the hole 14A and the opening 14B can be formed (see FIG. 11A). The hole 14A
In forming the opening 14B (opening 14), higher accuracy is not required as far to the left, and an accuracy of about ± 5 μm is sufficient. Therefore, a normal lithography technique can be used.

[Step-420] Then, in the same manner as in [Step-120] of the first embodiment, the resist material layer 40 is formed on the entire surface including the bottom and side walls of the opening 14 by a known spin coating method. (See FIG. 11B).

[Step-430] Next, as in [Step-130] of the first embodiment, energy rays (specifically, ultraviolet rays) are applied to the resist material layer 40 without using an exposure mask. Is irradiated. That is, while rotating the support 10, the resist material layer 40 is irradiated with energy rays (ultraviolet rays) at an incident angle θ that is not 0 degree with respect to the normal of the support 10 based on a so-called oblique exposure method. 40 exposures are performed (see FIG. 11C). Then
By developing the resist material layer 40, the opening 1
4 is selectively removed from the bottom of the resist material layer 40, thereby exposing the cathode electrode 11 at the bottom of the opening 14 (see FIG. 12A).

[Step-440] Then, similarly to [Step-140] of the first embodiment, the electron-emitting portion 15 is formed on the surface of the cathode electrode 11 exposed at the bottom of the opening 14.

[Step-450] Next, in the same manner as in [Step-150] of the first embodiment, a so-called lift-off method for removing the resist material layer 40 is performed. As a result, the electron emission portion forming layer 41 on the resist material layer 40 is also removed, and the cathode electrode 11 exposed at the bottom of the opening 14 is removed.
The electron-emitting portion 15 composed of the electron-emitting portion forming layer 41 is formed only on the surface (see FIG. 12C).

[Step-460] Then, the conductive material layer 13A for a gate electrode is patterned, thereby forming the gate electrode 1A.
Form 3 Specifically, the conductive material layer for gate electrode 1
Forming a mask layer on 3A based on lithography technology,
By using the mask layer as an etching mask and patterning the gate electrode conductive material layer 13A in a stripe shape, the mask layer may be removed.

In [Step-440], for example,
The electron emission portion 15 made of graphite powder paint may be formed by a spin coating method. In this case,
After [Step-450], it is preferable to perform a heat treatment at 400 ° C. for 30 minutes in order to remove the organic solvent in the electron emission portion 15.

[Step-470] Then, the same steps as [Step-160] of the first embodiment are performed to complete the display device.

The manufacturing method described above is applied to the second embodiment.
Alternatively, the present invention can be applied to the manufacturing method described in the third embodiment. Specifically, when the method described in Embodiment 4 is applied to the manufacturing method described in Embodiments 2 and 3, [Step-210] and [Step-31]
0], the same step as [Step-410] may be executed, and after [Step-250] and [Step-350], the same step as [Step-460] may be executed. The flow of each step when the manufacturing method of the fourth embodiment is applied to the manufacturing method described in the third embodiment is shown in [Case 4] of FIG.
Shown in the sequence.

(Embodiment 5) Embodiment 5 relates to the manufacturing method according to the third aspect of the present invention. Hereinafter, the manufacturing method of the fifth embodiment will be described with reference to FIGS. 13 to 15 which are schematic partial end views of the support and the like. In the fifth embodiment also, a flat field emission device is manufactured. Here, the electron emission portion is made of tungsten (W) formed by a sputtering method. The flow of each step of the manufacturing method according to the fifth embodiment is shown by the sequence of [Case 5] in FIG.

[Step-500] First, in the same manner as in [Step-100] of the first embodiment, a striped cathode electrode 1 made of ITO is formed on a support 10 made of glass.
Form one. The striped cathode electrode 11
Extend in the left-right direction of the drawing. Thereafter, an insulating layer 12 made of SiO ₂ is formed on the entire surface by, for example, a CVD method.

[Step-510] Next, a stripe-shaped gate electrode 13 is formed on the insulating layer 12 in the same manner as in [Step-110] of the first embodiment.
Then, a hole and an opening (opening 14) are formed in the insulating layer 12, and the cathode electrode 11 is exposed at the bottom of the opening 14 (see FIG. 13A). Striped gate electrode 1
Reference numeral 3 extends in the 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, about 1 to 3000 openings 14 may be formed in a region (electron emission region) for one pixel.

[Step-520] Then, in the same manner as in [Step-120] of the first embodiment, a resist material layer 40 is formed on the entire surface including the bottom and side walls of the opening 14 by a known spin coating method. (See FIG. 13B). The resist material layer 40 was formed of a positive resist (AZP4210 manufactured by Clariant Japan KK).

[Step-530] Next, the resist material layer 40 on the insulating layer 12 and the gate electrode 13 and on the side walls of the hole 14A and the opening 14B.
A light-shielding film 42 made of chromium (Cr) having a thickness of about 0.2 μm is formed thereon by a sputtering method (see FIG. 13C). Specifically, the light-shielding film 42 is formed at an angle of incidence other than 0 ° with respect to the normal to the support 10 by oblique vacuum evaporation while rotating the support 10. As a result, the resist material layer 40 located at the bottom of the opening 14
No light-shielding film 42 is deposited on this portion. The formation of the light-shielding film 42 is performed in an atmosphere in which the resist material layer 40 is not exposed to light.
The light shielding film 42 is formed at a temperature (for example, 110 ° C.) or lower at which the photosensitivity of 0 is not impaired.

[Step-540] Next, the resist material layer 40 is irradiated with energy rays (specifically, ultraviolet rays) without using an exposure mask. Here, the incident angle of the energy rays (ultraviolet rays) to the resist material layer 40 is set to be parallel to the normal line of the support 10 (see FIG. 14A).
Thus, only the portion 40B of the resist material layer 40 located at the bottom of the opening 14 is exposed.

Next, the light-shielding film 42 is removed by wet etching, and the resist material layer 40 is further developed to selectively remove the exposed portion 40B of the resist material layer 40 from the bottom of the opening 14. Then, the cathode electrode 11 is exposed at the bottom of the opening 14 (FIG. 14B).
reference). AZ300M manufactured by Clariant Japan KK
The resist material layer 40 was developed using IF as a developing solution.

[Step-550] Then, similarly to [Step-140] of the first embodiment, an electron-emitting portion 15 is formed on the surface of the cathode electrode 11 exposed at the bottom of the opening 14. Specifically, an electron emission portion forming layer 41 made of tungsten (W) is formed on the entire surface by sputtering (see FIG. 14C). The surface of the cathode electrode 11 exposed at the bottom of the opening 14 and the resist material layer 40
An electron emission portion forming layer 41 is deposited on the upper surface.

[Step-560] Then, in the same manner as in [Step-150] of the first embodiment, acetone, NaOH,
Using a resist stripper (for example, AZ Remover 200 manufactured by Clariant Japan KK), the resist material layer 4
A so-called lift-off method for removing 0 is performed. As a result, the electron emission portion forming layer 41 on the resist material layer 40 is also removed, and the cathode electrode 1 exposed at the bottom of the opening 14 is removed.
The electron emission portion 15 composed of the electron emission portion forming layer 41 is formed only on the surface of the substrate 1 (see FIG. 15). After that, it is preferable that the insulating layer 12 is isotropically etched to expose the edge of the opening of the gate electrode 13.

[Step-570] Thereafter, the same steps as [Step-160] of the first embodiment are performed to complete the display device.

In the fifth embodiment, [Step-53
0], a light-shielding film is formed by an oblique evaporation method, and the resist material layer 40 is exposed without using an exposure mask, so that the finally obtained electron-emitting portion 15 is located at the center of the bottom of the opening 14. As a result, even if the display device is enlarged, it is possible to form the electron-emitting portion 15 having no displacement with respect to the gate electrode 13.

The manufacturing method described in the second embodiment can be applied to the manufacturing method in the fifth embodiment described above.

The manufacturing method according to the third embodiment can be applied to the manufacturing method according to the fifth embodiment. The flow of each step of such a manufacturing method is shown by the sequence of [Case 6] in FIG. Specifically, after executing [Step-500] to [Step-540], [Step-330] to [Step-3] of the third embodiment are performed.
50] may be performed.

(Embodiment 6) Embodiment 6 is a modification of the manufacturing method described in Embodiment 5, and relates to a manufacturing method according to a fourth aspect of the present invention. Hereinafter, the manufacturing method of the sixth embodiment will be described with reference to FIGS. 16 to 18 which are schematic partial end views of a support and the like, but the sixth embodiment is the same as the fifth embodiment. Is manufactured. The flow of each step of the manufacturing method according to the sixth embodiment is shown by the sequence of [Case 7] in FIG.

[Step-600] First, in the same manner as in [Step-100] of the first embodiment, a striped cathode electrode 1 made of ITO is formed on a support 10 made of glass.
Form one. The striped cathode electrode 11
Extend in the left-right direction of the drawing. Thereafter, an insulating layer 12 made of SiO ₂ is formed on the entire surface by, for example, a CVD method.

[Step-610] Next, in the same manner as in [Step-410] of the fourth embodiment, a sheet-shaped conductive material layer 13A for a gate electrode having a hole 14A is formed on the insulating layer. An opening 14B is formed in the insulating layer 12 (FIG. 1).
6 (A)).

[Step-620] Thereafter, in the same manner as in [Step-520] of the fifth embodiment, the resist material layer 40 is formed on the entire surface including the bottom and the side wall of the opening 14 by a known spin coating method. (See FIG. 16B).

[Step-630] Then, in the same manner as in [Step-530] of the fifth embodiment, the resist material layer 40 on the gate electrode conductive material layer 13A and the holes 14 are formed.
A light-shielding film 42 of chromium (Cr) having a thickness of about 0.2 μm is formed on the resist material layer 40 on the side walls of the opening A and the opening 14B by a sputtering method (see FIG. 16C). Specifically, the light-shielding film 42 is formed at an angle of incidence other than 0 ° with respect to the normal to the support 10 by oblique vacuum evaporation while rotating the support 10. As a result, the resist material layer 40 located at the bottom of the opening 14
No light-shielding film 42 is deposited on this portion.

[Step-640] Next, in the same manner as in [Step-540] of the fifth embodiment, energy rays (specifically, ultraviolet rays) are applied to the resist material layer 40 without using an exposure mask. Is irradiated. Here, the angle of incidence of the energy ray (ultraviolet light) on the resist material layer 40 is determined by the support 1
It is assumed that it is parallel to the normal line of 0 (see FIG. 17A). As a result, the resist material layer 4 located at the bottom of the opening 14
Only the 0 portion 40B is exposed. Next, the light shielding film 42
Is removed by wet etching, and the exposed portion 40B of the resist material layer 40 is selectively removed from the bottom of the opening 14 by further developing the resist material layer 40. The electrode 11 is exposed (see FIG. 17B).

[Step-650] Then, similarly to [Step-140] of the first embodiment, the electron-emitting portion 15 is formed on the surface of the cathode electrode 11 exposed at the bottom of the opening. Specifically, an electron emission portion forming layer 41 made of tungsten is formed on the entire surface by a sputtering method (see FIG. 17C). An electron emission portion forming layer 41 is deposited on the surface of the cathode electrode 11 exposed at the bottom of the opening 14 and on the resist material layer 40.

[Step-660] Then, in the same manner as in [Step-560] of the fifth embodiment, a so-called lift-off method of removing the resist material layer 40 is performed. As a result, the electron emission portion forming layer 41 on the resist material layer 40 is also removed, and the cathode electrode 11 exposed at the bottom of the opening 14 is removed.
The electron-emitting portion 15 composed of the electron-emitting portion forming layer 41 is formed only on the surface (see FIG. 18).

[Step-670] Then, the gate electrode conductive material layer 13A is patterned in the same manner as in [Step-460] of the fourth embodiment to form the gate electrode 13. Specifically, a mask layer is formed on the gate electrode conductive material layer 13A based on a lithography technique, and the gate electrode conductive material layer 13A is patterned in a stripe shape using the mask layer as an etching mask.
The mask layer may be removed.

[Step-680] Then, a display device is completed by executing the same steps as [Step-160] of the first embodiment.

The manufacturing method described above is applied to the second embodiment.
Alternatively, the manufacturing method described in Embodiment Mode 3 can be applied. Specifically, when the manufacturing method described in the second embodiment is applied to the method described in the sixth embodiment, the same steps as in [Step-230] are performed instead of [Step-650]. do it. When the manufacturing method described in Embodiment 3 is applied to the method described in Embodiment 6, instead of [Step-650] to [Step-660], [Step-330] to [Step] -350]. The manufacturing method according to the sixth embodiment is different from the manufacturing method according to the third embodiment.
The flow of each step in the case of applying the manufacturing method described in [1] is shown by the sequence of [Case 8] in FIG.

(Embodiment 7) Embodiment 7 is also a modification of the manufacturing method described in Embodiment 5, and relates to a manufacturing method according to a fifth aspect of the present invention. Hereinafter, the manufacturing method of the seventh embodiment will be described with reference to FIGS. 19 to 21 which are schematic partial end views of a support and the like, but the seventh embodiment is similar to the fifth embodiment. Is manufactured. The flow of each step of the manufacturing method according to the seventh embodiment is shown by the sequence of [Case 9] in FIG.

[Step-700] First, in the same manner as in [Step-100] of the first embodiment, a striped cathode electrode 1 made of ITO is formed on a support 10 made of glass.
Form one. The striped cathode electrode 11
Extend in the left-right direction of the drawing. The striped cathode electrode 11 extends in the left-right direction of the drawing. Thereafter, an insulating layer 12 made of SiO ₂ is formed on the entire surface by, for example, a CVD method.

[Step-710] Next, a mask layer is formed on the entire surface based on the lithography technique, and the insulating layer 12 is etched by RIE using the mask layer as an etching mask to form an opening 14B in the insulating layer 12. Form. After that, the mask layer is removed. Thus, the opening 14B can be formed in the insulating layer 12 (see FIG. 19A). In forming the opening 14B, higher accuracy is not required as far to the left, and it is sufficient that the accuracy is approximately ± 5 μm. Therefore, a normal lithography technique can be used.

[Step-720] Then, in the same manner as in [Step-520] of the fifth embodiment, a resist material layer 40 is formed on the entire surface including the bottom and the side wall of the opening 14B by a known spin coating method. (See FIG. 19B).

[Step-730] Then, similarly to [Step-530] of the fifth embodiment, the resist material layer 40 on the insulating layer 12 and the resist material layer 40 on the side wall of the opening 14B are formed. , About 0.2μ thickness by sputtering method
A light-shielding film 42 made of m chromium (Cr) is formed (see FIG. 19C). Specifically, the light-shielding film 42 is formed at an angle of incidence other than 0 ° with respect to the normal to the support 10 by oblique vacuum evaporation while rotating the support 10. Thus, the light shielding film 42 is not deposited on the portion of the resist material layer 40 located at the bottom of the opening 14B.

[Step-740] Next, in the same manner as in [Step-540] of the fifth embodiment, energy rays (specifically, ultraviolet rays) are applied to the resist material layer 40 without using an exposure mask. Is irradiated. Here, the angle of incidence of the energy ray (ultraviolet light) on the resist material layer 40 is determined by the support 1
It is assumed that it is parallel to the normal line of 0 (see FIG. 20A). Thus, only the portion 40B of the resist material layer 40 located at the bottom of the opening 14B is exposed. Next, the light shielding film 4
2 is removed by wet etching, and further, the exposed portion 40B of the resist material layer 40 is selectively removed from the bottom of the opening 14B by developing the resist material layer 40. The cathode electrode 11 is exposed (see FIG. 20B).

[Step-750] Then, similarly to [Step-140] of the first embodiment, the electron-emitting portion 15 is formed on the surface of the cathode electrode 11 exposed at the bottom of the opening 14B. Specifically, an electron emission portion forming layer 41 made of tungsten is formed on the entire surface by sputtering (see FIG. 20C). The surface of the cathode electrode 11 exposed at the bottom of the opening 14B and the resist material layer 40
An electron emission portion forming layer 41 is deposited on the upper surface.

[Step-760] Then, a so-called lift-off method for removing the resist material layer 40 is performed in the same manner as in [Step-560] of the fifth embodiment. As a result, the electron emission portion forming layer 41 on the resist material layer 40 is also removed, and the cathode electrode 1 exposed at the bottom of the opening 14B is removed.
The electron emission portion 15 composed of the electron emission portion forming layer 41 is formed only on the surface of the substrate 1 (see FIG. 21A).

[Step-770] Then, a conductive material layer for a gate electrode is formed on the insulating layer 12 by an oblique vacuum evaporation method. The conductive material layer for the gate electrode is not deposited on the bottom of the opening 14B. Then, the gate electrode 13 having the hole 14A communicating with the opening 14B provided in the insulating layer 12 is formed on the insulating layer 12 by patterning the conductive material layer for the gate electrode by lithography and etching. Is possible ((B) of FIG. 21)
reference). The striped gate electrode 13 extends in a direction perpendicular to the plane of the drawing.

[Step-780] Next, a display device is completed by executing the same steps as [Step-160] of the first embodiment.

The second embodiment is different from the above-described manufacturing method in the second embodiment.
Alternatively, the manufacturing method described in Embodiment Mode 3 can be applied. Specifically, when the manufacturing method described in Embodiment 2 is applied to the method described in Embodiment 7, the same steps as [Step-230] are performed instead of [Step-750]. do it. When the manufacturing method described in Embodiment 3 is applied to the method described in Embodiment 7, instead of [Step-750] to [Step-760], [Step-330] to [Step] -350]. The manufacturing method according to the seventh embodiment is different from the manufacturing method according to the third embodiment.
The flow of each step in the case of applying the manufacturing method described in [1] is shown by the sequence of [Case 10] in FIG.

As described above, 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 electron emission portion corresponds to a plurality of openings. It can also be.

A structure in which a focusing electrode is formed above the gate electrode may be adopted. 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. A particularly effective member when the 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 display device is assumed. It is. 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, by extending along a predetermined arrangement direction of the field emission elements, a common focusing effect can be exerted on a plurality of field emission elements. Can also.

When the converging electrode is provided, the gate electrode may be used in the sequence of [Case 1] and [Case 2] shown in FIG. 1 or in the sequence of [Case 5] and [Case 6] shown in FIG. After forming the gate electrode by patterning the conductive material layer for stripes into a stripe shape, a second
After forming a focusing electrode on the second insulating layer, a second opening penetrating through the second insulating layer is formed in the second insulating layer. 2nd electrode
A hole communicating with the opening may be formed, an opening communicating with the hole may be formed in the insulating layer, and the steps subsequent to the formation of the resist material layer may be performed.

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 to 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
Lead (Pb) -based high-temperature solder such as _1.0 (melting point 309 ° C);
A 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 three members have been joined, the space surrounded by the cathode panel CP, the anode panel AP, the frame, and the adhesive layer can be evacuated to a vacuum. When evacuation is performed after the joining, the pressure of the atmosphere during the joining may be either normal pressure or reduced pressure, and the gas constituting the atmosphere may be the air, or may be 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 manufacturing method according to the fifth aspect of the present invention, instead of [Step-770], the gate electrode is formed of a band-shaped or sheet-shaped metal foil having a hole formed thereon, and An insulating layer as a gate electrode support is formed on the metal foil so that the metal foil is in contact with the top surface of the insulating layer, and the hole is located above the opening provided in the insulating layer. May be stretched.
In this case, one electron emitting portion may be formed below the plurality of holes formed in the metal foil, or one electron emitting portion may be formed below the one hole 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.

[0159]

In the present invention, since the resist material layer is exposed without using an exposure mask, the finally obtained electron-emitting portion is securely positioned in the center of the bottom of the opening in a self-aligned manner. It is possible to do. As a result, the distance from the electron-emitting portion to the edge of the gate electrode opening can be made uniform, and the electron-emitting characteristics of the electron-emitting portion in the display device become uniform. In addition, since the electron-emitting portion can be formed in a self-aligned manner, the number of exposure masks to be used can be reduced, and the number of alignment steps during exposure of the resist material layer is also reduced. Furthermore, as a result of being able to perform high-precision patterning as compared with proximity exposure, the distance from the electron-emitting portion to the end of the gate electrode opening can be reduced, and the driving voltage can be reduced.
The display circuit can be simplified. As a result, even if the display device is enlarged, a display device with high display quality and low power consumption without display unevenness can be realized while reducing manufacturing costs.

[Brief description of the drawings]

FIG. 1 is a flowchart of each step of a manufacturing method according to Embodiments 1 to 4 of the present invention.

FIG. 2 is a flowchart of each step of a manufacturing method according to a fifth embodiment and a sixth embodiment of the invention.

FIG. 3 is a flowchart of each step of a manufacturing method according to Embodiment 7 of the present invention;

FIG. 4 is a schematic partial end view of a support and the like for describing a method of manufacturing the cold cathode field emission device of the first embodiment of the invention.

FIG. 5 is a schematic partial end view of a support and the like for explaining the method for manufacturing the cold cathode field emission device of the first embodiment of the invention, following FIG. 4;

FIG. 6 is a schematic partial end view showing the cold cathode field emission display according to the first embodiment of the invention;

FIG. 7 is a schematic perspective view of a part of the anode panel and the cathode panel.

FIG. 8 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 2 of the present invention.

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

FIG. 10 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 3 of the present invention.

FIG. 11 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 4 of the present invention.

FIG. 12 is a schematic partial end view of a support and the like for explaining a method of manufacturing the cold cathode field emission device according to the fourth embodiment of the invention, following FIG. 11;

FIG. 13 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 5 of the present invention.

FIG. 14 is a schematic partial end view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the fifth embodiment of the invention, following FIG. 13;

FIG. 15 is a schematic partial end view of a support and the like for explaining the method for manufacturing the cold cathode field emission device according to the fifth embodiment of the present invention, following FIG. 14;

FIG. 16 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 6 of the present invention.

FIG. 17 is a schematic partial end view of a support and the like for explaining the method of manufacturing the cold cathode field emission device according to the sixth embodiment of the invention, following FIG. 16;

FIG. 18 is a schematic partial end view of a support and the like for explaining the method for manufacturing the cold cathode field emission device according to the sixth embodiment of the invention, following FIG. 17;

FIG. 19 is a schematic partial end view of a support and the like for describing a method for manufacturing a cold cathode field emission device according to Embodiment 7 of the present invention.

FIG. 20 is a schematic partial end view of the support and the like for explaining the method for manufacturing the cold cathode field emission device of the seventh embodiment of the invention, following FIG. 19;

FIG. 21 is a schematic partial end view of a support and the like for explaining the method for manufacturing the cold cathode field emission device according to the seventh embodiment of the invention, following FIG. 20;

FIG. 22 is a schematic partial end view of a substrate and the like for describing a method of manufacturing an anode panel.

FIG. 23 is a schematic view showing a configuration example of a conventional cold cathode field emission display device having a Spindt-type element.

FIG. 24 is a schematic partial end view of a support and the like for explaining a method of manufacturing a conventional flat 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 a conventional flat type cold cathode field emission device following FIG. 24;

[Explanation of symbols]

CP: cathode panel, AP: anode panel, 10: support, 11: cathode electrode, 12
... an insulating layer, 13 ... a gate electrode, 14 ... an opening, 14A ... a hole, 14B ... an opening provided in the insulating layer, 15 ... an electron emission part, 20 ... ..Substrates, 2
1 ... black matrix, 22 ... phosphor layer,
23 ... anode electrode, 24 ... frame, 30 ...
Scanning circuit, 31 ... control circuit, 32 ... acceleration power supply,
40 ... resist material layer, 40A ... resist material layer portion located at the center of the bottom of the opening, 40B ...
Exposure portion of resist material layer, 41: electron emission portion forming layer, 42: light shielding film, 50: photosensitive film, 51
... Sensitive area, 52 ... Remainder of photosensitive film (exposure,
Photosensitive film after development), 53 ... mask, 54 ...
Opening, 60: conductive composition layer, 70: selective growth region of carbon thin film, 71: metal particles, 72: carbon thin film

Claims (22)

[Claims] (A) forming a cathode electrode on a support; (B) forming an insulating layer on the cathode electrode and the support; and (C) forming an opening in the insulating layer. (D) a step of forming a resist material layer on the entire surface including the bottom and side walls of the opening; and (E) irradiating the resist material layer with energy rays without using an exposure mask. Selectively removing the resist material layer from the bottom of the opening by developing the layer, thereby exposing the cathode electrode at the bottom of the opening; and (F) cathode electrode exposed at the bottom of the opening. Forming a cold cathode field emission device on the substrate. 2. The method according to claim 2, further comprising the step of forming a gate electrode having a hole on the insulating layer between the step (B) and the step (C). 2. The method for manufacturing a cold cathode field emission device according to claim 1, wherein the resist material layer is irradiated with energy rays at an incident angle other than 0 degree with respect to a normal line. 3. The incident angle is such that a portion of the resist material layer located at the center of the bottom of the opening is not irradiated with energy rays.
5. The method for manufacturing a cold cathode field emission device according to item 1. 4. The method according to claim 2, further comprising a step of removing the resist material layer after the step (F). 5. The method according to claim 1, further comprising: a step of forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening; and a step of removing the resist material layer between the steps (E) and (F). The method according to claim 2, wherein in the step (F), an electron emission portion is formed on the underlayer. 6. A step of forming a conductive material layer for a gate electrode having a hole on an insulating layer between the step (B) and the step (C). Patterning the conductive material layer for an electrode, thereby forming a gate electrode, wherein in the step (E), the energy beam is resisted at an incident angle other than 0 degree with respect to the normal to the support. 2. The method according to claim 1, wherein the irradiation is performed on the material layer. 7. The incident angle is such that a portion of the resist material layer located at the center of the bottom of the opening is not irradiated with energy rays.
5. The method for manufacturing a cold cathode field emission device according to item 1. 8. The method according to claim 6, further comprising a step of removing the resist material layer after the step (F) and before patterning the conductive material layer for a gate electrode. A method for manufacturing a cold cathode field emission device. 9. The method according to claim 9, further comprising the steps of: forming a base layer on the surface of the cathode electrode exposed at the bottom of the opening; and removing the resist material layer between the steps (E) and (F). The method according to claim 6, wherein, in the step (F), an electron-emitting portion is formed on the underlayer. 10. The method according to claim 1, wherein said step (B) and said step (C)
Forming a gate electrode having a hole on the insulating layer; and between the steps (D) and (E), on the resist material layer on the insulating layer and the gate electrode, and on the side wall of the opening. 2. The method for manufacturing a cold cathode field emission device according to claim 1, further comprising a step of forming a light shielding film on the resist material layer. 11. The step of forming the light-shielding film comprises the step of forming the light-shielding film by physical vapor deposition at an incident angle other than 0 ° with respect to the normal to the support. The method for manufacturing a cold cathode field emission device according to claim 10. 12. The method according to claim 1, further comprising a step of removing the resist material layer after the step (F).
0. The method for manufacturing a cold cathode field emission device according to item 0. 13. The method according to claim 13, wherein said step (E) and said step (F)
Forming an underlayer on the surface of the cathode electrode exposed at the bottom of the opening; and removing the resist material layer. In the step (F), an electron emission portion is formed on the underlayer. The method of manufacturing a cold cathode field emission device according to claim 10, wherein the device is formed. 14. The method according to claim 14, wherein said step (B) and said step (C)
Forming a gate electrode conductive material layer having a hole on the insulating layer, between the steps (D) and (E), on the resist material layer on the gate electrode conductive material layer, and in the opening; Forming a light-shielding film on the resist material layer on the side wall; and, after the step (F), patterning the conductive material layer for a gate electrode, thereby forming a gate electrode. 2. The method for manufacturing a cold cathode field emission device according to claim 1, wherein: 15. The method according to claim 15, wherein the step of forming the light-shielding film comprises a step of forming the light-shielding film by physical vapor deposition at an incident angle other than 0 ° with respect to the normal to the support. The method for manufacturing a cold cathode field emission device according to claim 14. 16. The method according to claim 14, further comprising a step of removing the resist material layer after the step (F) and before patterning the gate electrode conductive material layer. A method for manufacturing a cold cathode field emission device. 17. The method according to claim 17, wherein said step (E) and said step (F)
Forming an underlayer on the surface of the cathode electrode exposed at the bottom of the opening; and removing the resist material layer. In the step (F), an electron emission portion is formed on the underlayer. The method according to claim 14, wherein the cold cathode field emission device is formed. 18. A method according to claim 18, wherein said step (D) and said step (E)
Forming a light-shielding film on the resist material layer on the insulating layer and on the resist material layer on the side wall of the opening; and after the step (F), communicating with the opening provided in the insulating layer. The method according to claim 1, further comprising forming a gate electrode having a hole on the insulating layer. 19. The method according to claim 19, wherein the step of forming the light-shielding film comprises a step of forming the light-shielding film by physical vapor deposition at an incident angle other than 0 ° with respect to the normal to the support. The method for manufacturing a cold cathode field emission device according to claim 18. 20. The method according to claim 18, further comprising a step of removing the resist material layer after the step (F) and before forming a gate electrode on the insulating layer. A method for manufacturing a cold cathode field emission device. 21. A method according to claim 18, wherein said step (E) and said step (F)
Forming an underlayer on the surface of the cathode electrode exposed at the bottom of the opening; and removing the resist material layer. In the step (F), an electron emission portion is formed on the underlayer. The method according to claim 18, wherein the cold cathode field emission device is formed. 22. A pixel comprising: a plurality of cold cathode field emission devices; an anode electrode opposed to the plurality of cold cathode field emission devices; and a phosphor layer, wherein each pixel comprises a plurality of cold cathode field emission devices. A method for manufacturing a cold cathode field emission display device in which a cathode panel on which a cathode field emission device is formed, and an anode panel on which an anode electrode and a phosphor layer are formed are joined at their peripheral portions, (A) forming a cathode electrode on a support; (B) forming an insulating layer on the cathode electrode and the support; and (C) forming an opening in the insulating layer. Forming; (D) forming a resist material layer on the entire surface including the bottom and side walls of the opening; and (E) irradiating the resist material layer with energy rays without using an exposure mask. Developing the resist material layer to selectively remove the resist material layer from the bottom of the opening, thereby exposing the cathode electrode at the bottom of the opening; and (F) exposing the cathode electrode at the bottom of the opening. A method for manufacturing a cold cathode field emission display device, wherein the method includes at least a step of forming an electron emission portion on a cathode electrode.