JPH10284284A - Antistatic film and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spacer antistatic film, which does not need to be made extremely thin, is easy to control in thickness and has high stability, and a display device using the same. SOLUTION: This antistatic film 24 has a semiconducting film 25 as a first layer, having a film thickness of 10 nm to 1 μm, and a layer 26 as a second layer with a film thickness of 1 nm to 20 nm, made from a material different from the first layer, on the surface of the first layer. Also, the first layer 25 is an alloy nitride film formed by combining at least one kind selected from among Al, B, and Si with at least one kind selected from among Cr, Ti, and Ta. The second layer 26 is preferably either Hf-N, Hf-O, Pt, or Au.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antistatic film, and
The present invention relates to an image display device to which an antistatic film is applied.

[0002]

2. Description of the Related Art Conventionally, two types of electron emitting devices, a hot cathode device and a cold cathode device, are known. Among these, among the cold cathode devices, for example, a surface conduction type emission device, a field emission type device (hereinafter referred to as FE type), a metal / insulating layer / metal type emission device (hereinafter referred to as MIM type), and the like are known. I have.

[0003] As a surface conduction type emission element, for example,
M. I. Elinson, Radio Eng. Ele
ctron Phys. , 10, 1290, (196
5) and other examples described later are known.

The surface conduction electron-emitting device utilizes a phenomenon in which an electron is emitted when a current flows in a small-area thin film formed on a substrate in parallel with the film surface. As this surface conduction type emission element, Sn described by Elinson et al.
In addition to those using the O ₂ thin film, those using the Au thin film [G. Dittmer: “Thin Solid Fi
lms ", 9,317 (1972)] and In ₂ O ₃ /
According to SnO ₂ thin film [M. Hartwell an
d C.I. G. FIG. Fonstad: "IEEE Tran
s. ED Conf. “, 519 (1975)] and those using carbon thin films [Hisashi Araki et al .: Vacuum, Vol. 26,
No. 1, 22 (1983)].

[0005] As a typical example of the element structure of these surface conduction electron-emitting devices, FIG. Hartwel
1 shows a plan view of an element according to the present invention. In FIG. 1, reference numeral 1 denotes a substrate, and 2 denotes a conductive thin film made of a metal oxide formed by sputtering. The conductive thin film 2 is formed in an H-shaped planar shape as shown. By subjecting the conductive thin film 2 to an energization process called energization forming described below,
The electron emission part 3 is formed. The interval L in the figure is 0.5 to
1 [mm] and W are set at 0.1 [mm].
For convenience of illustration, the electron emitting portion 3 is shown in a rectangular shape at the center of the conductive thin film 2, but this is a schematic one, and the position and shape of the actual electron emitting portion are faithfully represented. Not necessarily.

[0006] M. In the above-described surface conduction electron-emitting device, including the device by Hartwell et al., It is general to form the electron-emitting portion 3 by subjecting the conductive thin film 2 to an energization process called energization forming before electron emission. there were. That is, energization forming is
A constant DC voltage across the conductive thin film 2, or
For example, a DC voltage which is boosted at a very slow rate of about 1 V / minute is applied and energized to locally break, deform or alter the conductive thin film 2, and the electron emitting portion in a state of being electrically high in resistance 3 is formed. still,
A crack is generated in a part of the conductive thin film 2 that has been locally broken, deformed, or altered. When an appropriate voltage is applied to the conductive thin film 2 after the energization forming, electrons are emitted in the vicinity of the crack.

[0007] Examples of the FE type are described in, for example, W.S. P.
Dyke & W. W. Dolan, "Fie-ld em
issue ", Advance in Electr
on Physics, 8, 89 (1956) or C.I. A. Spindt, "Physical pr
operations of thin-filmfield
de emission cathodes with
molybdenium cones ", J. App.
l. Phys. , 47, 5248 (1976).

As a typical example of the FE type device configuration, FIG. A. 1 shows a cross-sectional view of a device by Spindt et al. In the figure, 4 is a substrate, 5 is an emitter wiring made of a conductive material, 6 is an emitter cone, 7 is an insulating layer, and 8 is a gate electrode. In the present device, by applying an appropriate voltage between the emitter cone 6 and the gate electrode 8, field emission is caused from the tip of the emitter cone 6.

As another element configuration of the FE type, FIG.
There is also an example in which an emitter and a gate electrode are arranged on a substrate almost in parallel with the plane of the substrate, instead of the laminated structure shown in FIG.

As an example of the MIM type, for example,
C. A. Mead, “Operation of tu
nnel-emission Devices, J. et al. A
ppl. Phys. , 32, 646 (1961).

FIG. 19 shows a typical example of an MIM type device configuration.
Shown in The figure is a sectional view, in which 9 is a substrate, 10 is a lower electrode made of metal, 11 is a thin insulating layer having a thickness of about 100 Å, and 12 is a thickness of 80 to 30.
The upper electrode is made of a metal of about 0 Å.
In the MIM type, electrons are emitted from the surface of the upper electrode 12 by applying an appropriate voltage between the upper electrode 12 and the lower electrode 10.

The above-mentioned cold cathode device can obtain electrons at a lower temperature than the hot cathode device, and therefore does not require a heater for heating. Therefore, the structure is simpler than that of the hot cathode element, and a fine element can be produced. Also,
Even if a large number of elements are arranged on a substrate at a high density, problems such as thermal melting of the substrate hardly occur. In addition, unlike the hot cathode device, which operates by heating the heater, the response speed is slow, and the cold cathode device also has the advantage that the response speed is fast.

For this reason, research for applying the cold cathode device has been actively conducted.

For example, a surface conduction electron-emitting device has the advantage that a large number of devices can be formed over a large area because it has a particularly simple structure and is easy to manufacture among cold cathode devices. Therefore, for example, Japanese Patent Application Laid-Open No.
As disclosed in JP-A-332-332, a method for arranging and driving a large number of elements has been studied. Also,
As for the application of the surface conduction electron-emitting device, for example, an image forming apparatus such as an image display device and an image recording device, and a charged beam source have been studied.

Particularly, as an application to an image display device, for example, as disclosed in US Pat. No. 5,066,883, JP-A-2-257551 and JP-A-4-28137 by the present applicant, An image display device using a combination of a conduction emission device and a phosphor that emits light when irradiated with an electron beam has been studied. An image display device using a combination of a surface conduction electron-emitting device and a phosphor is expected to have better characteristics than other conventional image display devices. For example, it can be said that it is superior in that it does not require a backlight because it is a self-luminous type and that it has a wide viewing angle, as compared with a liquid crystal display device that has become popular recently.

A method of arranging and driving a large number of FE types is disclosed, for example, in US Pat. No. 4,904,895 of the present application. Further, as an example in which the FE type is applied to an image display device, for example, R.F. The flat panel display reported by Meyer et al. Is known. [R. Meye
r: “Recent Development onM
micro-tips Display at LET
I ", Tech. Digest of 4th In
t. Vacuum Microelectronics
Conf. , Nagahama, pp .; 6-9 (19
91)] Further, an example in which a number of MIM types are arranged and applied to an image display device is disclosed in, for example, Japanese Patent Application Laid-Open No. 3-55-1990 by the present applicant.
738.

Among the image forming apparatuses using the above-described electron-emitting devices, a flat display device having a small depth has been attracting attention as a replacement for a cathode-ray tube display device because of its space saving and light weight. .

FIG. 1 is a perspective view showing an example of a display panel section constituting a flat-panel type image display device, in which a part of the panel is cut away to show the internal structure.

In the figure, 13 is a rear plate, 14 is a side wall,
Reference numeral 15 denotes a face plate, and the rear plate 13, the side wall 14, and the face plate 15 form an envelope (airtight container) for maintaining the inside of the display panel at a vacuum.

A substrate 16 is fixed to the rear plate 13. On the substrate 16, a cold cathode element 17 is provided with N ×
M pieces are formed. (N and M are positive integers of 2 or more and are appropriately set according to the target number of display pixels.)
The N × M cold cathode elements 17 are wired by M row wirings 18 and N column wirings 19 as shown in FIG. The substrate 16 and the cold cathode device 1
7. The part constituted by the row direction wiring 18 and the column direction wiring 19 is called a multi-electron beam source. In addition, an insulating layer (not shown) is formed between at least the portions where the row wirings 18 and the column wirings 19 intersect, so that electrical insulation is maintained.

On the lower surface of the face plate 15, a phosphor film 20 made of a phosphor is formed, and phosphors (not shown) of three primary colors of red (R), green (G), and blue (B) are applied. Divided. A black body (not shown) is provided between the respective color phosphors forming the fluorescent film 20, and a metal back 21 made of Al or the like is formed on the surface of the fluorescent film 20 on the rear plate 13 side. ing.

Dx1 to Dxm, Dy1 to Dyn and Hv are electric connection terminals having an airtight structure provided for electrically connecting the display panel to an electric circuit (not shown). Dx1 to Dxm are electrically connected to the row wiring 18 of the multi-electron beam source, Dy1 to Dyn are electrically connected to the column wiring 3114 of the multi-electron beam source, and Hv is electrically connected to the metal back 21.

The inside of the hermetic container is maintained at a vacuum of about 10 −6 Torr, and as the display area of the image display device increases, the rear plate 13 due to a pressure difference between the inside of the hermetic container and the outside. In addition, means for preventing deformation or destruction of the face plate 15 is required. Rear plate 13 and face plate 14
In addition to increasing the weight of the image display device, the method of increasing the thickness of the image display causes image distortion and parallax when viewed from an oblique direction. On the other hand, in FIG. 1, a structural support (called a spacer or a rib) 22 made of a relatively thin glass plate and supporting the atmospheric pressure is provided. In this manner, the distance between the substrate 16 on which the multi-beam electron source is formed and the face plate 15 on which the fluorescent film 20 is formed is usually kept at a sub-millimeter to several millimeters, and the inside of the hermetic container is kept at a high vacuum as described above. Have been.

In the image display apparatus using the display panel described above, when a voltage is applied to each cold cathode element 17 through the external terminals Dx1 to Dxm and Dy1 to Dyn,
Electrons are emitted from each cold cathode element 17. At the same time, several hundred [V] are applied to the metal back 21 through the outer terminal Hv.
The emitted electrons are accelerated by applying a high voltage of a few kV to collide with the inner surface of the face plate 15. As a result, the phosphors of each color forming the fluorescent film 20 are excited and emit light, and an image is displayed.

[0025]

The display panel of the image display device described above has the following problems.

First, there is a possibility that spacer charging may be caused by a part of electrons emitted from the vicinity of the spacer 22 hitting the spacer 22 or ions ionized by the action of the emitted electrons adhere to the spacer. is there. The electrons emitted from the cold cathode element 17 due to the charging of the spacer are bent in their trajectories, reach a position different from the normal position on the phosphor, and the image near the spacer is distorted and displayed.

Second, a high voltage of several hundred V or more (that is, a high electric field of 1 kV / mm or more) is applied between the multi-beam electron source and the face plate 15 in order to accelerate the electrons emitted from the cold cathode device 17. Since the voltage is applied, creeping discharge on the surface of the spacer 22 is concerned. In particular, when the spacer is charged as described above, discharge may be induced.

To solve this problem, a proposal has been made to remove the charge by making a minute current flow through the spacer. There, a high-resistance thin film is formed on the surface of an insulating spacer so that a minute current flows on the surface of the spacer.

The charging characteristics of the spacer antistatic film are greatly affected by the secondary electron emission efficiency at a depth of about 100 ° from the surface and the surface shape. However, in the case of a film having a thickness of up to about 100 °, the reproducibility and stability of film formation become a problem, so the actual film thickness must be set to about 500 ° to 2000 °. Precious metals and some nitrides have a very small secondary electron emission coefficient and are suitable for antistatic films. However, with the preferred film thickness described above, it is possible to set an appropriate resistance value as an antistatic film for spacers. Very difficult.

Although the island-shaped film is considered to be effective in preventing static electricity due to secondary electron emission, it has a problem as an antistatic film for the spacer for the same reason.

The present invention overcomes the above disadvantages of the conventional spacer, and does not require an extremely thin film thickness, is easy to control the film thickness, and has high stability. It is an object to provide an image display device used.

[0032]

According to the present invention, a film having a thickness of 1 on the surface is provided.
An alloy nitride film in which at least one selected from Al, B, and Si having a second layer having a thickness of 20 nm to 20 nm and at least one selected from Ti, Ta, and Cr are combined. It is an antistatic film of 1 to 10 ⁸ Ωcm.

FIG. 2 is a schematic cross-sectional view of the antistatic film of the present invention. Reference numeral 23 denotes an insulating member to be subjected to antistatic, and 24 denotes an antistatic film formed on the surface of the insulating member 23. The antistatic film 24 includes an alloy nitride film 25 and a second layer 26 formed on the surface thereof. The second layer 26 is made of HfN, Hf-
It is selected from O, Pt, and Au.

FIG. 3 shows another structure of the antistatic film of the present invention. The antistatic film 24 is formed of the alloy nitride film 3 and the second layer 4 and the alloy nitride film 3 and the second layer 26. It is composed of an oxide film or an oxynitride film 27 of the alloy formed on the boundary.

The present invention also relates to a flat display device (electron beam arrangement) using the above-mentioned antistatic film as a spacer.
As shown in FIG. 1 (which will be described in detail later), a substrate 16 on which a plurality of cold cathode devices 17 are formed and a transparent face plate 15 on which a fluorescent film 20 as a fluorescent material is formed are opposed via a spacer 22. A display device having a structure in which the spacer 22 has a specific resistance of 0.1 to
10 ⁸ Ωcm alloy nitride film and Hf-N, Hr-
A display device, wherein the display device is covered with a second layer selected from O, Pt, and Au.

The electron beam apparatus of the present invention may have the following form.

The electron beam device is an accelerating electrode in which the electrode accelerates electrons emitted from the electron source. The electron beam device irradiates the target with the electrons emitted from the cold cathode device in accordance with an input signal, thereby forming an image. Forming an image forming apparatus. In particular, an image display device in which the target is a phosphor is provided.

The cold cathode device is a cold cathode device having a conductive film including an electron emitting portion between a pair of electrodes, and is particularly preferably a surface conduction type emitting device.

The electron source is a simple matrix-shaped electron source having a plurality of cold cathode elements arranged in a matrix with a plurality of row wirings and a plurality of column wirings.

The electron source is provided with a plurality of rows of cold cathode elements each having a plurality of cold cathode elements arranged in parallel connected at both ends (referred to as a row direction), and arranged in a direction perpendicular to the wiring (column direction). A control electrode (also referred to as a grid) disposed above the cold cathode device along with the cold cathode device forms a ladder-shaped electron source for controlling electrons from the cold cathode device.

According to the concept of the present invention, the present invention is not limited to an image forming apparatus suitable for display, but may be used as an alternative light source such as a light emitting diode of an optical printer comprising a photosensitive drum and a light emitting diode. Alternatively, the above-described image forming apparatus can be used. In this case, by appropriately selecting the above-mentioned m row-directional wirings and n column-directional wirings, the present invention can be applied not only to a linear light emitting source but also to a two-dimensional light emitting source. In this case, the image forming member is not limited to a substance that emits light directly, such as a phosphor used in the following embodiments, and a member that forms a latent image by electron charging can also be used.

Further, according to the concept of the present invention, the present invention is applicable to a case where a member to be irradiated with electrons emitted from an electron source is other than an image forming member such as a phosphor, as in an electron microscope. Is applicable. Therefore, the present invention can also take a form as a general electron beam apparatus that does not specify a member to be irradiated.

[Operation] As described above, the antistatic film of the present invention is provided with the second layer on the surface of the conductive spacer to control the surface shape or the secondary electron emission ability, thereby improving the antistatic ability. It is intended. As a result, the charge amount of each spacer is reduced, and a high-quality image display device without bending of the beam or discharge of the spacer portion can be realized. (1) According to the present invention, a film having a thickness of 1
A semiconductive film having a thickness of 0 nm to 1 μm, and a second layer formed on the surface thereof and having a thickness of 1 nm to 20 made of a material different from that of the first layer.
With an antistatic film characterized by having an nm layer,
The following effects can be obtained.

By coating the first layer with a chemically and physically stable semiconductive film with the above thickness, a stable and appropriate resistance value of the film which is not affected by various factors received during the assembly process. Can be defined.

On the other hand, the second layer has a lower secondary electron emission efficiency than the material of the first layer and is preferable as an antistatic material. However, since the resistance is low, it is necessary to maintain an appropriate resistance value as a spacer antistatic film. In this case, a material which must be formed very thin and which is extremely unstable when used alone can be used.

Similarly, a material whose secondary electron emission efficiency is small but whose specific resistance is too high and the charge elimination ability is inferior (the charge elimination speed becomes slower as the resistance value becomes higher) also has the charge elimination function in the first layer. Can be used.

When charging is caused by secondary electron emission, the antistatic ability depends on the material at a depth of about 10 nm from the surface. On the other hand, the ability of static elimination (charge removal) depends on the resistance value of the entire film. Therefore, by separating these functions into two layers, it is possible to produce an antistatic film having higher performance than the conventional single film structure. (2) The first layer is an alloy nitride film in which at least one type selected from Al, B, and Si and at least one type selected from Cr, Ti, and Ta are combined. The following effects can be obtained by the prevention film.

The first layer using these materials makes it possible to form an antistatic film having a stable resistance value, which is not affected by various factors during the assembly process. Surface layer (second
When the material of the layer) is used alone, an appropriate resistance value and a stable resistance value cannot be obtained. (3) The second layer is formed of Hf-N, Hf-O, P
The following effects can be obtained by the antistatic film characterized by being any one of t and Au.

Here, by using the above-mentioned material for the surface, the antistatic effect can be enhanced as compared with the case where the above-mentioned material is used alone as the first layer. (4) The antistatic film having an oxide or oxynitride layer of the alloy at the interface between the first layer and the second layer has the following effects.

When the above-described antistatic film having a two-layer structure is subjected to a heat treatment and oxidized to a certain depth, the antistatic function of the second layer provides higher performance than that of the one-layer structure, as described above. An antistatic film can be made. (5) The antistatic film, wherein the specific resistance after forming both the first layer and the second layer is 0.1 to 10 ⁸ Ωcm, has the following effects. . By defining such a resistance value, the accumulated electric charge is removed (the lower the resistance, the better), the power consumption is in an appropriate range (the power consumption increases if the resistance is too low), and thermal runaway occurs. Prevent (if resistance is too low, thermal runaway is easy)
be able to. (6) In a display device having a structure in which a substrate on which a plurality of cold cathode type electron-emitting devices are formed and a transparent substrate on which a luminescent material is formed are opposed to each other via a spacer, the antistatic film is formed of the spacer The following effects can be obtained by the antistatic film characterized by being formed on the surface.

It is possible to suppress the charge of the spacer and prevent the image from being disturbed due to the disturbance of the electron trajectory around the spacer. (7) In a display device having a structure in which a substrate on which a plurality of cold-cathode-type electron-emitting devices are formed and a transparent substrate on which a light-emitting material is formed face each other via a spacer, the spacer is formed by the antistatic film. The following operation and effect can be obtained by the display device characterized by comprising the coated insulating member.

If an inexpensive insulating member is used, the cost can be reduced. Further, the insulating member is required to have a strength for supporting the atmospheric pressure (it is difficult to provide the strength only with the antistatic film). (8, 9) The spacer is electrically connected to an electron source driving wiring, and the spacer is electrically connected to an emission electron acceleration electrode. The following operational effects can be obtained by the display device described above.

By electrically connecting to both electrodes,
Elimination of electric charge (Electric drive wiring is dropped to ground) The effect on the beam trajectory is negligible and a uniform electric field can be created that does not cause a problem (Electrification is eliminated if not connected to the accelerating electrode) However, the discharge and the distortion of the electric field occur, so that a clear image cannot be obtained.) (10) The cold cathode type electron-emitting device is also a display device characterized in that it is a surface conduction type electron-emitting device, and it can be used without being limited to the surface conduction type.

[0054]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has a thickness of 1 to 20 n on the surface.
m is an alloy nitride film having a second layer of m. Alloy is Cr, T
at least one selected from i, Ta, and Al, B, S
At least one selected from i is used in combination. Further, the specific resistance of the alloy nitride film is 0.1 to 10 ⁸ Ωcm.
Is an antistatic film.

FIG. 2 is a schematic cross-sectional view of the antistatic film of the present invention. Reference numeral 23 denotes an insulating member to be subjected to antistatic, and reference numeral 24 denotes an antistatic film formed on the surface of the insulating member 23. The antistatic film 24 includes an alloy nitride film 25 and a second layer 26 formed on the surface thereof. The second layer 26 is made of HfN, Hf-
It is selected from O, Pt, and Au.

FIG. 3 shows another structure of the antistatic film of the present invention.
And an oxide film or oxynitride film 27 of the above alloy formed at the boundary between the second layer 26 and the alloy nitride film 25 and the second layer 26.
Consists of

The present invention also relates to a flat display device (electron beam device) using the above antistatic film as a spacer.
As shown in FIG. 1 (which will be described in detail later), a substrate 16 on which a plurality of cold cathode elements 17 are formed and a transparent face plate 15 on which a fluorescent film 20 as a light emitting material is formed are opposed to each other via a spacer 22. Display device having a structure in which the spacer 22 has a specific resistance of 0.1 to
A display device characterized by being coated with an alloy nitrogen compound film having a resistivity of 10 ⁸ Ωcm and a second layer selected from HfN, Hf-O, Pt and Au formed on the surface thereof.

In the display device of the present invention, the spacer 2
One side of 2 is electrically connected to the wiring on the substrate 16 on which the cold cathode device is formed. The opposite side is electrically connected to an acceleration electrode (metal back 21) for causing electrons emitted from the cold cathode device to collide with a light emitting material (fluorescent film 20) with high energy. That is, a current obtained by substantially dividing the acceleration voltage by the resistance value of the antistatic film flows through the antistatic film formed on the surface of the spacer.

[Resistance value Rs of spacer] The resistance value Rs of the spacer is set to a desirable range from the viewpoint of antistatic and power consumption. The surface resistance R □ is preferably 10 ¹² Ω or less from the viewpoint of antistatic. In order to obtain a sufficient antistatic effect, the resistance is more preferably 10 ¹¹ Ω or less. The lower limit of the surface resistance depends on the shape of the spacer and the voltage applied between the spacers, but is preferably at least 10 ⁵ Ω.

[Thickness of Antistatic Film] The thickness t of the antistatic film formed on the insulating material is preferably in the range of 10 nm to 1 μm. Although it varies depending on the surface energy of the material, the adhesion to the substrate, and the substrate temperature, generally 10 n
The thin film having a thickness of m or less is formed in an island shape, and has an unstable resistance and poor reproducibility. On the other hand, when the film thickness t is 1 μm or more, the film stress increases, the risk of film peeling increases, and the film formation time becomes longer, resulting in poor productivity. Therefore, the film thickness is 50 to 500 n
m is desirable.

[Surface Resistance R □ of Antistatic Film] Surface Resistance R
□ is ρ / t, and from the preferable range of R □ and t described above, the specific resistance ρ of the antistatic film is 0.1 to 10 ⁸ Ωc.
m is preferred. Further, in order to realize more preferable ranges of the surface resistance and the film thickness, ρ is preferably set to 10 ² to 10 ⁶ Ωcm.

[Temperature Coefficient of Resistance of Spacer] As described above, the temperature of the spacer rises when current flows through the antistatic film formed thereon or when the entire display generates heat during operation. If the resistance temperature coefficient of the antistatic film is a large negative value, the resistance value decreases when the temperature increases, the current flowing through the spacer increases, and the temperature further increases. And the current continues to increase until the power supply limit is exceeded. The value of the temperature coefficient of resistance at which such a runaway of current occurs is empirically a negative value and the absolute value is 1% or more. That is, the temperature coefficient of resistance of the antistatic film is -1.
% Is desirable.

[Material for Antistatic Film] As materials having antistatic film characteristics, metal nitrides and metal oxides are excellent. Among metal oxides, oxides of chromium, nickel and copper are preferred materials. The reason is considered to be that these oxides have a relatively low secondary electron emission efficiency and are difficult to be charged even when electrons emitted from the electron-emitting device hit the spacer. Other than these, metals are preferable because of their low secondary electron emission efficiency. In particular, noble metals such as Pt and Au are not easily oxidized, and have an advantage that they are not oxidized during the assembly process.

However, it is difficult to adjust the resistance of the above-mentioned metal oxide or metal to a specific resistance range which is desirable as an antistatic film, or the resistance easily changes depending on the atmosphere. When a film is formed, there is a problem in controllability of resistance.

The resistance of a nitride of an alloy combining two or more elements can be controlled in a wide range from a good conductor to an insulator by adjusting the selection and composition of the elements. Further, it is a stable material that has a small change in resistance value in a display device manufacturing process described later. Further, the material has a temperature coefficient of resistance of less than -1% and is practically easy to use.
As a combination of elements, some of transition metals that form low-resistance nitrides such as Ti, Cr, and Ta, and Al,
Some kinds are selected and combined from elements for forming a high-resistance nitride such as B and Si.

[Composition of alloy] The resistance value can be adjusted by adjusting the composition of these elements. The specific resistance value cannot be unequivocally specified because it depends on the transition metal element contained in the alloy nitride film or the film forming conditions. 5 at% to 18 at%, Ti is 24 at% to 40 a
t% and Ta are 36 at% to 50 at%. [Thickness of Second Layer] The antistatic film of the present invention is obtained by laminating a second layer 26 on the surface of the alloy nitride film 23 as shown in FIG. The resistance value of the entire antistatic film 24 is substantially determined by the resistance value of the alloy nitride film, and the second layer has an effect of suppressing charging. As described above, since the resistance of the second layer depends on the atmosphere, the resistance of the second layer is が of the resistance of the antistatic film.
As described above, more preferably, the thickness of the second layer should be determined so as to be 10 times or more. When the specific resistance of the material used for the second layer is high, it is difficult to quickly release the electric charge accumulated on the surface, so that the thickness of the second layer is limited,
A value not exceeding 0 nm is preferred.

On the other hand, a thin film is different depending on a film forming method, and cannot be said unconditionally. However, a film having a thickness of about 10 nm or less becomes an island-like film that is not continuous. With a too thin film,
The exposed area of the first layer becomes large, and the charging characteristics are affected by the material of the first layer. In this case, the advantage of using a material that is difficult to be charged for the second layer is impaired. The secondary electron emission efficiency that determines the charging characteristics is greatly affected by the characteristics from the surface to 5 to 7 nm. Considering the controllability of the film thickness rate of the film formation, the thickness of the second layer is 1 to 20 nm.
Is suitable.

[Method of Forming Alloy Nitride Film]
It is formed on an insulating member by thin film forming means such as sputtering, reactive sputtering in a nitrogen gas atmosphere, electron beam evaporation, ion plating, and ion assisted evaporation. HfN and Hf-O can also be manufactured by the same thin film forming method for the second layer. Pt and Au are sputtering methods,
It can be formed by a thin film forming method such as electron beam evaporation, ion plating, and ion beam sputtering.

The alloy nitride film and the second layer may be formed by different apparatuses, but by continuously laminating, the adhesion of the second layer is enhanced.

[Method of Manufacturing Image Display Device] The antistatic film of the present invention has been described with respect to the prevention of spacer electrification of a flat display device. However, the present invention is not limited to this and can be used as an antistatic film in other applications.

Next, the configuration and manufacturing method of a display panel of an image display device to which the present invention is applied will be described with reference to specific examples.

FIG. 1 is a perspective view of a display panel used in the embodiment, in which a part of the panel is cut away to show the internal structure.

In the figure, 13 is a rear plate, 14 is a side wall,
Reference numeral 15 denotes a face plate, and 13 to 15 form an airtight container for maintaining the inside of the display panel at a vacuum. When assembling an airtight container, it is necessary to seal the joints of each member to maintain sufficient strength and airtightness.For example, apply frit glass to the joints, and in air or nitrogen atmosphere, 400-50
Sealing was achieved by firing at 0 degrees for 10 minutes or more.
A method of evacuating the inside of the airtight container to a vacuum will be described later. In addition, since the inside of the hermetic container is maintained at a vacuum of about 10 −6 [Torr], the inside of the hermetic container is prevented from being destroyed due to an atmospheric pressure, an unexpected impact, or the like.
A spacer 22 is provided as an atmospheric pressure resistant structure.

A substrate 16 is fixed to the rear plate 13, and N × M cold cathode elements 17 are formed on the substrate. (N and M are positive integers of 2 or more and are appropriately set according to the target number of display pixels. For example, in a display device for displaying high-definition television, N = 3000 and M = 1000 or more is desirable.) The N × M cold cathode elements are:
Simple matrix wiring is performed by M row direction wirings 18 and N column direction wirings 19. The portion constituted by the components 16 to 19 is called a multi-electron beam source.

The material, shape and manufacturing method of the cold cathode device are not limited as long as the multi-electron beam source used in the image display device of the present invention is an electron source in which cold cathode devices are arranged in a simple matrix wiring. Therefore, for example, a cold cathode device such as a surface conduction type emission device, an FE type, or an MIM type can be used.

Next, the structure of a multi-electron beam source in which surface conduction electron-emitting devices (described later) as cold cathode devices are arranged on a substrate and arranged in a simple matrix manner will be described.

FIG. 4 is a plan view of the multi-electron beam source used for the display panel of FIG. On the substrate 16, surface conduction type emission elements similar to those shown in FIG. 5 described later are arranged, and these elements are wired in a simple matrix by row-direction wiring electrodes 18 and column-direction wiring electrodes 19. An insulating layer (not shown) is formed between the electrodes at the intersections of the row direction wiring electrodes 18 and the column direction wiring electrodes 19 to maintain electrical insulation.

FIG. 5 shows a cross section along the line AA 'in FIG.

The multi-electron source having such a structure is as follows.
After the row direction wiring electrode 18, the column direction wiring electrode 19, the interelectrode insulating layer (not shown), the device electrode of the surface conduction electron-emitting device and the conductive thin film are formed in advance on the substrate, the row direction wiring electrode 18 and the column are formed. It was manufactured by supplying power to each element via the directional wiring electrode 19 and performing an energization forming process (described below) and an energization activation process (described below).

In this embodiment, the substrate 16 of the multi-electron beam source is fixed to the rear plate 13 of the airtight container. However, when the substrate 16 of the multi-electron beam source has a sufficient strength. Alternatively, the substrate 16 of the multi-electron beam source may be used as the rear plate of the airtight container.

On the lower surface of the face plate 15,
A fluorescent film 20 is formed. Since this embodiment is a color display device, three primary color phosphors of red (R), green (G), and blue (G) used in the field of CRT are separately applied to the portion of the fluorescent film 20. . The phosphors of the respective colors are separately applied in stripes as shown in FIG. 6A, for example, and black conductors 28 are provided between the stripes of the phosphors. The purpose of providing the black conductor 28 is to prevent the display color from being shifted even if there is a slight shift in the irradiation position of the electron beam, and to prevent the reflection of external light to prevent a decrease in display contrast. And preventing charge-up of the fluorescent film by the electron beam. Although graphite is used as a main component for the black conductor 28, any other material may be used as long as it is suitable for the above purpose.

The method of applying the phosphors of the three primary colors is not limited to the stripe arrangement shown in FIG. 6A, but may be, for example, a delta arrangement as shown in FIG. Other arrangements may be used.

When a monochrome display panel is manufactured, the phosphor film 20 may be made of a single-color phosphor material, and the black conductive material may not necessarily be used.

A metal back 21 known in the field of CRTs is provided on the surface of the fluorescent film 20 on the rear plate side. The purpose of providing the metal back 21 is to improve the light utilization rate by mirror-reflecting a part of the light emitted from the fluorescent film 20, to protect the fluorescent film 20 from the collision of negative ions, and to increase the electron beam acceleration voltage. To act as an electrode for applying an electric field, or to act as a conductive path for the excited electrons of the fluorescent film 20. The metal back 21 is
Was formed on the face plate substrate 15, the surface of the fluorescent film was subjected to a smoothing treatment, and Al was formed thereon by vacuum evaporation. When a fluorescent material for low voltage is used for the fluorescent film 20, the metal back 21 is not used.

Although not used in the present embodiment, for the purpose of applying an acceleration voltage and improving the conductivity of the fluorescent film, a transparent material made of, for example, ITO is used between the face plate substrate 15 and the fluorescent film 20. Electrodes may be provided.

FIG. 7 is a schematic cross-sectional view taken along the line AA 'of FIG. 1, and the numbers of the respective parts correspond to those of FIG. The spacer 22 is formed by forming a high-resistance film 24 on the surface of the insulating member 23 for the purpose of preventing electrification, and the inside of the face plate 15 (the metal back 21 and the like) and the surface of the substrate 16 (the row wiring 18).
Alternatively, it is made of a member having a low resistance film 29 formed on the contact surface of the spacer facing the column direction wiring 19), and is arranged in a necessary number and at a necessary interval to achieve the above object. , Is fixed to the inside of the face plate and the surface of the substrate 16 by the bonding material 30. Also, the high resistance film 24
Is formed on at least the surface of the insulating member 23 that is exposed to the vacuum in the airtight container, and the face plate 15 is formed via the low-resistance film 29 and the bonding material 30 on the spacer 22. (Metal back 21 or the like) and the surface of substrate 16 (row direction wiring 18 or column direction wiring 1).
9) is electrically connected. In the embodiment described here, the spacer 22 has a thin plate shape, is arranged in parallel with the row wiring 18, and is electrically connected to the row wiring 18.

The spacers 22 include the row wiring 18 and the column wiring 19 on the substrate 16 and the face plate 1.
5 must have an insulating property enough to withstand a high voltage applied to the metal back 21 on the inner surface, and have a conductivity enough to prevent the surface of the spacer 22 from being charged. This is as described above.

As the insulating member 23 of the spacer 22,
For example, quartz glass, glass having a reduced impurity content such as Na, soda lime glass, and ceramic members such as alumina can be used. The insulating member 23 preferably has a coefficient of thermal expansion close to that of the member forming the airtight container and the substrate 16.

As described above, the surface resistance of the high-resistance film 24 is 10 5 [Ω / Ω] in consideration of maintaining the antistatic effect and suppressing power consumption due to leakage current.
[□] to 10 to the 12th power [Ω / □], and the various materials described above are used as the material.

For the low resistance film 29, it is sufficient to select a resistance value sufficiently lower than that of the high resistance film 24. Ni, Cr, A
metals, such as u, Mo, W, Pt, Ti, Al, Cu, Pd, or alloys; and Pd, Ag, Au, RuO ₂ ,
It is appropriately selected from a printed conductor composed of a metal such as Pd-Ag or a metal oxide and glass, a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor material such as polysilicon.

The bonding material 30 is such that the spacer 22 is formed in the row direction wiring 1.
8 and the metal back 21 so as to be electrically connected to each other.
It is necessary to have conductivity. That is, frit glass to which a conductive adhesive, metal particles, or a conductive filler is added is preferable.

Also, Dx1 to Dxm and Dy1 to Dy
n and Hv are air-tightly structured electrical connection terminals provided for electrically connecting the display panel to an electric circuit (not shown). Dx1 to Dxm are electrically connected to the row wiring 18 of the multi-electron beam source, Dy1 to Dyn are electrically connected to the column wiring 19 of the multi-electron beam source, and Hv is electrically connected to the metal back 21 of the face plate.

To evacuate the inside of the hermetic container to a vacuum, after assembling the hermetic container, an exhaust pipe (not shown) and a vacuum pump are connected, and the inside of the hermetic container is raised to the power of 10 −7 [T
orr]. Thereafter, the exhaust pipe is sealed, but a getter film (not shown) is formed at a predetermined position in the airtight container immediately before or after the sealing in order to maintain the degree of vacuum in the airtight container. The getter film is, for example, a film formed by heating and depositing a getter material containing Ba as a main component by a heater or high-frequency heating,
Due to the adsorption action of the getter film, the inside of the airtight container is 1 × 10−5 or 1 × 10−7 [Torr].
Is maintained at a vacuum degree.

In the image display device using the display panel described above, when a voltage is applied to each of the cold cathode elements 17 through the external terminals Dx1 to Dxm and Dy1 to Dyn,
Electrons are emitted from each cold cathode element 17. At the same time, several hundred [V] are applied to the metal back 21 through the outer terminal Hv.
The emitted electrons are accelerated by applying a high voltage of a few kV to collide with the inner surface of the face plate 15. As a result, the phosphors of each color forming the fluorescent film 20 are excited and emit light, and an image is displayed.

Normally, the voltage applied to the surface conduction electron-emitting device 17 of the present invention, which is a cold cathode device, is about 12 to 16 [V].
The distance d between the metal back 21 and the cold cathode element 17 is 0.1
[Mm] to about 8 [mm], and the voltage between the metal back 21 and the cold cathode element 17 is about 0.1 [kV] to about 10 [kV].

The basic structure and manufacturing method of the display panel according to the embodiment of the present invention and the outline of the image display device have been described above.

Next, a method of manufacturing the multi-electron beam source used for the display panel of the above embodiment will be described. The material, shape, and manufacturing method of the cold cathode device are not limited as long as the multi-electron beam source used for the image display device of the present invention is an electron source in which cold cathode devices are arranged in a simple matrix. Therefore, for example, a surface conduction type emission element, an FE type, or M
A cold cathode device such as an IM type can be used.

However, in a situation where a display device having a large surface screen and an inexpensive display device is required, among these cold cathode devices, a surface conduction type emission device is particularly preferable. That is, in the FE type, since the relative position and shape of the emitter cone and the gate electrode greatly affect the electron emission characteristics, extremely high-precision manufacturing technology is required, but this achieves a large area and a reduction in manufacturing cost. Is a disadvantageous factor. Further, in the MIM type, it is necessary to make the thicknesses of the insulating layer and the upper electrode thin and uniform, which is also a disadvantageous factor in achieving a large area and a reduction in manufacturing cost. On the other hand, since the surface conduction electron-emitting device has a relatively simple manufacturing method, it is easy to increase the area and reduce the manufacturing cost. In addition, the inventors have found that among the surface conduction electron-emitting devices, those in which the electron-emitting portion or its peripheral portion is formed of a fine particle film have particularly excellent electron-emitting characteristics and can be easily manufactured. Therefore, it can be said that it is most suitable for use in a multi-electron beam source of a high-luminance, large-screen image display device. Therefore, in the display panel of the above embodiment, a surface conduction electron-emitting device having the electron-emitting portion or its peripheral portion formed of a fine particle film was used. Therefore, the basic structure, manufacturing method and characteristics of a suitable surface conduction electron-emitting device will be described first, and then the structure of a multi-electron beam source in which a large number of devices are arranged in a simple matrix will be described.

(Suitable Device Configuration and Manufacturing Method of Surface Conduction Emission Device) The typical configuration of a surface conduction electron-emitting device in which an electron-emitting portion or its peripheral portion is formed of a fine particle film is a flat type or a vertical type. Kinds are given.

(Planar surface conduction electron-emitting device) First, the structure and manufacturing method of a plane surface conduction electron-emitting device will be described. FIG. 8 is a plan view (a) and a cross-sectional view (b) for explaining the configuration of a planar surface conduction electron-emitting device. In the figure, 16 is a substrate, 31 and 32 are device electrodes, 33 is a conductive thin film, 34 is an electron emitting portion formed by energization forming, and 35 is a thin film formed by energization activation.

As the substrate 16, for example, various glass substrates such as quartz glass and blue plate glass, various ceramics substrates such as alumina, or an insulating layer made of, for example, SiO ₂ is laminated on the various substrates described above. A substrate or the like can be used.

The device electrodes 31 and 32 provided on the substrate 16 so as to be in parallel with the substrate surface are made of a conductive material. For example, Ni, Cr, A
Metals such as u, Mo, W, Pt, Ti, Cu, Pd, Ag and the like, alloys of these metals, metal oxides such as In ₂ O ₃ -SnO ₂ , and semiconductors such as polysilicon A material may be appropriately selected from the above and used. An electrode can be easily formed by using a combination of a film forming technique such as vacuum deposition and a patterning technique such as photolithography and etching. However, the electrode can be formed by other methods (for example, printing technique). I can't wait.

The shapes of the device electrodes 31 and 32 are appropriately designed according to the application purpose of the electron-emitting device. Generally, the electrode spacing L is usually designed by selecting an appropriate value from the range of several hundreds of angstroms to several hundreds of micrometers. It is in the range of ten micrometers. As for the thickness d of the device electrode, an appropriate value is usually selected from the range of several hundred angstroms to several micrometers.

A fine particle film is used for the conductive thin film 33. The fine particle film described here refers to a film including a large number of fine particles as constituent elements (including an island-shaped aggregate). When the fine particle film is examined microscopically, usually, a structure in which the individual fine particles are arranged apart from each other, a structure in which the fine particles are adjacent to each other, or a structure in which the fine particles overlap each other is observed.

The particle size of the fine particles used in the fine particle film is in the range of several Angstroms to several thousand Angstroms, and preferably in the range of 10 Angstroms to 200 Angstroms. Further, the thickness of the fine particle film is appropriately set in consideration of various conditions described below. That is, the element electrode 31
Alternatively, conditions necessary for good electrical connection with 32, conditions necessary for satisfactorily performing energization forming described later, conditions necessary for setting the electric resistance of the fine particle film itself to an appropriate value described later, and the like. It is. Specifically, it is set in the range of several Angstroms to several thousand Angstroms, but the range is preferably between 10 Angstroms and 500 Angstroms.

Materials that can be used to form the fine particle film include, for example, Pd, Pt, Ru, Ag,
Au, Ti, In, Cu, Cr, Fe, Zn, Sn, T
a, W, Pb and other metals, PdO, Sn
Oxides such as O ₂ , In ₂ O ₃ , PbO, Sb ₂ O ₃ , HfB ₂ , ZrB ₂ , LaB ₆ , CeB
Boride such as ₆ , YB ₄ , GdB ₄ ,
carbides such as iC, ZrC, HfC, TaC, SiC, WC, etc., nitrides such as TiN, ZrH, HfN, semiconductors such as Si, Ge, carbon, and the like. It is appropriately selected from these.

As described above, the conductive thin film 33 is formed of a fine particle film.
It was set to be included in the range of 3 to 10 7 [ohm / sq].

Since it is desirable that the conductive thin film 33 and the device electrodes 31 and 32 be electrically connected well, they have a structure in which a part of each of them overlaps.
In the example of FIG. 8, the overlapping method is as follows.
Although the device electrode and the conductive thin film are laminated in this order, the substrate, the conductive thin film and the device electrode may be laminated in this order from the bottom in some cases.

The electron emitting section 34 is formed of a conductive thin film 33.
Are formed in a part of the surface, such as a crack, and have a higher electrical property than the surrounding conductive thin film.
The cracks and the like are formed by performing a later-described energization forming process on the conductive thin film 33. Fine particles having a particle size of several Angstroms to several hundred Angstroms may be arranged in the crack. Since it is difficult to accurately and accurately show the actual position and shape of the electron-emitting portion, they are schematically shown in FIG.

Further, the thin film 35 is a thin film made of carbon or a carbon compound, and covers the electron emitting portion 34 and the vicinity thereof. After the energization forming process, the thin film 35
It is formed by performing an energization activation process described later.

The thin film 35 is made of any one of single-crystal graphite, polycrystalline graphite, and amorphous carbon, or a mixture thereof, and has a film thickness of 500 [Å] or less, but preferably 300 [Å] or less. More preferred. Since it is difficult to accurately show the actual position and shape of the thin film 35, they are schematically shown in FIG. Also, in the plan view (a), the thin film 35
The device in which a part of is removed is shown.

The basic structure of the preferred elements has been described above. In the examples, the following elements were used.

That is, blue glass was used for the substrate 16, and Ni thin films were used for the element electrodes 31 and 32. The thickness d of the device electrode is 1000 [angstrom], and the electrode interval L
Was 2 [micrometers].

Pd or P as the main material of the fine particle film
Using dO, the thickness of the fine particle film was about 100 [angstrom], and the width W was 100 [micrometer].

Next, a description will be given of a method of manufacturing a preferred flat surface conduction electron-emitting device. (A) to (d) of FIG.
Is a cross-sectional view for explaining the manufacturing process of the surface conduction electron-emitting device, and the notation of each member is the same as in FIG.

1) First, device electrodes 31 and 32 are formed on a substrate 16 as shown in FIG.

When forming, the substrate 1
After sufficiently cleaning 6 with a detergent, pure water, and an organic solvent, the material of the device electrode is deposited (for example, a vacuum film forming technique such as a vapor deposition method or a sputtering method may be used). . After that, the deposited electrode material is patterned using photolithography and etching technology,
A pair of device electrodes (31 and 32) shown in FIG.

2) Next, a conductive thin film 33 is formed as shown in FIG.

In the formation, first, an organic metal solution is applied to the substrate (a), dried, heated and baked to form a fine particle film, and then patterned into a predetermined shape by photolithography and etching. . here,
The organic metal solution is a solution of an organic metal compound whose main element is a material of fine particles used for the conductive thin film (specifically, Pd was used as a main element in this example.
In the embodiment, the dipping method is used as the coating method, but other methods such as a spinner method and a spray method may be used. ).

As a method for forming a conductive thin film made of a fine particle film, a method other than the method of applying an organometallic container used in this embodiment, for example, a vacuum evaporation method, a sputtering method, or the like.
Alternatively, a chemical vapor deposition method or the like may be used.

3) Next, as shown in FIG. 13C, an appropriate voltage is applied between the device electrodes 31 and 32 from the forming power source 36 to perform the energization forming process, and the electron emission portion 34 is turned on. Form.

The energization forming treatment is to energize the conductive thin film 34 made of a fine particle film, and to appropriately break, deform, or alter a part of the conductive thin film 34 to change to a structure suitable for emitting electrons. This is the process that causes In a portion of the conductive thin film made of the fine particle film which has been changed to a structure suitable for emitting electrons (that is, the electron emitting portion 34), an appropriate crack is formed in the thin film. Note that the electrical resistance measured between the device electrodes 31 and 32 is significantly increased after the formation, as compared to before the electron emission portion 34 is formed.

FIG. 10 shows an example of an appropriate voltage waveform applied from the forming power supply 36 in order to describe the energization method in more detail. When forming a conductive thin film made of a fine particle film, a pulse-like voltage is preferable. In the case of this embodiment, a pulse width T is used as shown in FIG.
One triangular wave pulse was continuously applied at a pulse interval T2. At that time, the peak value Vpf of the triangular wave pulse was sequentially increased. In addition, monitor pulses Pm for monitoring the state of formation of the electron-emitting portions 34 were inserted at appropriate intervals between the triangular-wave pulses, and the current flowing at that time was measured by the ammeter 37.

In the embodiment, for example, in a vacuum atmosphere of about 10 −5 [Torr], for example, the pulse width T1 is 1 [millisecond] and the pulse interval T2 is 1
0 [millisecond], and the peak value Vpf is set to 0.
The pressure was increased by 1 [V]. Then, the monitor pulse Pm was inserted at a rate of one every time five triangular waves were applied. The monitor pulse voltage Vpm was set to 0.1 [V] so as not to adversely affect the forming process. The electric resistance between the device electrodes 31 and 32 is 1
When the current reaches a level of × 10 6 [ohm], that is, the current measured by the ammeter 37 when the monitor pulse is applied is 1 × 1.
At the stage when the power becomes 0 or less than the seventh power [A], the energization related to the forming process is terminated.

The above method is a preferable method for the surface conduction electron-emitting device of the present embodiment, and for example, the design of the surface conduction electron-emitting device such as the material and film thickness of the fine particle film or the element electrode interval L is changed. In such a case, it is desirable to appropriately change the energization conditions accordingly.

4) Next, as shown in FIG. 9D, an appropriate voltage is applied between the element electrodes 31 and 32 from the activating power supply 38 to carry out an energization activating process, thereby performing electron emission. Improve characteristics.

The energization activation process is a process of energizing the electron-emitting portion 34 formed by the energization forming process under appropriate conditions and depositing carbon or a carbon compound in the vicinity thereof (in the figure). Shows a deposit made of carbon or a carbon compound as the member 35.) Note that by performing the energization activation process, the emission current at the same applied voltage can be typically increased by 100 times or more as compared with before the energization activation process.

Specifically, 10 minus the fourth power to 1
By applying a voltage pulse periodically in a vacuum atmosphere within the range of 0 to the fifth power [Torr], carbon or a carbon compound originating from an organic compound existing in the vacuum atmosphere is deposited. The deposit 35 is any of single crystal graphite, polycrystalline graphite, and amorphous carbon, or a mixture thereof, and has a thickness of 500 Å or less, more preferably 300 Å or less.

In order to explain the energization method in more detail, FIG. 11A shows an example of an appropriate voltage waveform applied from the activation power supply 38. In the present embodiment, the energization activation process is performed by periodically applying a rectangular wave of a constant voltage. Specifically, the voltage Vac of the rectangular wave is 14 [V], and the pulse width T3 is 1 [mm]. Second] and the pulse interval T4 is 10 [milliseconds]. The above-mentioned energization conditions are preferable conditions for the surface conduction electron-emitting device of this embodiment, and when the design of the surface conduction electron-emitting device is changed, it is desirable to appropriately change the conditions accordingly.

Reference numeral 39 shown in FIG. 9D denotes an anode electrode for capturing an emission current Ie emitted from the surface conduction electron-emitting device, and is connected to a DC high-voltage power supply 40 and an ammeter 41. (When the activation process is performed after the substrate 16 is incorporated into the display panel, the phosphor screen of the display panel is used as the anode electrode 39.) While the voltage is applied from the activation power supply 38, The emission current Ie is measured by the total 41 to monitor the progress of the energization activation process, and the operation of the activation power supply 38 is controlled. An example of the emission current Ie measured by the ammeter 41 is shown in FIG. 11B. When the pulse voltage is started to be applied from the activation power supply 38, the emission current Ie increases with the passage of time, but eventually saturates. And hardly increase. As described above, when the emission current Ie is substantially saturated, the application of the voltage from the activation power supply 38 is stopped, and the energization activation process ends.

The above-mentioned energization conditions are preferable conditions for the surface conduction electron-emitting device of the present embodiment, and if they are changed in the design of the surface conduction electron-emitting device, the conditions should be changed accordingly. desirable.

As described above, the planar surface conduction electron-emitting device shown in FIG. 9E was manufactured.

(Vertical Type Surface Conduction Emission Element) Next, another typical configuration of a surface conduction type emission element in which the electron emission portion or its periphery is formed of a fine particle film, that is, a vertical type surface conduction emission device. The configuration of the element will be described.

FIG. 12 is a schematic sectional view for explaining the basic structure of the vertical type. In the figure, reference numeral 42 denotes a substrate, 43 and 44 denote element electrodes, 45 denotes a step forming member, and 46 denotes a fine particle film. The used conductive thin film, 47 is an electron emitting portion formed by the energization forming process, and 48 is a thin film formed by the energization activation process.

The difference between the vertical type and the flat type described above is that one of the device electrodes (43) is formed with a step forming member 45.
The conductive thin film 46 is provided on the step forming member 4.
5 in that it covers the side surfaces. Therefore, the element electrode interval L in the planar type shown in FIG. 8 is set as the step height Ls of the step forming member 45 in the vertical type.
For the substrate 42, the device electrodes 43 and 44, and the conductive thin film 46 using the fine particle film, the materials listed in the description of the flat type can be used in the same manner. For the step forming member 45, an electrically insulating material such as SiO ₂ is used.

Next, a method of manufacturing a vertical surface conduction electron-emitting device will be described. FIGS. 13A to 13F are cross-sectional views for explaining a manufacturing process.
Same as 2.

1) First, as shown in FIG. 13A, an element electrode 44 is formed on a substrate 42.

2) Next, as shown in FIG. 13B, an insulating layer for forming a step forming member is laminated. The insulating layer may be formed by stacking, for example, SiO ₂ by a sputtering method, but another film forming method such as a vacuum evaporation method or a printing method may be used.

3) Next, as shown in FIG. 13C, an element electrode 43 is formed on the insulating layer.

4) Next, as shown in FIG. 14D, a part of the insulating layer is removed by using, for example, an etching method to expose the element electrode 44.

5) Next, as shown in FIG. 14E, a conductive thin film 46 using a fine particle film is formed. For the formation, as in the case of the flat type, a film forming technique such as a coating method may be used.

6) Next, as in the case of the flat type, the energization forming process is performed to form an electron emission portion (the same process as the flat type energization forming process described with reference to FIG. 9C). Just do it.)

7) Next, similarly to the case of the above-mentioned planar type, an activation process is performed to deposit carbon or a carbon compound in the vicinity of the electron emission portion (the planar type energizing described with reference to FIG. 9D). The same processing as the activation processing may be performed.)

As described above, the vertical type surface conduction electron-emitting device shown in FIG.

(Characteristics of Surface Conduction Emitting Element Used in Display Device) The element structure and manufacturing method of the planar and vertical surface conduction electron-emitting devices have been described above. Next, the characteristics of the element used in the display device will be described. Is described.

FIG. 14 shows typical examples of (emission current Ie) versus (device applied voltage Vf) characteristics and (device current If) versus (device applied voltage Vf) characteristics of the device used in the display device. . Note that the emission current Ie is significantly smaller than the element current If, and it is difficult to show the same current on the same scale.
Since these characteristics are changed by changing design parameters such as the size and shape of the element, the two graphs are shown in arbitrary units.

The element used in the display device has the following three characteristics regarding the emission current Ie. Primarily,
When a voltage higher than a certain voltage (hereinafter referred to as a threshold voltage Vth) is applied to the element, the emission current Ie sharply increases. On the other hand, when the voltage is lower than the threshold voltage Vth, the emission current Ie is increased.
e is hardly detected.

That is, the non-linear element has a clear threshold voltage Vth with respect to the emission current Ie.

Secondly, since the emission current Ie changes depending on the voltage Vf applied to the element, the emission current Ie varies with the voltage Vf.
The magnitude of e can be controlled.

Third, since the response speed of the current Ie emitted from the element is faster with respect to the voltage Vf applied to the element, the amount of charge of the electrons emitted from the element depends on the length of time during which the voltage Vf is applied. Can control.

Because of the above characteristics, the surface conduction electron-emitting device could be suitably used for a display device. For example, in a display device in which a large number of elements are provided corresponding to the pixels on the front screen, display can be performed by sequentially scanning the display screen by using the first characteristic. That is,
The driving element has a threshold voltage Vt according to a desired light emission luminance.
h or higher, and a voltage lower than the threshold voltage Vth is applied to the non-selected elements. By sequentially switching the elements to be driven, the display screen can be sequentially scanned and displayed.

Further, since the emission luminance can be controlled by using the second characteristic or the third characteristic, gradation display can be performed.

(Structure of a multi-electron beam source in which a large number of elements are arranged in a simple matrix) Next, the structure of a multi-electron beam source in which the above-described surface conduction electron-emitting elements are arranged on a substrate and arranged in a simple matrix will be described.

FIG. 4 is a plan view of the multi-electron beam source used for the display panel of FIG. On the substrate, surface conduction type emission elements similar to those shown in FIG. 8 are arranged, and these elements are wired in a simple matrix by row direction wiring electrodes 18 and column direction wiring electrodes 19. An insulating layer (not shown) is formed between the electrodes at the intersections of the row direction wiring electrodes 18 and the column direction wiring electrodes 19 to maintain electrical insulation.

FIG. 5 shows a cross section along the line AA 'in FIG.

Incidentally, the multi-electron source having such a structure is as follows.
After the row direction wiring electrode 18, the column direction wiring electrode 19, the interelectrode insulating layer (not shown), the device electrode of the surface conduction electron-emitting device and the conductive thin film are formed in advance on the substrate, the row direction wiring electrode 18 and the column are formed. The device was manufactured by supplying current to each element via the directional wiring electrode 19 and performing an energization forming process and an energization activation process.

FIG. 15 is a block diagram showing a schematic configuration of a driving circuit for performing television display based on an NTSC television signal. In the figure, a display panel 49 corresponds to the above-described display panel, and is manufactured and operates as described above. The scanning circuit 50 scans a display line, and the control circuit 51 generates a signal to be input to the scanning circuit. The shift register 52 shifts data for each line, and the line memory 53 stores the shift register 5.
The data for one line from 2 is input to the modulation signal generator 54. The synchronization signal separation circuit 55 separates the synchronization signal from the NTSC signal.

Hereinafter, the function of each unit of the apparatus shown in FIG. 15 will be described in detail.

First, the display panel 49 is connected to an external electric circuit via terminals Dx1 to Dxm, terminals Dy1 to Dyn, and a high voltage terminal Hv. Among them, the terminals Dx1 to Dxm are connected to a multi-electron beam source provided in the display panel 49, that is, a cold cathode element arranged in a matrix of m rows and n columns in one row (n
A scanning signal for sequentially driving each element is applied. On the other hand, to the terminals Dy1 to Dyn, a modulation signal for controlling the output electron beams of the n elements for one row selected by the scanning signal is applied. The high voltage terminal Hv is connected to the DC voltage source Va by, for example, 5 kV.
This is an accelerating voltage for applying sufficient energy to the electron beam output from the multi-electron beam source to excite the phosphor.

Next, the scanning circuit 50 will be described. The circuit includes m switching elements (schematically indicated by S1 to Sm in the figure), and each switching element includes an output voltage of a DC voltage source Vx or 0 [V] ( (Ground level), and is electrically connected to the terminals Dx1 to Dxm of the display panel 49. Each of the switching elements S1 to Sm operates based on the control signal Tscan output from the control circuit 51. However, in practice, it can be easily configured by combining switching elements such as FETs. . Note that the DC voltage source Vx is
Based on the characteristics of the electron-emitting device illustrated in FIG. 14, a constant voltage is set so that the driving voltage applied to the device that is not scanned is equal to or lower than the electron emission threshold voltage Vth.

The control circuit 51 has a function of matching the operation of each unit so that appropriate display is performed based on an image signal input from the outside. Based on the synchronization signal Tsync sent from the synchronization signal separation circuit 55 described below, Tscan, Tsft and Tmr
Generate y control signals. The synchronization signal separation circuit 55
A circuit for separating a synchronization signal component and a luminance signal component from an NTSC television signal input from the outside, and can be easily configured by using a frequency separation (filter) circuit as is well known. is there. The synchronizing signal separated by the synchronizing signal separating circuit 55 is composed of a vertical synchronizing signal and a horizontal synchronizing signal as is well known, but is shown here as a Tsync signal for convenience of explanation. On the other hand, the luminance signal component of the image separated from the television signal is referred to as DA for convenience.
This signal is indicated as a TA signal, and is input to the shift register 52.

The shift register 52 is for serially / parallel converting the DATA signal input serially in time series for each line of an image, and is based on a control signal Tsft sent from the control circuit 51. Works. That is, the control signal Tsft is
Can be paraphrased as a shift lock. The data for one line of the serial / parallel-converted image (corresponding to the drive data for n electron-emitting devices) is Id1
To the shift register 52 as n signals of Idn.
Is output by

The line memory 53 is a storage device for storing data for one line of an image for a required time only.
The contents of Id1 to Idn are stored as appropriate according to the control signal Tmry sent from the control circuit 51. The stored contents are output as I'd1 to I'dn and input to the modulation signal generator 54.

The modulation signal generator 54 controls the electron-emitting device 17 according to each of the image data I'd1 to I'dn.
Are output to be applied to the electron-emitting devices 17 in the display panel 49 through terminals Dy1 to Dyn.

As described with reference to FIG. 14, the surface conduction electron-emitting device according to the present invention has the following basic characteristics with respect to the emission current Ie. That is, electron emission has a clear threshold voltage Vth (8 [V] in a surface conduction electron-emitting device of an embodiment described later), and electron emission occurs only when a voltage equal to or higher than the threshold Vth is applied. Also, the electron emission threshold V
For a voltage equal to or greater than th, the emission current Ie also changes according to the change in the voltage, as shown in the graph of FIG. For this reason, when a pulse-like voltage is applied to the device, for example, when a voltage equal to or lower than the electron emission threshold Vth is applied, no electron emission occurs. An electron beam is output from the conduction type emission device. At this time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm.
In addition, it is possible to control the total amount of charges of the output electron beam by changing the pulse width Pw.

Therefore, as a method of modulating the electron-emitting device in accordance with the input signal, a voltage modulation method, a pulse width modulation method, or the like can be employed. When performing the voltage modulation method, a circuit of the voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 54. be able to. When the pulse width modulation method is performed, the modulation signal generator 54 generates a voltage pulse having a constant peak value, and modulates the width of the voltage pulse appropriately according to input data. Circuit can be used.

The shift register 52 and the line memory 53
Can be adopted as a digital signal type or an analog signal type. That is, the serial / parallel conversion and storage of the image signal may be performed at a predetermined speed.

When the digital signal type is used, it is necessary to convert the output signal DATA of the synchronization signal separation circuit 55 into a digital signal. For this purpose, an A / D converter is provided at the output of the synchronization signal separation circuit 55. Just do it. In this connection, the circuit used for the modulation signal generator differs slightly depending on whether the output signal of the line memory 53 is a digital signal or an analog signal. That is, in the case of the voltage modulation method using a digital signal, the modulation signal generator 54 includes, for example, D / D
An A conversion circuit is used, and an amplification circuit and the like are provided as needed. In the case of the pulse width modulation method, the modulation signal generator 54 includes, for example, a high-speed oscillator, a counter (counter) for counting the number of waves output from the oscillator, and a comparator for comparing the output value of the counter with the output value of the memory. (Comparator) is used. If necessary, an amplifier for amplifying the pulse width modulated signal output from the comparator to the drive voltage of the electron-emitting device can be added.

In the case of the voltage modulation method using an analog signal, an amplification circuit using, for example, an operational amplifier or the like can be used as the modulation signal generator 54, and a shift level circuit or the like can be added as necessary. In the case of the pulse width modulation method, for example, a voltage controlled oscillation circuit (VCO) can be employed, and an amplifier for amplifying the voltage up to the drive voltage of the electron-emitting device can be added as necessary.

In the image display apparatus to which the present invention can be applied, the electron emission element is applied by applying a voltage to each of the electron emission elements via the external terminals Dx1 to Dxm and Dy1 to Dyn. Occurs. A high voltage is applied to the metal back 21 or the transparent electrode (not shown) via the high voltage terminal Hv to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 20 and emit light to form an image.

The configuration of the image display apparatus described here is an example of an image forming apparatus to which the present invention can be applied, and various modifications can be made based on the concept of the present invention. The input signal is described in the NTSC system. However, the input signal is not limited to the NTSC system, but may be a PAL or SECAM system or a TV signal (MUSE system or other high-definition TV) system including a larger number of scanning lines. Can also be adopted.

[0172]

The present invention will be described in more detail with reference to the following examples.

In each of the embodiments described below, as the multi-electron beam source, N × M (N = 307) of the above-described type having an electron emission portion in the conductive fine particle film between the electrodes is used.
A multi-electron beam source was used in which the surface conduction electron-emitting devices (2, M = 1024) were matrix-wired (see FIGS. 1 and 4) by M row-directional wirings and N column-directional wirings.

Example 1 High Resistance Film A Ti—Al alloy nitride film was formed by simultaneously sputtering Ti and Al targets with a high frequency power supply. The sputtering gas is a mixed gas of Ar: N ₂ of 1: 2 and the total pressure is 1 mTorr.
It is. The insulating member is made of soda lime glass, Ti and A
The specific resistance of the alloy nitride film was changed by adjusting the high frequency power applied to the target. Ti concentration 31a
At the time of t%, the specific resistance was 5 × 10 ⁴ Ωcm. An Hf-N film was formed to a thickness of 10 nm on the surface of the Ti-Al alloy nitride film having a thickness of 60 nm by a sputtering method to obtain a sample A.

(Example 2: High resistance film) A Cr target was used instead of Ti in Example 1, and Cr-Al
An alloy nitride film was formed to a thickness of 200 nm. The sputtering gas was the same as in Example 1, the high-frequency power of Cr and Al was adjusted, and the specific resistance was 4.0 × 10 ⁵ Ωc with 5.8 at% of Cr.
m was obtained. A sample B was obtained by continuously forming a 1 nm thick Pt film on the surface of a 4 × 10 ⁵ Ωcm Cr—Ar alloy nitride film using the same apparatus as the alloy nitride film. As a result of SEM observation of this film, it was found that Pt formed a discontinuous island-like film.

(Embodiment 3: High resistance film)
Instead of using a Ta target, Ta-Al
An alloy nitride film was formed to a thickness of 200 nm. Sputter gas is real
Same as the first embodiment, adjusting high frequency power of Ta and Al
When the composition of Ta is 31 at%, the specific resistance is 3.0 × 10 3
^FiveAn Ωcm alloy nitride film was obtained. Au film on this surface
1nm thick, by e-beam evaporation
Sample C was obtained. As a result of SEM observation of this film, Example 2 and
Similarly, a discontinuous island-like film was formed.

(Example 4: High resistance film) Cr-BN was deposited by simultaneously sputtering targets of Cr and B by RF sputtering. The thickness is 100 nm. The sputtering gas is a mixed gas of Ar: N ₂ = 7: 3,
The total pressure was 0.45 Pa. The composition is adjusted by adjusting the high-frequency power applied to the Cr and B targets.
When r was 11.6 at%, a film having a specific resistance of 1 × 10 ⁴ Ωcm was obtained. The thickness is about 200 nm. Hf-
A sample D was obtained by forming an N film to a thickness of 10 nm by a sputtering method.

(Example 5: High resistance film) Cr and Si-N
Was simultaneously sputtered by RF sputtering to form a Cr—Si—N film. The sputtering gas is A
A mixed gas of r: N ₂ = 7: 1 and the total pressure was 0.40 Pa. The composition was adjusted by adjusting the high frequency power applied to the Cr and Si targets, and when Cr was 3.8 at%, a film having a specific resistance of 1 × 10 ⁵ Ωcm was obtained. The film thickness is about 100
nm. A sample E was obtained by forming a 1 nm thick Pt film on this surface by electron beam evaporation.

(Example 6: High resistance film) The sample B prepared in Example 2 was heat-treated at 450 ° C in the air to obtain a sample F. The resistance of Sample B did not change even after the heat treatment. SI
As a result of measuring the thickness of the oxide layer by MS (secondary ion mass spectrometer), oxygen was detected from a depth of about 25 mm from the surface of the Cr-Al alloy nitride film, and Cr- was detected at the boundary between the alloy nitride film and the Pt film. An Al alloy oxide film is formed. Since the oxygen concentration of the oxide film near the alloy nitride film is low,
An oxynitride film is formed in this region.

Example 7 Sample A produced in Example 1 was heat-treated at 450 ° C. in the atmosphere to obtain Sample G. As a result of the heat treatment, the resistance value of Sample A increased about 10 times. SIMS
As a result of measuring the oxide layer thickness with a (secondary ion mass spectrometer), oxygen was detected from a depth of about 25 nm from the surface of the Cr-Al alloy nitride film, and the alloy nitride film and the second layer (Hf-O,
At the boundary of the (Hf-N film), a Cr-Al alloy oxide film is formed. Since the oxygen concentration of the oxide film near the alloy nitride film is low, an oxynitride film is formed in this region. When surface composition analysis was performed by ESCA, oxygen and a trace amount of nitrogen were detected on the surface, and Hf-O and Hf-N were present on the surface.

(Comparative Example) As a comparative example, a sample having only one antistatic film was prepared. An Au island film was formed on quartz glass as an insulating member by RF sputtering with a thickness of 3 nm. The specific resistance of the obtained Au film was 3 × 10 ⁵ Ω.

Further, as another comparative example, a sample in which the thickness of the second layer was increased was manufactured. The same Cr-Al-N as described in Example 2 was applied on quartz glass as an insulating member.
A film was formed to a thickness of 00 nm, and Pt was formed thereon to a large thickness of 40 nm. This is designated as Sample I.

[Results] The samples A to E on which the antistatic film of the present invention was formed and the sample H of the comparative example were each tested at 425 ° C.
The resistance after heat treatment, in vacuum, and after heat treatment at 200 ° C. in vacuum was measured.

The results were as shown in FIG.
Although the resistance value greatly fluctuates, the antistatic film of the present invention is stable without any significant change. That is, the Au island film shown in the comparative example has a specific resistance value in a preferable range as an antistatic film, but has poor stability of the resistance value. However, since the resistance change of the antistatic film of the present invention is small even after the heat treatment, the antistatic film is particularly effective for use in a vacuum environment such as an electron beam display, or for applications including a high-temperature heat treatment and a vacuum heat treatment in a manufacturing process. is there.

Further, the thickness of the second layer of Pt was set to 40 nm.
The sample I of the comparative example has a specific resistance of 10 ^-FiveΩcm
Resistance value as a spacer antistatic film for slave display
Is too low to apply enough high pressure.

(Embodiment 8: Spacer) Next, the structure of a display panel of a display device to which the present invention is applied will be described with reference to a specific example.

FIG. 1 is a perspective view of a display panel used in the embodiment, in which a part of the panel is cut away to show the internal structure.

In the figure, 13 is a rear plate, 14 is a support frame (side wall), 15 is a face plate,
The inside of the display panel is maintained at a vacuum by 4 and 15. A substrate 16 is fixed to the rear plate 13. On the substrate, 1920 × 480 surface conduction electron-emitting devices 17 are formed as cold cathode electron-emitting devices. In FIG. 1, the numbers are shown in a simplified manner.

In this embodiment, the substrate 16 of the multi-electron beam source is fixed to the rear plate 13 of the airtight container. However, if the substrate 16 of the multi-electron beam source has a sufficient strength, The substrate 16 of the multi-electron beam source may be used as the rear plate of the airtight container.

FIG. 4 is a plan view of the multi-electron beam source used for the display panel 16 of FIG. On the substrate, surface conduction electron-emitting devices are arranged, and these devices are wired in a simple matrix by X-direction wiring electrodes 18 and Y-direction wiring electrodes 19. An insulating layer (not shown) is formed between the X-direction electrodes 18 and the Y-direction wiring electrodes 19 at the intersections of the electrodes to maintain electrical insulation.

FIG. 5 shows a cross section along the line AA 'in FIG.

(Flat-Type Surface-Conduction-Type Emission Element) The element configuration of the flat-type surface-conduction-type emission element used in this embodiment will be described with reference to FIG. In the figure, 16 is a substrate, 31 and 3
Reference numeral 2 denotes an element electrode; 33, a conductive thin film; 34, an electron-emitting portion formed by energization forming; and 35, a thin film formed by energization activation.

The substrate 16 is made of various glass substrates such as quartz glass and blue plate glass, various ceramics substrates such as alumina, or SiO ₂ on the above various substrates.
Insulating layer or the like can be used.

The device electrodes 31 and 32 provided on the substrate 16 so as to be opposed to the substrate surface in parallel to each other are formed of a conductive material. For example, Ni, Cr, A
Metals such as u, Mo, W, Pt, Ti, Cu, Pd, Ag and the like, alloys of these metals, metal oxides such as In ₂ O ₃ -SnO ₂ , and semiconductors such as polysilicon A material may be appropriately selected from the above and used. An electrode can be easily formed by using a combination of a film forming technique such as vacuum evaporation and a patterning technique such as photolithography and etching. However, the electrode can be formed by other methods (for example, printing technique). No problem.

The shapes of the device electrodes 31 and 32 are appropriately designed according to the application purpose of the electron-emitting device. Generally, the electrode interval L is usually designed by selecting an appropriate numerical value from the range of several tens of meters to several hundreds of micrometers. An appropriate value is selected from the range of ten micrometers.

A fine particle film is used for the portion of the conductive thin film 33. The fine particle film mentioned here refers to a film containing a large number of fine particles as constituent elements (including an island-shaped aggregate). When the fine particle film is examined microscopically, usually, a structure in which individual fine particles are spaced apart from each other or a structure in which fine particles overlap each other is observed.

The particle size of the fine particles used for the fine particle film is in the range of several angstrom to several hundred nanometers, and particularly preferably in the range of 1 to 20 nanometers. Further, the thickness of the fine particle film is appropriately set in consideration of various conditions described below. That is, the conditions necessary for good electrical connection to the device electrode 31 or 32, the conditions necessary for good energization forming described below, and the electric resistance of the fine particle film itself to an appropriate value described later. And other conditions required. Specifically, it is set within a range of several Angstroms to several hundreds of nanometers.
Between nanometers.

Materials that can be used to form the fine particle film include, for example, Pd, Pt, Ru, Ag, A
u, Ti, In, Cu, Cr, Fe, Zn, Sn, T
a, W, Pb and other metals, PdO, Sn
Oxides such as O ₂ , In ₂ O ₃ , PbO, Sb ₂ O ₃ , HfB ₂ , ZrB ₂ , LaBL ₆ , Ce
Borides such as B ₆ , YB ₄ , GdB ₄ ,
Carbides such as TiC, ZrC, HfC, TaC, SiC, and WC, nitrides such as TiN, ZrN, and HfN; semiconductors such as Si and Ge; and carbon. It is appropriately selected from these.

As described above, the conductive thin film 33 was formed of a fine particle film, and its surface resistance was set to be in the range of 10 3 to 10 7 ohms. Since it is desirable that the conductive thin film 33 and the element electrodes 31 and 32 be electrically connected well, a structure is adopted in which a part of each of them overlaps. In the example of FIG. 8, the layers are stacked in the order of the substrate, the device electrode, and the conductive thin film in the example shown in FIG. 8, but may be stacked in the order of the substrate, the conductive thin film, and the device electrode from the bottom in some cases. Absent.

The electron-emitting portion 34 is a portion such as a crack formed in a part of the conductive thin film 33, and has an electrically higher resistance than the surrounding conductive thin film. The cracks and the like are formed by applying a current forming process to the conductive thin film 33. The energization forming process is performed on the conductive thin film 33 made of a fine particle film.
This is a process in which a portion of the structure is appropriately destroyed, deformed, or altered by applying an electric current to change the structure into a structure suitable for emitting electrons. In a portion of the conductive thin film made of the fine particle film which has been changed to a structure suitable for emitting electrons (that is, the electron emitting portion 34), an appropriate crack is formed in the thin film. Note that the electrical resistance measured between the device electrodes 31 and 32 is significantly increased after the formation, as compared to before the electron emission portion 34 is formed.

The thin film 35 is a thin film made of carbon or a carbon compound, and covers the electron emitting portion 34 and its vicinity.

After the energization forming process, the thin film 35
It was formed by performing an activation process.

The thin film 35 is made of any one of single-crystal graphite, polycrystalline graphite, and amorphous carbon, or a mixture thereof, and has a thickness of 50 nm or less, and more preferably 17 nm or less. preferable.

The energization activation process is a process of energizing the electron-emitting portion 34 formed in the energization forming process under appropriate conditions and depositing carbon or a carbon compound in the vicinity thereof (in the figure). Shows a deposit made of carbon or a carbon compound as the member 35.) Note that by performing the energization activation process, the emission current at the same applied voltage can be typically increased by 100 times or more as compared with before the energization activation process. Specifically, 10 minus 4th power to 10 minus 5th power T
By applying a voltage pulse periodically in a vacuum atmosphere within the range of orr, carbon or a carbon compound derived from an organic compound existing in the vacuum atmosphere is deposited. The deposit 35 is any one of single-crystal graphite, polycrystalline graphite, and amorphous carbon, or a mixture thereof, and has a thickness of 50 nanometers or less, more preferably 17 nanometers or less.

The basic structure of the preferred elements has been described above. In the examples, the following elements were used.

That is, blue glass was used for the substrate 16 and Ni thin films were used for the device electrodes 31 and 32. The thickness d of the device electrode was 100 nanometers, and the electrode interval L was 20 micrometers. Pd as main raw material for fine particle membrane
Alternatively, PdO is used, the thickness of the fine particle film is about 10 nanometers, and the width W is 100 micrometers.

The multi-electron source having such a structure is as follows.
After the X-direction wiring electrode 18, the Y-direction wiring electrode 19, the interelectrode insulating layer (not shown), the device electrode of the surface conduction electron-emitting device and the conductive thin film are formed on the substrate in advance, the X-direction wiring electrode 18 and the Y-direction The device was manufactured by supplying power to each element via the wiring electrode 19 and performing an energization forming process and an energization activation process.

(Spacer) Length 40 mm, width 2.8 m
Glass having the same quality as a rear plate having a thickness of 0.2 mm and a thickness of 0.2 mm was used as an insulating member. As the antistatic film, a film obtained by laminating Pt as the second layer on the Cr—Al alloy nitride film used in Example 2 was used. The thickness is 200 nm. The present invention is not limited to this, and the antistatic film of the present invention can be used.

Next, as a low-resistance film 29 (FIG. 7), a Pt film having a thickness of 0.1 μm was formed in a 17 μm band parallel to the connection portion between the face plate and the rear plate.

The spacer is connected to the metal back on the X-direction wiring and the face plate using conductive frit glass. As the conductive frit glass, a mixture of frit glass and conductive fine particles whose surface is coated with gold is used, and is electrically connected to the antistatic film on the spacer surface and the X-directional wiring or face plate.

When the X-direction wiring and the Y-direction wiring of the display device having the above structure were connected to an image signal circuit (not shown) to display a television image, the light emission position shift near the spacer was slight, and there was no practical problem. Was something.

As a comparative example, the Cr-A prepared in Example 2 was used.
An 1N antistatic film was formed on the same insulating member without providing the second layer of Pt and used as a spacer. At this time, when the television image was displayed, the light emission position shift near the spacer was slight, but the shift amount was larger than that of the sample having the second layer. This difference became clearer as the amount of electrons emitted from the electron source increased. At this time, the light emission position shift is a shift from a position to which the beam should be irradiated assuming that the spacer is not charged.

As the cold cathode type electron-emitting device, in addition to the above-mentioned planar type surface-conduction type electron-emitting device, a vertical surface-conduction type electron-emitting device whose sectional film diagram is shown in FIG. 12 can also be used. Field emission electron-emitting devices other than the surface conduction electron-emitting device can also be used.

Note that the shape of the spacer is shown in FIG.
As shown in (a), a shape composed of a plate-like member having a matrix-like opening corresponding to the position of each electron source is also conceivable.
Further, a shape having a linear opening as shown in FIG.

[0215]

As described above, according to the present invention,
A material that is difficult to be charged even if the resistance value is unstable is used as the second layer on the outermost surface with a thickness of 1 nm to 20 nm, and a chemically and physically stable semiconductive film is used as the first layer with a thickness of 10 nm to 10 nm.
By forming the antistatic film into a two-layer structure such that the antistatic film is used at 1 μm, a variation in resistance value is small even after the subsequent heating step, and an antistatic film having a stable resistance value can be obtained.

Further, the antistatic film of the present invention has a specific resistance of 1
Since at 0 ⁸ [Omega] cm or less, it is easy to adjust the surface resistance of the antistatic effect can be obtained, and it has high stability. Further, by applying this antistatic film to the spacer, it is possible to manufacture a display device having no image unevenness.

Further, according to the present invention, the first layer is chemically and
By coating a physically stable semiconductive film with the above film thickness, a stable and appropriate resistance value of the film which is not affected by various factors received during the assembling process can be defined.

On the other hand, the second layer has a lower secondary electron emission efficiency than the material of the first layer and is preferable as an antistatic material. However, since the resistance is low, the second layer has an appropriate resistance as a spacer antistatic film. In this case, a material which must be formed very thin and which is extremely unstable when used alone can be used.

Similarly, a material whose secondary electron emission efficiency is small but whose specific resistance is too high and the charge elimination ability is inferior (the charge elimination speed becomes slower as the resistance value becomes higher) also has the charge elimination function in the first layer. Can be used.

When charging is caused by secondary electron emission, the antistatic ability depends on a material having a depth of about 10 nm from the surface. On the other hand, the ability of static elimination (charge removal) depends on the resistance value of the entire film. Therefore, by separating these functions into two layers, it is possible to produce an antistatic film having higher performance than the conventional single film structure.

[Brief description of the drawings]

FIG. 1 is a perspective view of an image display device according to an embodiment of the present invention, in which a part of a display panel is cut away.

FIG. 2 is a schematic sectional view of an antistatic film of the present invention.

FIG. 3 is a schematic sectional view of another antistatic film of the present invention.

FIG. 4 is a plan view of a substrate of the multi-electron beam source used in the embodiment.

FIG. 5 is a cross-sectional view of a planar surface conduction electron-emitting device used in an example.

FIG. 6 is a plan view illustrating a phosphor array of a face plate of the display panel.

FIG. 7 is a sectional view of a spacer of the display device of the present invention.

FIGS. 8A and 8B are a plan view and a cross-sectional view, respectively, of a planar surface conduction electron-emitting device used in an example.

FIG. 9 is a cross-sectional view showing a manufacturing process of the planar surface conduction electron-emitting device.

FIG. 10 is a waveform chart of an applied voltage in the energization forming process.

FIG. 11 shows an applied voltage waveform (a) during the energization activation process;
The figure which shows the change (b) of emission current Ie.

FIG. 12 is a sectional view of a vertical surface conduction electron-emitting device.

FIG. 13 is a sectional view showing a manufacturing process of the vertical surface conduction electron-emitting device.

FIG. 14 is a graph showing typical characteristics of a surface conduction electron-emitting device used in an example.

FIG. 15 is a block diagram showing a schematic configuration of a driving circuit of the image display device according to the embodiment of the present invention.

FIG. 16 is a diagram showing a change in resistance value between an example and a comparative example.

FIG. 17 is a view showing an example of a conventionally known surface conduction electron-emitting device.

FIG. 18 is a view showing an example of a conventionally known FE element.

FIG. 19 is a view showing an example of a conventionally known MIM type element.

FIG. 20 is a schematic view showing another shape of the spacer.

[Explanation of symbols]

 Reference Signs List 23 Insulating member 24 Antistatic film 25 Alloy nitride film 26 Second layer 27 Alloy oxide film or oxynitride film

Claims (10)

[Claims] A first layer having a thickness of 10 nm on a substrate;
An antistatic film comprising: a 1 μm semiconductive film; and, as a second layer, a layer having a thickness of 1 nm to 20 nm made of a material different from that of the first layer on the surface thereof. 2. The method according to claim 1, wherein the first layer is an alloy nitride film in which at least one type selected from Al, B, and Si and at least one type selected from Cr, Ti, and Ta are combined. Item 7. The antistatic film according to Item 1. 3. The Hf-N, Hf-O, P
3. The antistatic film according to claim 1, wherein the film is any one of t and Au. 4. The antistatic film according to claim 1, further comprising an oxide or oxynitride layer of the alloy at an interface between the first layer and the second layer. . 5. The method according to claim 1, wherein the specific resistance after forming both the first layer and the second layer is 0.1 to 10 ⁸ Ωcm. Antistatic film. 6. A display device having a structure in which a substrate on which a plurality of cold cathode type electron-emitting devices are formed and a transparent substrate on which a light emitting material is formed are opposed to each other via a spacer, wherein the antistatic film is formed of the spacer. The antistatic film according to any one of claims 1 to 5, wherein the antistatic film is formed on a surface. 7. A display device having a structure in which a substrate on which a plurality of cold cathode type electron-emitting devices are formed and a transparent substrate on which a light emitting material is formed are opposed to each other via a spacer. A display device comprising an insulating member coated with the antistatic film according to any one of the preceding claims. 8. The display device according to claim 7, wherein said spacer is electrically connected to a wiring for driving an electron source. 9. The device according to claim 7, wherein the spacer is electrically connected to an emission electron acceleration electrode.
The display device according to the above. 10. The electron emission device according to claim 7, wherein said cold cathode electron emission device is a surface conduction electron emission device.
The display device according to claim 1.