JPH0620590A - Electron emission element, light emission element and image display - Google Patents

Abstract

PURPOSE:To provide an electron emission element used in an electron source which can be made to correspond to enlargement of an image display. CONSTITUTION:Ni and an alloy material of Ni containing 5-20mol% Ag are used in the electrode 2 and surface electrode layer 3 of an electron emission element, respectively, the element being formed inside a vacuum container fabricated by adhesion through heating. The electric heat treatment voltage of the element can then be restrained from rising even at a heating process for sealing, and cracking of a substrate due to partial heating does not take place, so multi-electron emitting elements can be increased in number and used as an electron emission source to correspond to enlargement of an image display.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron-emitting device, particularly a surface-conduction electron-emitting device, a light-emitting device that emits a phosphor by using an electron beam, and an image display device using these.

[0002]

2. Description of the Related Art Conventionally, as a device which can emit electrons with a simple structure, for example, MI Elinson (M.
I. A cold cathode device announced by Elinson et al. Is known [Radio Engineering Electron Physics] (Radio Eng. Elec).
tron. Phys. ) Volume 10, 1290-1296
P. 1965].

This utilizes a phenomenon in which electrons are emitted from a thin film having a small area formed on a substrate by flowing an electric current in parallel with the film surface, and is generally called a surface conduction electron-emitting device. Has been.

As the surface conduction electron-emitting device, one using a SnO ₂ (Sb) thin film developed by Elinson et al., One using an Au thin film [G. Ditmer "Sin Solid Films" (G. Dittme
r: "Thin Solid Films"), 9 volumes, 3
Page 17, (1972)], by ITO thin film [M. Hartwell and CG Fonst (M. Hartwell and CG Fonst)
ad: "IEEE Trans.ED Conf.")
519, (1975)] by carbon thin film [Hiraki Araki et al., "Vacuum", Vol. 26, No. 1, p. 22,
(1983)] and the like are reported.

FIG. 20 shows a typical device configuration of these surface conduction electron-emitting devices. In the figure, 201 and 202 are electrodes for obtaining electrical connection, 203 is a thin film made of an electron emitting material, 204 is a substrate, and 205 is an electron emitting portion.

Conventionally, in these surface conduction electron-emitting devices, an electron-emitting portion is formed in advance by an electric heating process called forming before the electron emission. That is, by applying a voltage between the electrode 201 and the electrode 202, the thin film 203 is energized, and the Joule heat generated thereby locally destroys, deforms or modifies the thin film 203, resulting in an electrically high resistance state. The electron emission unit 205
The electron emission function is obtained by forming the.

Further, as a result of diligent studies, the present inventors have found that a new-type surface conduction electron-emitting device, that is, a surface-conduction type electron-emitting device in which an electron-emitting member is arranged between electrodes and an electron-emitting portion is provided by subjecting it to an electric current treatment. -Shaped electron-emitting devices have been disclosed (Japanese Patent Application Laid-Open Nos. 1-279542 and 1-3207).
No. 25, etc.).

Generally, in the surface conduction electron-emitting device, the electrode spacing between the pair of electrodes 201 and 202 is 0.
01 μm to 100 μm, and the sheet resistance of the electron emission portion is 1 × 10 ³ Ω / □ to 1 × 10 ⁹ Ω / □.

When this device is used as an electron-emitting device, in order to fly an electron beam, 1 × 10 ^-4 to 1 × 1
A vacuum of 0 ^-7 Torr is suitable. That is, the surface conduction electron-emitting device is placed in a vacuum container, a face plate is provided vertically above the device to form an electron-emitting device, a voltage is applied between the electrodes, and an electron beam obtained from the electron-emitting portion is fluorescent. It can be used as a light emitting element or an image display device by emitting light by irradiating the body.

The above-mentioned degree of vacuum is 1 × 10 ⁻⁹ to 1 × 10 ⁻¹⁰ as the degree of vacuum of other cold cathode devices such as field emission devices.
Although it requires about Torr, it can be used in a low vacuum and can be easily manufactured.

FIG. 22 is a view showing an element cross section of this surface conduction electron-emitting device. 221 is a substrate, 222 is electrodes arranged on the substrate, and electrode intervals 224 are close to each other.
Is formed.

Reference numeral 225 denotes an electron emitting material, which is arranged at least within the electrode gap 224. Specifically, for example, a Ni thin film having a thickness of about 1000Å is used as the electrode 222, SnO ₂ or Pd fine particle film is used as the electron emission material 225, glass is used as the substrate 221, and the electrode interval 224 is 2 μm wide.
The length is 300 μm.

Further, a face plate (not shown) having a phosphor and an anode electrode is arranged on the surface facing the element substrate, heated at 450 ° C. for 30 minutes, and melted and sealed with frit glass to form a vacuum container. To make. When a voltage is applied to the electrode interval 224 under a vacuum degree of 1 × 10 ⁻⁵ Torr in this vacuum container, electrons are emitted from the electron emission material 225, and the electrons are accelerated by the acceleration potential of the anode electrode and collide with the phosphor to emit light. Cause

When a voltage is applied to this electron-emitting device, the SnO ₂ or Pd fine particle film, which is the electron-emitting material, is electrically heated at the first voltage application, and the fine particles become islands to form a discontinuous state film. An electron emitting portion is formed. After that, when a voltage of about 14 V is applied to the electrode gap 224, electrons are emitted.

Further, conventionally, as a light emitting element and a flat-panel display device using phosphor light emission by an electron beam, those which emit light by irradiating the phosphor with field emission electrons from the surface of the ultrafine projections have been researched and developed. There is.

As such means, the conventional Infoma
tion Display 1/89 P17-P19
"Advanced technology flat
As described in "cold-cathode CRTs", it has a structure in which ultrafine projections made of metal and a gate electrode for applying a high electric field thereto are arranged close to each other on a substrate with a dimension of 1 μm or less.

In this structure, as shown in FIG. 24, an insulating layer 242 having a thickness of about 3/4 μm is provided on a substrate 241, a gate electrode 243 having an opening having a diameter of about 1 μm is provided thereon, and a metal is used. And the gate electrode 243.
It is arranged at the center of the opening diameter of, and a high electric field is generated by the voltage applied to the gate electrode 243, and an electron flow is generated from the ultrafine protrusion 244.

Further, for the device having such a structure, as shown in FIG.
As shown in FIG. 5, above the substrate 241, via a columnar spacer 252 provided on the substrate or on the counter plate 251,
By disposing the phosphor surface 253 on the facing plate 251, a light emitting element can be obtained. Here, a voltage can be applied to the anode electrode 254, and electrons emitted from the ultra-fine projections 244 can be acceleratedly irradiated onto the phosphor surface 253 to cause the phosphor surface to emit light. In the figure, the phosphor is shown as an ellipse for convenience.

Further, an element having such a structure is shown in FIG.
It is possible to provide a plurality of electron sources to form one screen as shown in FIG. In the figure, 261 is the ultrafine projection 24.
24 is a horizontal scanning electrode connected to the back surface of the No. 4, and FIG.
Is a vertical signal electrode corresponding to the gate electrode 243 of FIG.
Now, when an appropriate voltage is applied to the horizontal scanning electrode 261 and the vertical signal electrode 262, electrons are arbitrarily generated from the ultrafine protrusions 244.
It is selectively released. The emitted electrons are acceleratingly irradiated by applying a voltage to the phosphor surface 253 of the counter plate, which is a vacuum container,
Images can be displayed. In addition, in the vacuum container, the space between the phosphor surface 253 and the ultrafine projections 244 is formed by the spacer 2.
52 to form an atmospheric pressure resistant structure.

The size of the spacer 252 is 50 μm × 50.
If the voltage applied to the phosphor surface 253 is up to 1 kV, the creeping breakdown voltage of the spacer 252 is maintained and abnormal discharge does not occur.

Further, when displaying a color image, FIG.
The phosphor surface 252 of R6 is R (red), G (green), B
The color phosphors of the three primary colors (blue) are separately coated.

At this time, since the color phosphors have different luminous efficiencies, in order to obtain a color image of uniform brightness for each color, the amount of electron beams colliding with each phosphor is determined by the voltage of the horizontal scanning electrode 261 and the vertical signal electrode 262. The drive is complicatedly regulated and controlled.

[0023]

However, as in the above-mentioned conventional example, in order to melt and seal the frit glass at the time of manufacturing the vacuum container, the electron-emitting device is subjected to the sealing heating process at 450 ° C. for about 30 minutes. Therefore, there is a drawback that the voltage is increased until the electric heating treatment of the fine particle film is completed. For example, in the conventional electron-emitting device as shown in FIG. 22, the energization heat treatment voltage was about 5 V when the sealing heating process was not performed, while the energization heating process voltage was about 5 V when the sealing heating process was performed. Raised to 13V and required more power.

When a large number of electron-emitting devices are arranged on the same wiring due to the increase in the heating voltage for energization, the larger the number of arranged electron-emitting devices, the more power is required and the multi-electron-emitting devices are used. It becomes a big problem at the time of manufacturing the image display device and the like. That is, a large power supply is required, the number of electron-emitting devices arranged on the same wiring is limited to the power supply performance limit, and a large amount of power is applied to the device substrate to cause local heating due to Joule heat. The problem is that the substrate cracks.

Further, in order to reduce the rise in the energization heat treatment voltage in the sealing heating step, precise control such as lowering the heating temperature in the sealing heating step and shortening the heating time is performed, but the productivity is improved. Considering the above, a simpler countermeasure is required.

Further, for example, an electron-emitting device of a conventional example as shown in FIG. 20 may be used, particularly 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Tor.
When driven for a long time in a low vacuum of about r, as shown in FIG. 23, the contamination 231 adheres to the positive electrode side and the positive electrode side electrode 201 around the electron emission portion 205, and the contamination 231 expands. The electron emitting portion 205 is filled up,
There is a problem that the amount of electron emission decreases gradually.

In particular, when a plurality of these elements are arranged and a face plate is provided vertically above the elements to form an image forming apparatus, the amount of electron emission decreases within a time period shorter than the durability period required for a normal image display apparatus. As a result, the brightness required for displaying an image cannot be obtained.

Further, in the light emitting device and the image display device as shown in FIGS. 25 and 26, electrons emitted from the ultrafine protrusions 244 are applied to the phosphor surface 253 of the counter plate 251 which is a vacuum container by applying a voltage. The phosphor is emitted by accelerated irradiation. Therefore, it is necessary to dispose the spacer 252 having a withstand voltage against the applied voltage in the vacuum container to form a space and to have an atmospheric pressure resistant structure, and there are the following drawbacks. 1) Spacers with a high withstand voltage are required to have a columnar shape with a high aspect ratio, and the number of manufacturing steps is large. Spacers are formed on these substrates while preventing deterioration of electron-emitting devices such as ultra-fine protrusions or phosphors. Difficult to do. 2) In the color image display device, the color phosphor facing plates, which are separately coated in the three primary colors of red, green and blue, are precisely aligned above the electron-emitting device regions such as the ultrafine protrusions on the corresponding substrates. It must be fixed by sealing, and in a high-definition pixel, a shift easily occurs at the time of sealing and a color shift occurs. 3) In color image display, since the color phosphors of the three primary colors of red, green and blue have different luminous efficiencies, complicated voltage drive control is required to obtain a uniform color image. 4) Since the space between the electron-emitting device and the phosphor is large and the emitted electrons fly and spread, it is difficult to make the bright spot of the light-emitting phosphor extremely small.

As described above, in the light emitting element or the image display device, the manufacturing process is complicated, and it is difficult to realize high definition and large screen.

Therefore, the object of the present invention is to reduce the rise of the energization heat treatment voltage in the sealing heating step, prevent the substrate from cracking due to the treatment, and use it as an electron source corresponding to a large area. It is to provide an electron-emitting device.

Another object of the present invention is to provide an electron-emitting device which does not deteriorate in electron emission characteristics due to aging even when it is driven in a vacuum with a low degree of vacuum.

Still another object of the present invention is to provide a light emitting element which is easy to manufacture and is capable of displaying a high-definition and large-area image, and an image display device using the same.

[0033]

Means and Actions for Solving the Problems In order to achieve the above object, the means constructed in the first aspect of the present invention is such that at least a metal electrode and an electron-emitting material are placed in a vacuum container produced by heat bonding. In a surface conduction electron-emitting device having a substrate arranged thereon, at least a surface electrode layer of the metal electrode is made of an alloy of the metal electrode material, and an oxide of the alloy has an electric conductivity of the metal electrode material alone. That is, the electric conductivity should be higher than that of the oxide.

According to the first aspect of the present invention, when the surface electrode layer of the electrode of the electron-emitting device is made of an oxide, it is made of an alloy metal material having a lower resistance than that of the electrode material alone. Include an alloy in which the electrode material is Ni and the surface electrode layer is laminated with an alloy of Ni and Ag or Li to reduce the increase in the energization heat treatment voltage of the electron-emitting device that has undergone the sealing and heating step of the vacuum container. Furthermore, even if the number of electron-emitting devices arranged on the same wiring is further increased, electric current heating can be performed, and cracking of the substrate due to local heat generation during electric current heating is prevented. It is a thing.

The first aspect of the present invention will be described in detail below.

The following can be considered as one of the causes of the increase in the energization heat treatment voltage of the conventional electron-emitting device. That is, the surface of the electrode that is in contact with the electron emitting material is oxidized by the sealing heat treatment, and the contact resistance increases, so that the voltage rises. At this time, if the electron-emitting material is fine particles and the film thickness is thin and partially discontinuous, the fine-particle film of the electron-emitting material is on the upper layer but the electrode material on the lower layer is subjected to the sealing heat treatment. At times, the degree of oxidation by reacting with oxygen in the atmosphere increases. If the oxide film at the electrode interface is about 100 Å or more, the contact resistance rapidly increases. This increase in resistance lowers the voltage applied to the electron-emitting material during the energization heat treatment, and consequently increases the energization heat treatment voltage. The degree of influence of this increase in contact resistance on the applied heat treatment voltage depends on the electric resistance value of the electron-emitting material. That is, the lower the resistance of the electron-emitting material, the more it is affected by the voltage drop, so that a higher voltage is required as compared with an element whose contact resistance is essentially zero. For example, if the contact resistance value increases and becomes the same as the resistance value of the electron emitting material, the same amount of power as that consumed by the electron emitting material will be consumed in the contact resistance portion. Therefore, the energization heat treatment voltage consumes more than twice as much power as the element without the sealing heat treatment, including the voltage drop due to the wiring resistance.

Next, the first aspect of the present invention will be described with reference to the drawings.

FIG. 1 is a sectional view of an electron-emitting device showing a first embodiment of the present invention.

In the figure, 1 is a substrate made of a glass material, 2 is an electrode made of a thin film, 3 is a surface electrode layer, which is laminated on the electrode 2. The pair of electrodes 2 and the surface electrode layer 3 are arranged with an electrode interval 4. An electron emitting material 5 is arranged on the surface electrode layer in the electrode gap 4 and in the vicinity thereof.

In this embodiment, the surface electrode layer 3 is a metal and an alloy with the electrode material. The specific resistance of the oxide of this alloy is made of a material having a smaller value than the specific resistance when the electrode material alone is oxidized.

For example, when the electrode material is Ni and a Ni alloy containing 10 mol% of Ag is used as the surface electrode layer 3, the surface electrode layer is oxidized by the heat bonding step at the time of sealing the vacuum container, and Ag is oxidized. Even if added NiO, its specific resistance is about 1 Ω · cm. Compared with this, the specific resistance of the ideal stoichiometric oxide film of Ni as the electrode material is 10 ¹³
It exhibits an insulation property of Ω · cm or more, and the deviation from the stoichiometry of Ni and O, which is close to the maximum, is 10 ³ Ω · cm even with Ni _0.995 O, and generally exhibits a high resistance of 10 ⁵ Ω · cm or more. .

As described above, in the case of the electrode material alone, the surface of the electrode is oxidized by the heat-sealing process to increase the resistance. When the electrical conductivity of this oxide film shows, for example, a P-type semiconductor, an N-type semiconductor, or a metal type, the hole concentration, conduction electron concentration, and oxygen ion concentration are increased by adding appropriate additives. The electric conductivity can be increased and the specific resistance can be reduced.

In the first aspect of the present invention, the material of the electrode and the surface electrode layer is 5 to 20 mol in the case of Ni electrode.
% Ag or Li to increase the hole concentration in the P-type semiconductor of the NiO surface layer. Further, in the case of a Zn electrode, one in which 1 to 4 mol% of Al is added to increase the conduction electron concentration in the N-type semiconductor of the ZnO surface layer,
20 mol% of Ca or Gd is added to increase the oxygen ion concentration in the metal type conductive layer of the ZrO ₂ surface layer.
Furthermore, in the case of a Cr electrode, 0.35-1.4 mol
% Ti or 1.25 to 5 mol% Ni to increase the oxygen ion concentration in the metal type conductive layer of the CrO ₂ surface layer to increase the electric conductivity and reduce the specific resistance. .

If the concentration of the metal added as the alloy material is less than the above range, the object of the present invention cannot be sufficiently achieved, and within the above range, the addition amount and the oxide of the alloy are The electric conductivity increases, but when it exceeds the above range, it tends to decrease.

By using the above-mentioned electrode and surface electrode layer material, even if the laminated portion of the electrode surface layer and the fine particle film which is the electron-emitting material is oxidized during the sealing and heating step of the vacuum container, the electrical connection portion is formed. The increase in contact resistance at the interface of the laminated portion can be greatly reduced as compared with the conventional case, and the increase in energization heat treatment voltage can be reduced.

Further, since the Ni electrode material which has been used conventionally can be used, there is also an advantage that it can be used as it is without changing the manufacturing process and driving conditions of the conventional electron-emitting device.

In the first aspect of the present invention, as the method for forming the surface electrode layer, the electrodes are deposited by a vacuum deposition method to a required thickness, and then the alloy metal material is continuously co-evaporated in addition to the electrode material. A method of depositing to the required thickness of the surface electrode layer is used. In addition to this, the electrode is vacuum-deposited, an alloy metal material excluding the electrode material is deposited as an ultrathin film of several tens of liters on the upper layer, and the surface electrode layer is formed by alloying at the temperature during the sealing heating process. This is possible depending on the alloy starting temperature.

Further, it goes without saying that all the electrode materials may be alloys.

Since the first electron-emitting device of the present invention does not cause the substrate to crack due to the electric current heating treatment, a plurality of these can be arranged to form a large-sized electron source, and a face plate is arranged to face this to manufacture an image display device. In this case, a large area image can be displayed.

Next, the second aspect of the present invention made to solve the problem that the electron emission characteristic of the electron-emitting device deteriorates due to the adhesion of contaminants to the electron-emitting portion due to driving in a vacuum of a low vacuum degree. Describe.

That is, according to the second aspect of the present invention, on the insulating substrate having the step portion, the low resistance portion made of the electron-emitting material electrically connected to sandwich the step portion and the low resistance portion are energized. In a surface conduction electron-emitting device in which a pair of electrodes are provided and an electron-emitting portion is formed near the upper surface of the step portion, the electron-emitting portion is formed at a position higher than at least the low resistance portion on the positive electrode side. It is an element.

FIG. 2 is an element configuration diagram showing the second embodiment of the present invention, and FIG. 3 is a sectional view taken along line AA ′ of FIG. In the figure, 21 is a positive electrode, 22 is a negative electrode, and 23
Is an electron emitting material, 24 is an insulating substrate, 25 is a step forming member, 26 is an electron emitting portion, 27 is a step, and 28 is a DC power source.

As shown in the figure, in the second electron-emitting device of the present invention, unlike the conventional electron-emitting device shown in FIGS. 20 and 21, the position of the electron-emitting portion 26 is the position of the positive electrode 21 and the positive electron. It is higher than the emission material.

Since the second electron-emitting device of the present invention has a step between the electrodes similarly to the electron-emitting device disclosed by the present inventors in Japanese Patent Laid-Open No. 2-247940, the shape and position of the electron-emitting portion are accurately designed. Therefore, the electron emission characteristics can be controlled, and the reproducibility of the device can be obtained.

That is, the electron emitting portion is generated in the vicinity of the step portion by the electric heating process, and the direction of the electric current is formed on the upper side, the lower side, or the side surface of the step portion depending on the kind of the particulate material, the thickness of the step, and the like. be able to. In the second aspect of the present invention, among these, the electron emitting portion is provided on the upper side of the step portion, and the voltage is applied by using the electrode positioned on the upper side of the step portion as the negative electrode and the electrode positioned on the lower side as the positive electrode. This prevents the electron emitting portion from being filled with contaminants accumulated on the side electrode.

That is, in the surface conduction type element, as shown in FIG. 4, in the vicinity of the electron emitting portion 26, electrons are emitted at an angle toward the positive electrode side, but a part thereof is emitted from the positive electrode side electrode. The electric field in the direction causes the electric field to drop onto the positive electrode 21.

At this time, in a low vacuum of about 10 ^-5 to 10 ^-4 Torr, it collides with the oil from the exhaust system, which exists in a small amount in the vacuum, and polymerizes or decomposes / accumulates, resulting in contamination.

Therefore, when the electron emission is continued for a long time in the low vacuum, the electron emission portion is filled up as shown in FIG. 23, which causes the electron emission amount to decrease.

In the second aspect of the present invention focusing on this point, the above problem is solved by providing the electron emitting portion at a position higher than at least the low resistance portion made of the electron emitting material on the positive electrode side to which contaminants adhere. .

That is, as shown in FIG. 5, even when the electron emission is continued for a long time in a low vacuum, the contamination 51 has the positive electrode 2 located at a position lower than the electron emission portion.
1 and the low resistance portion on the positive electrode side, the electron emission portion 2
6 is never filled.

As a result, it becomes possible to drive for a long time without lowering the electron emission amount even at a low vacuum degree.

Further, by arranging a plurality of these elements as an electron source,
When an image display device is manufactured using this, a stable bright image can be obtained without lowering the luminance even after long-time driving.

Next, the third light emitting device of the present invention will be described.

In a third aspect of the present invention, at least one electron-emitting device arranged on a substrate, a phosphor that receives irradiation of electrons emitted from the device, and a light-emitting device having a face plate are used. The light-emitting device is arranged so as to cover the electron-emitting portion of the electron-emitting device and has an electrical connection with any of the electrodes forming the electron-emitting device.

The third aspect of the present invention will be described in detail below with reference to the drawings.

FIG. 11 is a cross-sectional view of an element that best represents the third feature of the present invention.

In the figure, 111 is a substrate, and 11
Reference numerals 2a and 2b are electrodes formed on the substrate 111 and facing each other, and 113 is an electrode 1 on one side of the facing electrodes.
An insulating layer formed on 12b and 114 are electron emitting materials made of fine particles. Reference numeral 115 is a spacer made of glass beads and dispersed on the substrate 111, 116 is a face plate for forming a vacuum container, and the space between the substrate 111 and the face plate 116 is kept constant by the spacer 115. There is. Reference numeral 117 denotes a phosphor, which is supported on the substrate 111 and is arranged in a space with the face plate 116 so as to cover the electron emitting portion of the electron emitting material 114. The phosphor 117 is shown as an ellipse for convenience.

The part formed on the substrate 111 by the electrode 112 and the electron-emitting material 114 is called a surface conduction electron-emitting device. In this element, the electrode 11
When a voltage is applied between 2a and 2b, a current flows between the electrodes. When this voltage is set to 10 and several volts, electrons are emitted from the electron emitting portion 114 located between the electrodes. Here, the electron emission angle has various components, and the phosphor 117 is irradiated with and collides with the electron, and the phosphor 117 emits light.

The electrons that have collided with the phosphor 117 are generated by the electrode 11
It flows through 2a and the phosphor does not charge up.

The insulating layer 113 is formed in order to eliminate the leak component of the current flowing by the voltage applied between the electrodes, which is caused by the phosphor 117 arranged between the electrodes.

The electron-emitting device used in the third light-emitting device of the present invention is not limited to the surface conduction electron-emitting device shown in FIG. There are Spindt-type electron-emitting devices that emit electrons by field emission, MIM-type electron-emitting devices that sandwich an insulating layer between metal layers, and emit electrons by applying a voltage.

Further, in the electron-emitting device of the third light-emitting device of the present invention, as in the case of the surface conduction electron-emitting device or the Spindt-type electron-emitting device described above, an electron-emitting portion is formed in an opening such as an electrode gap or a gate electrode opening. In the case of using the element forming the above, it is preferable to use a phosphor having a particle diameter larger than the above-mentioned opening size and to have a minute space between the electron emitting portion and the phosphor.

As a result, the phosphor does not deposit in the opening, and it is possible to reliably eliminate the leak component of the current flowing through the phosphor due to the voltage applied between the electrodes.

In the third aspect of the present invention, the positional relationship between the electron-emitting device and the phosphor is important. Hereinafter, this point will be described.

For example, in the electron emission of the surface conduction electron-emitting device, it is considered that the emitted electron beam also has an energy of about 14 eV at maximum when the voltage between electrodes is 14V. Further, the emission angle of the emitted electron beam is conventionally considered to be emitted in various directions by observing the bright spot shape of a fluorescent plate having an anode electrode located at a certain distance from the emitting element. Therefore, the electrons emitted from the electron emitting portion made of the electron emitting material are emitted at various angles with an energy of about 14 eV, and cover the electron emitting portion to the phosphor disposed on the electrode interval. Irradiate and collide. Here, if the emission threshold voltage of the phosphor is about 10 eV or less, it is possible to sufficiently emit light. As a phosphor corresponding to this, there is a slow electron beam excitation phosphor represented by ZnO: Zn for a fluorescent display tube. The phosphor is arranged in the vicinity of the electron-emitting device so as to cover the electron-emitting device, and this interval can be adjusted by the thickness of the electrodes and the particle size of the phosphor.

Next, in the Spindt-type electron-emitting device, the electron emission is driven, for example, by setting the potential of the ultrafine protrusion to -20V and the potential of the gate electrode to + 20V. Therefore, it is considered that the emitted electron beam has an energy of about 40 eV at maximum. If the conventional light emitting device shown in FIG. 25 does not have the anode electrode, the electron trajectories of the emitted electrons travel along the electric field and collide with the gate electrode. However, even when the Spindt-type electron-emitting device is used as the electron-emitting device of the third light-emitting device of the present invention as shown in FIG. 11, the phosphor covers the gate electrode with the ultrafine projections as the electron-emitting region. , The orbits of the electron beam with which the anode electrode is irradiated cross the phosphor position, and the electron beam irradiates and collides with the phosphor with energy of about 40 eV or less to emit light.

In the conventional slow-electron-beam-excited phosphor described above, in order to suppress the voltage drop of the anode voltage due to the electric resistance of the phosphor, the resistance value of the phosphor layer having a thickness of about 30 μm is 500 Ω / It is as low as cm ² .

Therefore, if the phosphor is electrically connected to the gate electrode, the potential of the phosphor surface, which has a low resistance, becomes close to the gate electrode potential +20 V, and the probability that emitted electrons collide with the phosphor is reduced. It is significantly increased, and light can be emitted more efficiently.

When the MIM type electron-emitting device is used, the phosphor may be arranged on the upper metal layer. Due to the high electric field between the lower metal layer and the upper metal layer, the electrons penetrating the insulating layer and the upper metal layer have sufficient energy to cause the low-acceleration excited phosphor to emit light, and collide with the phosphor,
It can emit light.

In the third light emitting device of the present invention, the size of the bright spot due to the light emission of the phosphor is such that the electron emitting portion and the light emitting phosphor are close to each other, and therefore, the phosphors are arranged corresponding to the length of the electron emitting portion. It is almost the same as the size. Therefore, the electron-electron flight spread, which has occurred when the space between the electron-emitting portion and the light-emitting phosphor is large as in the conventional case, can be extremely suppressed.

Here, it is understood that the electrons may be injected into the phosphor and emit light even when the emission point of the electron is in contact with the phosphor. In particular, in the two-terminal electrode structure related to electron emission, it is possible to emit light even when the electron emission point and the phosphor are in contact with each other. Also, modulation of electron emission and ON
In the case of an electrode configuration of three terminals or more in which an electrode for turning on / off is added, electrical insulation may be partially formed so that no abnormality occurs in the injection of electrons into the phosphor.

Therefore, the third embodiment of the present invention as shown in FIG.
In the light emitting element of
Even when in contact with 7, it is possible to inject electrons into the phosphor and emit light.

Further, according to the third aspect of the present invention, since the phosphor is sandwiched and held between the substrate and the face plate, conventionally, the phosphor is arranged on the facing plate with a space. In this case, the light emission defect caused by the fall of the phosphor, which has occurred in the above case, does not occur.

As described above, since the phosphor is supported and arranged on the element substrate, the large vacuum space up to the counter plate, which is conventionally formed by the columnar spacer, becomes unnecessary, and the necessary phosphor layer is formed. It suffices to form a small vacuum space for the thickness of.

Therefore, in the conventional electron-beam fluorescent light emission type flat image display device, since the pixel defect occurs, the dispersed arrangement of beads or filler-like spacers, which has not been used very actively, should be used without a large pixel defect. You can

That is, assuming that the thickness of the phosphor layer is 20 μm, a glass bead spacer having a diameter of 20 μm may be used. In addition, as an example of the opening size of the electrode portion of the electron-emitting device, in the case of the surface conduction electron-emitting device, when one pixel of the image display device is formed with the electrode interval between the electron-emitting materials being 2 μm wide and 300 μm long, the diameter is 20 μm. Even if the glass bead spacers are dispersedly arranged in the electrode opening, which is the electron emitting portion, about 7% of the electron emission length is left as the non-emitting portion. In the case of the Spindt-type electron-emitting device, when the gate electrode opening has a diameter of 1 μm and one pixel of the image display device has a length of 300 μm and a width of 150 μm and a plurality of electron-emitting devices are arranged in a plane, a glass having a diameter of 20 μm is formed. Even if the bead spacer interferes with the electron emission of the electron-emitting device in the pixel, only 1% or less of the pixel area becomes the non-emission portion. If a glass bead spacer with a diameter of 100 μm is used to form a space of 100 μm as in the conventional example, about 33% of the surface conduction electron-emitting devices and about 18% of the Spindt-type electron emitting devices are not yet occupied in the pixel. Emission part occurs,
It becomes a pixel defect.

Further, in addition to glass beads and filler-like spacers, it is also possible to form thin-film spacers on the substrate with the same thickness as the thickness of the phosphor layer of 20 μm, for example.

Further, in the large screen display device, in order to prevent the driving voltage of the element from decreasing due to the voltage drop of the wiring resistance, the electrode wiring having a large film thickness is used. Here, it is also possible to make the electrode wiring a film thickness of 20 μm to form a low resistance wiring and use this convex wiring portion as it is as a spacer with the face plate. Here, the method of forming the electrode wiring is not limited to the thin film, and a plating method, a printing method or the like is used.

FIG. 17 is a cross-sectional view of an element showing another third embodiment of the present invention.

The third light emitting device of the present invention shown in FIG. 11 does not use the anode electrode provided on the counter plate as shown in the conventional example of FIG. 25, but the light emitting device shown in FIG. Gate electrode 14 having an opening on the electron emission portion 114
2 and the anode electrode 172 are formed on the device electrode 112 via the interlayer insulating layers 141 and 171 respectively.

Further, the face plate 116 and the substrate 111
The inner space of the vacuum container made of is formed by the thickness direction of the anode wiring 173.
Is used as a spacer. Reference numeral 174 is an insulating layer.

When a color image is displayed using the third light emitting device of the present invention as described above, a plurality of types of phosphors are selectively arranged on the anode electrode of each electron-emitting device, and the brightness of each phosphor is adjusted. In order to make the phosphor uniform, it is necessary to control the anode potential suitable for each phosphor. In the present invention, by electrically connecting the anode electrodes on which the same kind of phosphor is arranged and insulating them from the anode electrodes on which different kinds of phosphors are arranged, any anode electrode can be set to any potential. It is also possible to control.

In the third aspect of the present invention, the electrode material is not particularly limited, but it is preferable to use the electrode and surface electrode layer materials described in the first aspect of the present invention. That is, by using an alloy material that has a lower resistance than the electrode material alone when the surface electrode layer of the electrode becomes an oxide, the surface of the electrode that has undergone the sealing and heating step of the vacuum container is oxidized to have a high resistance, This is to prevent poor electrical connection with the phosphor in contact. If the electrical continuity between the phosphor and the electrode is poor, the phosphor may be charged up by the electrons injected from the electron-emitting device, and an overcurrent may temporarily flow, resulting in destruction of the device.

In the third aspect of the present invention, as a method for disposing the phosphor, the fact that the phosphor is arranged on the electron-emitting device is used to electrically drive the electrode of the electron-emitting device to perform electrophoresis. A method of arranging the phosphor on the electron-emitting device by the method can be used. As a result, the phosphors can be separately coated and the color phosphors can be arranged. Further, when the low resistance phosphor is used, the phosphors between the adjacent electron-emitting devices do not come into contact with each other, and the current leakage of the electron-emitting devices through the phosphor can be prevented.

Further, in the case of a high resistance phosphor having a resistance value such that electrons irradiated by the phosphor are allowed to flow as an electric current to the adjacent electrodes connected to the phosphor and the phosphor itself does not charge up, adjacent electron emission is performed. Since the current leakage can be extremely reduced by the phosphor between the elements, the phosphor may be arranged on the entire surface of the substrate. In this case, the placement of the phosphor is performed by using a sedimentation method in which the substrate is left standing in a dispersion solution of the phosphor,
It can be done easily.

As a method for arranging the phosphor, a general method such as a slurry method or a printing method can be used in addition to the above method.

As described above, in the third aspect of the present invention, since the phosphor is arranged on the electron-emitting device substrate, precise alignment between the face plate and the electron-emitting portion on the substrate becomes unnecessary. Further, it becomes possible to make the size of the bright spot of the luminescent phosphor extremely small, and further, to form the vacuum container by a simple method of using the dispersed arrangement of glass beads and the convex portion of the electron-emitting device as a spacer. Therefore, the light emitting element and the image display device can be manufactured by a simpler method, and higher definition and larger area can be achieved.

The luminous efficiency of the phosphor is generally higher as the particle size is larger. However, in view of the quality of the surface on which the phosphor is applied, the diameter of φ5 to 7 μm is actually commercially available.
This size is within a range that can be sufficiently used in the third aspect of the present invention, and it is possible to further increase the particle size to improve the luminous efficiency.

[0099]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 In this example, the first electron-emitting device of the present invention as shown in FIG. 1 was manufactured.

This manufacturing method will be described.

First, a lift-off resist pattern for electrode formation is formed on the substrate 1 made of soda-lime glass material that has been thoroughly washed and degreased by the photolithography method. Next, this substrate 1
Ni, which is an electrode material, was deposited on the upper surface by resistance heating vapor deposition to 700 Å. Ag so that the composition is continuously 10 mol%
Was vapor-deposited with Ni for 300 Å to deposit the electrode 2 and the surface electrode layer 3. After that, the resist pattern was peeled off and the unnecessary deposited film was lifted off to form the electrode gap 4. The electrode interval 4 was 2 μm wide and 300 μm long.

Next, a width of 1 μm was formed between the electrodes and in the vicinity thereof.
The polyimide resist was patterned so as to have openings having a length of 30 μm. 1.0 g of SnO ₂ fine particles was added here to methyl ethyl ketone: cyclohexane = 3: 1 800c
The organic dispersion solution dispersed in c was applied by a spin coater and baked at 250 ° C. for 12 minutes. Next, this polyimide resist was etched to remove unnecessary SnO ₂ fine particles to form a SnO ₂ fine particle film serving as the electron emitting material 5.

The electron-emitting device manufactured as described above was subjected to a current heating treatment by applying a voltage in a vacuum and the result was about 5
Completed with V. Separately from this, the substrate 1 on which the electron-emitting device is formed in order to arrange the present electron-emitting device in the vacuum container.
A face plate having a phosphor was disposed on the anode electrode so as to face the anode with a space interposed therebetween, and the frit glass was melted and adhered in the air by a sealing heating process at 450 ° C. for 30 minutes. After this sealing and heating process, the inside of the vacuum container was evacuated to perform an electric heating process, and the result was about 7
Completed with V. This voltage was almost the same even in the case of the multi electron-emitting device in which 100 electron-emitting devices were arranged in parallel on the wiring.

When an accelerating voltage was applied by an anode electrode (not shown) arranged on the counter plate by applying a voltage of 14 V to the electrode spacing 4 of the present element from the electrode 2, electrons were emitted from the electron emitting material portion and the anode electrode It collided with the upper phosphor (not shown) and emitted light.

At this time, the driving voltage of the electron-emitting device is almost the same as that of the electron-emitting device that emits light in the vacuum chamber without undergoing the above-mentioned sealing and heating process, and an increase in the driving voltage is recognized. There wasn't. Further, the same drive voltage was applied when a plurality of electron-emitting devices were driven.

The Ni electrode of this embodiment is a typical electrode used in the surface conduction electron-emitting device, and the difference from the conventional one is that Ag is added to the surface electrode layer.
Therefore, the element manufacturing process which has been conventionally used can be used as it is.

Further, this device has almost the same characteristics as that of the conventional device in terms of electron emission driving, and can be used similarly to the conventional device.

Example 2 In this example, 700 Å thick Cr was used as the electrode, and 300 Å thick 0.7 mol% Ti-added Cr was used as the surface electrode layer. The other members and the manufacturing method are the same as in the first embodiment. The energization heat treatment voltage of the electron-emitting device of this example was about 8 V, which could be made smaller than the conventional voltage of about 13 V without the surface electrode layer. Also, in the case of a multi electron-emitting device in which 100 electron-emitting devices are arranged in parallel on the wiring, the energization heat treatment voltage is about 8V.
Met.

Example 3 In this example, the second electron-emitting device of the present invention as shown in FIGS. 2 and 3 was produced.

The manufacturing method of this element is as follows. ． The insulating substrate (quartz substrate) 24 is thoroughly washed, and an insulating film serving as a step forming member is formed on this substrate by a vapor deposition technique or a liquid coating method which is usually used. Materials such as SiO ₂ , glass and alumina are suitable as the material, but SiO ₂ was used in this embodiment. Practically, the thickness is preferably 0.1 μm to 1.0 μm, and in this embodiment, it is 0.2 μm. ． Then, the insulator film is etched by a photolitho etching technique which is usually used to form the step forming member 25. ． Next, the electrodes 21 and 22 are formed by using a vapor deposition technique and a photolithographic etching technique. Any material may be used as the material for the electrodes as long as it has conductivity, but in the present embodiment, it was formed using Ni metal. The electrode 21 and the electrode 22 are formed so as to sandwich the step 27, and it is desirable that the electrode interval is practically set to 0.5 μm to 20 μm. In this embodiment, the electrode 21 and the electrode 22 are formed to have a gap of 5 μm. ． Next, fine particles of organic palladium, which is an electron emitting material, are dispersed and applied between the electrodes 21 and 22. As the organic palladium, Okuno Pharmaceutical Co., Ltd. CCP-4230 was used.

A tape or a resist film is provided on a portion where fine particles are not desired to be dispersed, and then organic palladium is applied by a dipping method or a spinner method. Then 1 at 300 ° C
It is fired for a period of time to decompose the organic palladium and form an electron emitting material in which palladium and palladium oxide are mixed. Next, the tape or the resist film was peeled off to form the electron emitting material 23 at a predetermined position. At this time, the diameters of the fine particles of palladium and palladium oxide were both 60Å to 150Å, but the present invention is not limited to this. ． Next, the electrode 22 on the step forming member 25 was connected to the power supply so that the electrode 21 on the quartz substrate 24 was on the positive side, and the electron emitting material 23 was energized. As a result, as shown in FIG. 2, the electron emitting portion 26 could be formed on the step forming member 25 along the step 27.

Here, it is practical that the thickness of the electron-emitting material before the energization treatment is several tens of liters to 200 liters, but the thickness is not limited to this. The sheet resistance of the electron emission material at this time is 1
It is about 0 ³ to 10 ⁸ Ω / □. Further, it is considered that the film thickness of the electron emitting material 23 including the step 27 is substantially uniform between the electrodes.

In this embodiment, the current flow direction is changed from the electrode 21 side to the electrode 22 side in the energization heat treatment, but by setting in this way, the electron emitting portion can be formed at the above-described position with good reproducibility. It was

Further, when the electron-emitting device of this embodiment was connected to the power source as described above and a lead-out electrode was provided vertically above the device to conduct a durability test, as shown in FIG.
It decreased to less than 20% within 1000 hours. On the other hand, as an example of a conventional element, when an element having no step was formed and a voltage was applied in a chamber having a vacuum degree of 1.0 × 10 ⁻⁴ Torr, as shown in FIG. The amount of electron emission has decreased by 60%.

As is clear from these results, the device structure of the present invention was able to reduce the deterioration of the electron emission amount over time.

Further, as the electrodes 21 and 22, the same material as in Example 1 was used, and the same electrode was added to the surface electrode layer of the Ni electrode by the same manufacturing method. As a result, in addition to the above effects, the same effects as in Example 1 were obtained.

Example 4 In this example, a second electron-emitting device of the present invention as shown in FIG. 8 was produced.

FIG. 9 is a sectional view taken along the line A-A 'in FIG.

First, the electrode 2 as shown in FIG. 8 is formed on the insulating substrate 24 by the same method as in the third to third embodiments.
1, 22 and the electron emitting material 23 and the step 25 are provided.

Next, a voltage is applied between the pair of electrodes 21 and 22 to energize the electron emitting material 23, and the electron emitting portion 2
6 was formed.

The electron-emitting device thus formed was placed in a vacuum and a voltage was applied to the extraction electrodes provided between the devices and vertically above the device, and the same results as in Example 3 were obtained. .

Further, as the electrodes 21 and 22, the same material as in Example 1 was used, and the same electrode was added to the surface electrode layer of the Ni electrode by the same manufacturing method. As a result, in addition to the above effects, the same effects as in Example 1 were obtained.

Embodiment 5 FIG. 10 shows an image display apparatus of this embodiment using the second electron-emitting device of the present invention, in which 101 is a grid electrode, 1
02 is an electron passage hole, 106 is a glass plate 103, 104
Of the phosphor, a face plate including a metal back 105, 107 is a bright spot of the phosphor.

Further, the electron sources shown by 21 to 27 are a plurality of the elements of the third embodiment arranged in a line.

In the image display device of this example, a voltage was applied so that the electrode 21 would become a positive electrode in a vacuum having a degree of vacuum of 1 × 10 ⁻⁴ Torr as in the case of Example 3, and electrons were emitted. Similar to Example 3, a bright image was obtained without the brightness decreasing for a long time. Furthermore, since the electron-emitting device of this embodiment has a step, the position and shape of the electron-emitting portion are accurately determined, and the amount of electron emission of each device becomes equal, so that a display screen with uniform brightness was obtained. .

Further, as the electrodes 21 and 22, the same materials as in Example 1 were used, and the same electrode was added to the surface electrode layer of the Ni electrode by the same manufacturing method. As a result, in addition to the above effects, the same effects as in Example 1 were obtained.

Example 6 In this example, the third light emitting device of the present invention as shown in FIG. 11 and an image display device as shown in FIG. 12 were produced using the same.

Hereinafter, a method of manufacturing the light emitting device and the image display device of this embodiment will be described.

First, the thickness is 1.1 mm, which has been thoroughly washed and degreased.
A Ti film having a thickness of 50Å was formed as a subbing layer on the substrate 111 made of the glass material by vacuum evaporation by the lift-off method.

Next, Ni having a thickness of 1000 Å to be the electrodes 112a and 112b and a thickness of 1000 as the insulating layer 113 is formed.
Å SiO ₂ was formed into an electrode shape.

Next, the upper surface of the electrode 112a on the opposite side and the insulating layer in the electrode gap portion were removed by photolithography.

Next, the width between the electrodes 112a and 112b is 2 μm.
An organic Pd solution (Catapaste CCP manufactured by Okuno Chemical Industries Co., Ltd.) was spin-coated at intervals of m by a lift-off method, and baked at 300 ° C. for 12 minutes to form a Pd fine particle film.

Next, IP was used as an electrophoretic electrodeposition solution for the phosphor.
1 g of aluminum nitrate electrolyte was dissolved in 40 l of A (isopropyl alcohol), and Zn having a particle size of about 5 μm was used.
100 g of O: Zn phosphor was dispersed.

The substrate 111 and the electrodeposition counter electrode were dipped in this electrodeposition solution, and a voltage of 15 V was applied between the electrode on the substrate 111 and the electrodeposition counter electrode for 5 minutes to obtain a phosphor by electrophoresis. 117 on the electrode 112a without the insulating layer 113,
Electrodeposition was carried out in the electrode interval and in the vicinity thereof.

Next, the substrate 1 obtained by taking out a dispersion liquid in which glass beads having a particle diameter of about 20 μm are dispersed in IPA from the electrodeposition liquid
It sprayed on 11, and the glass beads 115 were dispersed and arranged.

Next, the face plate 116 is attached to the substrate 11
1 and then, as shown in FIG. 12, the peripheral portion is sealed with frit glass 121 to form a container, and the inside of this container is evacuated to a vacuum of about 10 ⁻⁶ Torr and sealed to form a vacuum container. .

Through the above steps, the light emitting device and the image display device shown in FIGS. 11 and 12 can be obtained.

As described above, in this embodiment, it is not necessary to form and dispose the columnar high aspect ratio spacer between the face plate 116 and the substrate 111, and the light emitting element and the image display device can be manufactured more easily. I was able to.

Electrodes 112a and 11 of the light emitting device of this embodiment
When a voltage of 14 V is applied between 2b, electrons are emitted from the electron emitting material 114 made of fine particles, and the phosphor 117 emits light.

Further, in the image display device of FIG. 12, a voltage is applied between any of the electrodes 112a and 112b arranged in a plurality to selectively cause the phosphor on any electrode interval to emit light. Thus, a flat image display device can be obtained.

Example 7 In this example, a third light emitting device of the present invention as shown in FIG. 13 was produced.

In this figure, the substrate 111, the electrodes 112a,
112b, electron emission material 114, face plate 11
6 and the phosphor 117 are the same as those in the sixth embodiment. Reference numeral 131 denotes an electrode wiring made of a Cu material formed on the electrode 112b by a plating method and having a thickness of about 20 μm. Reference numeral 113 denotes a thickness made of a SiO ₂ material formed by applying and baking a liquid coating material on the electrodes 112b and the electrode wiring 131. About 5000Å
Is an insulating layer.

In this embodiment, the inner space of the vacuum container composed of the face plate 116 and the substrate 111 is the electrode wiring 131.
The electrode wiring 131 is used as a spacer.

After forming the vacuum container, the electrodes 112a, 112
When a voltage of 14 V was applied between points b, the phosphor 117 was able to emit light.

Based on the structure of this embodiment, an image display device was prepared in which an electron-emitting device and a phosphor were arranged on a 300 mm square substrate and the face plate was sealed. At this time,
It was possible to obtain uniform light emission over the entire screen.

Example 8 In this example, a third light emitting device of the present invention as shown in FIG. 14 and an image display device as shown in FIGS. 15 and 16 were produced using the same.

FIG. 14 is a sectional view of the element, and FIGS. 15 and 16 are vertical and horizontal sectional views of the image display device.

In this figure, the substrate 111, the electrodes 112,
The electron emitting material 114, the face plate 116, and the frit glass 121 are the same as those in the sixth embodiment. 141 is SiO
It is an interlayer insulating layer consisting of ₂ materials and having a thickness of about 5 μm.
It is formed on 12 by a vacuum deposition method and a photolithography etching method, and has an opening of 3 μm width on the interval between the electrodes 112. 142 is made of Ni material and has a thickness of about 5000
The gate electrode of Å is formed on the interlayer insulating layer 141 by a vacuum deposition method or a photolithography etching method.
143 is Cu formed on the gate electrode 142 by a plating method
The gate wiring is made of a material and has a thickness of about 20 μm.
Is an insulating layer made of SiO ₂ and having a thickness of about 2000 Å formed on the gate wiring 143 by a vacuum deposition method.
15R, 115G, and 115B are three types of low-speed electron beam excited color phosphors having a particle size of about 7 μm, which were selectively electrodeposited on the gate electrode by the electrophoresis method.

In this embodiment, the internal space of the vacuum container composed of the face plate 116 and the substrate 111 is the gate wiring 14
3 is formed in the thickness direction of the gate wiring 14
3 is used as a spacer.

15 and 16, the electrode 11
2 and the gate electrode 142 respectively connect a plurality of electron-emitting device portions in a line, and a plurality of these are arranged in parallel. The parallel arrangement of the electrode 112 and the gate electrode 142 is orthogonal to each other. Has become.

That is, in FIG. 15, the electrodes 112 are linearly arranged on the left and right in the lateral direction of the drawing, the electron-emitting materials 114 are arranged at three positions, and the electron-emitting device portions 11 at the three positions are arranged.
4 are connected in a line. On the other hand, the gate electrodes are linearly arranged on the electron-emitting device in the back and front in the direction perpendicular to the paper surface, and the gate electrodes adjacent to each other in the lateral direction on the paper surface are not connected.

In FIG. 16, the gate electrode 114 is rotated 90 degrees, and the gate electrodes 114 are arranged on the left and right in the lateral direction of the drawing, and the electrodes 112 are arranged on the back and front in the direction perpendicular to the drawing.

As can be seen from FIG. 15, color phosphors 151R (red), 151G (green) and 151B (blue) are arranged independently of each other. This is because when a fluorescent substance is electrodeposited by an electrophoresis method, a voltage is applied only to an arbitrary gate electrode line in a dispersion liquid of an arbitrary monochromatic color phosphor, and each monochromatic color phosphor is arranged. It has gained.

When a voltage of 14 V is applied to an arbitrary line of the electrode 112 of the present light emitting device, electrons are emitted from the electron emitting device portion connected to this selected line. Here, when -30 V is applied to an arbitrary line of the gate electrode 142 which is orthogonal to this line, emitted electrons cannot reach the phosphor on the electron-emitting device portion at the intersection of the lines, and light emission occurs. Absent. On the contrary, when +30 V is applied to an arbitrary line of the gate electrode 142, the emitted electrons reach the phosphor on the electron-emitting device portion at the intersection of the lines and emit light.
In this way, by applying a voltage to each of the orthogonal lines of the electrode 112 and the gate electrode 142, it is possible to select and display an arbitrary intersection and emission color, and it can be used as a color image display device. .

In this example, 151R (red) was used as the low-speed electron beam excited color phosphor material (Zn _0.2 , Cd
_0.8 ) S: Ag, Cl + In ₂ O ₃ phosphor, 151G
ZnO: Zn phosphor was used as (green) and ZnS: [Zn] + In ₂ O ₃ phosphor was used as 151B (blue).

As described above, in the present embodiment, since any color phosphor can be arranged on the substrate, precise alignment at the time of sealing the face plate and the substrate is unnecessary.

Further, based on the structure of this embodiment, the arrangement pitch of the electron-emitting devices is set to 50 μm in each of the vertical and horizontal directions, and 2
An image display device arranged within a 5 mm square was produced. At this time, there was no color shift with respect to the emission of the color phosphor.

Example 9 In this example, a third light emitting device of the present invention as shown in the device sectional view of FIG. 17 was produced.

In this figure, the substrate 111, the electrode 112, the electron emitting material 114, the face plate 116, the interlayer insulating layer 141, the gate electrode 142, and the color phosphor 117 are the same as in the eighth embodiment. Reference numeral 171 is an interlayer insulating layer made of a SiO ₂ material and having a thickness of about 5 μm, which is formed on the gate electrode 142 by a vacuum deposition method or a photolithography etching method, and has an opening of 4 μm width on the interval between the electrodes 112. . An anode electrode 172 made of Ni material and having a thickness of 5000 Å is formed on the interlayer insulating layer 171 by a vacuum deposition method or a photolithography etching method. Reference numeral 173 is an anode wire made of a Cu material and having a thickness of about 20 μm, which is formed on the anode electrode 172 by a plating method, and 174 is SiO formed on the anode wire 173 by a vacuum deposition method.
It is an insulating layer consisting of ₂ and having a thickness of about 2000Å. In this embodiment, the anode electrode 172 has a common potential of +50 V with respect to all the devices, including the case where a plurality of electron-emitting devices are arranged.

By applying 0 V or +14 V between the electrodes 112 of this element and -30 V or +30 V to the gate electrode 142 in the same manner as in Example 3, the emission of the phosphor is controlled to form a light emitting element and an image display device. I was able to.

In this embodiment, since the potential of the anode electrode 172 connected to the phosphor 117 is + 50V, the
It is considered that the energy of electrons colliding with the phosphor 117 is near 50 eV or less. It suffices that the anode potential is always the common potential and is in the applied state, and ON / OFF control accompanying image display is not necessary. Therefore, it becomes possible to use a phosphor having a higher light emission starting voltage without requiring complicated driving. Furthermore, higher brightness could be obtained with a phosphor having a low emission start voltage.

In the present embodiment, the potential of the anode electrode is made common to a plurality of electron-emitting devices, but it is not limited to this.

For example, when three types of color phosphors were used, it was possible to control the anode potential in accordance with each phosphor in order to make the brightness of each phosphor uniform.

That is, the anode electrode and the anode wiring are formed in a line form on one of the plurality of electron-emitting devices, and the plurality of lines are arranged in parallel. Each color phosphor was electrodeposited by the electrophoresis method and painted separately. In this way, the anode voltage suitable for the color phosphor on each anode electrode line could be applied during driving.

In this case, since the emitted electrons travel in the space surrounded by the interlayer insulating layers 141, 171, the gate electrode 142, and the anode electrode 172 for each phosphor pixel, even if the potentials of the adjacent anode electrodes are different. No electro-optical correction was necessary.

As described above, in the present embodiment, the phosphor emission can be performed in accordance with each phosphor without complicated voltage driving and electro-optical correction.

Further, in the case of monochrome display, if the sedimentation method is used for disposing the phosphor, it can be formed on the insulating layer. Therefore,
When the anode electrode 172 in FIG. 17 is provided as a transparent electrode such as ITO on the inner surface of the face plate 116 on the inner surface of the vacuum container, the potential of the phosphor can be similarly increased to further increase the brightness.

Embodiment 10 In this embodiment, in the third light emitting device of the present invention as shown in the device sectional view of FIG. 17, the anode electrode 172 is replaced by N.
i with 10 mol% Ag added to i with a thickness of 5000Å
An element was produced in the same manner as in Example 9 except that the i alloy was used.

The light emitting device of this example can be driven in the same manner as in Example 9, and since it is a vacuum container,
Heat treatment was carried out at 50 ° C. for 1 hour, and sealing with frit glass was performed. By this heat treatment, the specific resistance of the surface layer of the alloy Ni electrode became about 1 Ω · cm, and sufficient electrical conduction with the phosphor could be obtained.

Further, even when the anode electrode 172 was set to a potential of +50 V, the phosphor was not charged up and an overcurrent did not flow temporarily, and the element was not destroyed due to this.

Further, as the material of the anode electrode 172,
Even when a Cr alloy in which 2.5 mol% of Ni was added to Cr was used, similarly, overcurrent did not flow temporarily.

Furthermore, in the Ni alloy, when the addition amount of Ag is within the range of 5 mol% to 20 mol%, temporary overcurrent does not occur, and the same is true when Li is added within the above range. It was

In addition, in the Cr alloy, even when the addition amount of Ni is within the range of 1.25 mol% to 5 mol% and the addition amount of Ti is within the range of 0.35 mol% to 1.4 mol%, a temporary overcurrent is generated. It never happened.

Example 11 In this example, a third light emitting device of the present invention using a Spindt type electron emission device as shown in the device sectional view of FIG. 18 was produced.

In this figure, 111 is a glass substrate, and 1 is a glass substrate.
Reference numeral 81 is a horizontal scanning electrode made of a stripe-shaped Cr deposited film, 182 is an insulating layer made of a SiO ₂ deposited film, and 183 is a vertical signal electrode made of a Cr deposited film. The vertical signal electrode 183 has an opening with a diameter of about 1 μm by the photolithography etching method, and the insulating layer 182 also has an opening. 184 is an ultrafine protrusion made of Mo obtained by vacuum deposition. In the above configuration, the horizontal scanning electrode 18
By applying a voltage of −20 V to 1 and a voltage of +20 V to the vertical signal electrode 183, electrons are emitted from the ultrafine protrusion 184.

Reference numeral 117 is a low-speed electron beam excitation phosphor containing ZnO: Zn as a main component and having a particle size of 5 to 7 μm, and is arranged on the vertical signal electrode 183 and its opening by the sedimentation method.
Reference numeral 116 is a face plate made of glass, which forms a vacuum container together with the substrate 111.

In the light emitting device of this example, when electrons were emitted from the electron emitting device, the emitted electrons were injected into the phosphor 117 to emit light, which could be observed from the face plate 116 side.

Example 12 In this example, M as shown in the element sectional view of FIG.
A third light emitting device of the present invention using an IM type electron emitting device was produced.

In the figure, 111 is a glass substrate, and 1 is a glass substrate.
Reference numeral 91 is a lower metal layer made of Al deposited by a resistance heating vacuum deposition method, and 192 is an insulating layer made of high density Al ₂ O _{3 obtained} by anodizing Al in a 0.1% H ₃ BO ₄ electrolyte solution at a low growth rate. Is. Before the insulating layer 192 was oxidized, a recess was formed in the central electron emission region 193 by etching, and a step of protecting with a resist during oxidation was added.
The thickness of the insulating layer was made smaller than that of other regions by performing anodic oxidation once. Reference numeral 194 is an upper metal layer made of Au deposited by the resistance heating vacuum deposition method. Each metal 19
1, 194 are formed in a ribbon shape and have a structure orthogonal to each other. In the above structure, the insulating layer 192 has a thickness of 100.
Å, upper metal 194 thickness 100 Å, emission area 193
The electron emission amount was 0.36 μA when the applied voltage was 7.0 V and the diameter was 100 μm.

Reference numeral 117 denotes a ZnO: Zn phosphor, which is arranged on the upper metal layer 194 by the sedimentation method. Reference numeral 116 is a face plate made of glass, which forms a vacuum container together with the substrate 111.

In the light emitting device of this example, when electrons were emitted from the electron emitting device, the emitted electrons were injected into the phosphor 117 to emit light, which could be observed from the face plate 116 side.

[0183]

As described above, in the electron-emitting device according to the first aspect of the present invention in which the surface electrode layer is made of an alloy in which an additive is added to the electrode material, even if the sealing and heating process is performed, the device is turned on. The rise in heat treatment voltage can be suppressed to a small level,
Since the multi-electron emitting device can be implemented with lower power and a large amount of power is not applied to the device substrate, substrate cracking due to local heat generation unlike the conventional case does not occur.

Therefore, it is possible to further increase the number of elements of the multi-electron emitting device, and it can be used as an electron emitting source corresponding to an increase in the area of the image display device.

Furthermore, since it is carried out by an extremely simple structure and method in which the additive is simultaneously deposited at the time of depositing the electrode material, it is not necessary to drastically change the conventional manufacturing process.

Further, in the second electron-emitting device of the present invention in which the electron-emitting portion is formed at a position higher than at least the positive electrode side low-resistance portion, its durability is improved even in a vacuum of low vacuum, and The electron emission characteristics are not deteriorated due to the change.

Further, by forming the step on the substrate, the shape and position of the electron emitting portion can be controlled, and the device has a uniform electron emitting amount.

Further, by arranging a plurality of these elements as an electron source,
In the image display device using this, even if it is driven for a long time, there is no uneven brightness and no decrease in brightness, and a stable bright image can be obtained.

In the third light emitting device of the present invention, the phosphor is arranged on the electron emitting device substrate so as to cover the electron emitting portion,
In the case where the electron-emitting device has a structure having an opening for the electron-emitting portion, the particle size of the phosphor to be arranged is made larger than this opening size, so that the face plate of the vacuum container and the electron-emitting device substrate can be precisely adjusted. Alignment is no longer necessary. Since the distance until the emitted electrons collide with the phosphor, that is, the electro-optical space is extremely small, the spatial spread of the emitted electrons is made extremely small to make the spot size of the bright spot of the phosphor extremely small. It becomes possible to manufacture a high resolution image display device. The electron-optical space is very small, and the flight space of emitted electrons is the space formed by the phosphor film and the electron emission point on the substrate, which eliminates the conventional space between the face plate and the electron-emitting device substrate. Therefore, the spacer only needs to have a function of protecting the structure including the phosphor from the atmospheric pressure, and the spacer height is much smaller than the thickness of the phosphor as compared with the conventional structure, and the structure of the panel is simple. Therefore, the manufacturing is easy. At least the surface electrode layer of the electrode, when it becomes an oxide, by using an alloy material having a lower resistance than the oxide of the electrode material alone, even after undergoing the sealing heating step of the vacuum container, the electrode surface It is possible to prevent an increase in resistance, to sufficiently perform electrical connection between the phosphor and the electrode, and prevent the phosphor from being charged up. The image display device using this element is capable of high-definition and large-area image display.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a first electron-emitting device of the present invention.

FIG. 2 is a perspective view of a second electron-emitting device of the present invention.

3 is a cross-sectional view taken along the line AA ′ of FIG.

FIG. 4 is an explanatory diagram for explaining a state of electron emission.

FIG. 5 is an explanatory view for explaining a situation of contamination deposition when the second electron-emitting device of the present invention is driven.

FIG. 6 is a diagram showing the relationship between the driving time and the amount of emitted electrons of the second electron-emitting device of the present invention.

FIG. 7 is a diagram showing the relationship between the driving time and the amount of emitted electrons of an electron-emitting device of a conventional example.

FIG. 8 is a schematic view showing an embodiment of the second electron-emitting device of the present invention.

9 is a cross-sectional view taken along the line A-A ′ of FIG.

FIG. 10 is a schematic configuration diagram of an image forming apparatus using the second electron-emitting device of the present invention.

FIG. 11 is an element cross-sectional view showing an example of the third light emitting element of the present invention.

FIG. 12 is a cross-sectional view when the device of FIG. 11 is formed in a vacuum container.

FIG. 13 is an element cross-sectional view showing another embodiment of the third light emitting element of the present invention.

FIG. 14 is an element cross-sectional view showing another embodiment of the third light-emitting element of the present invention.

15 is a cross-sectional view of the device of FIG. 14 formed in a vacuum container.

16 is a cross-sectional view of the device of FIG. 14 formed in a vacuum container.

FIG. 17 is an element cross-sectional view showing another embodiment of the third light emitting element of the present invention.

FIG. 18 is an element cross-sectional view showing another embodiment of the third light emitting element of the present invention.

FIG. 19 is an element cross-sectional view showing another embodiment of the third light-emitting element of the present invention.

FIG. 20 is a configuration diagram of a conventional electron-emitting device.

21 is a cross-sectional view taken along the line A-A ′ of FIG.

FIG. 22 is a cross-sectional view of a conventional electron-emitting device.

FIG. 23 is an explanatory diagram for explaining a situation of accumulation of contaminants at the time of driving an electron-emitting device of a conventional example.

FIG. 24 is a cross-sectional view of a conventional electron-emitting device.

FIG. 25 is a cross-sectional view of a conventional light emitting device.

FIG. 26 is a configuration diagram of an image display device using a light emitting element of a conventional example.

[Explanation of symbols]

 1 Substrate 2 Electrode 3 Surface Electrode Layer 4 Electrode Interval 5 Electron Emitting Material 21, 22 Electrode 23 Electron Emitting Material 24 Insulating Substrate 25 Step Forming Member 26 Electron Emitting Section 27 Step Difference 28 Power Supply 51 Contamination 101 Grid Electrode 102 Electron Passing Hole 103 Glass Plate 104 Phosphor 105 Metal back 106 Face plate 107 Phosphor bright spot 111 Substrate 112, 112a, 112b Electrode 113 Insulating layer 114 Electron emitting material 115 Spacer 116 Face plate 117 Phosphor 121 121 Frit glass 131 Electrode wiring 141 Interlayer insulating layer 142 Gate electrode 143 Gate wiring 144 Insulating layer 151R Phosphor (red) 151G Phosphor (green) 151B Phosphor (blue) 171 Interlayer insulating layer 172 Anode electrode 173 Anode wiring 174 Insulating layer 181 Horizontal running Electrode 182 Insulation layer 183 Vertical signal electrode 184 Ultrafine protrusion 191 Lower metal 192 Insulation layer 193 Electron emission region 194 Upper metal 201, 202 Electrode 203 Thin film 204 Electron emission part 205 Substrate 221 Substrate 222 Electrode 224 Electrode spacing 225 Electron emission material 231 Contamination 232 Power source 241 Substrate 242 Insulating layer 243 Gate electrode 244 Ultra fine protrusion 251 Counter plate 252 Spacer 253 Fluorescent substance 254 Anode electrode 261 Horizontal scanning electrode 262 Vertical signal electrode

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoto Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kumi Iwai 3-30-2 Shimomaruko, Ota-ku, Tokyo Kya Non-Incorporated (72) Inventor Toshihiko Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (17)

[Claims] 1. An electron-emitting device comprising a substrate having at least a metal electrode and an electron-emitting material arranged in a vacuum container produced by heat bonding, wherein at least a surface electrode layer of the metal electrode is made of the metal electrode material. An electron-emitting device comprising an alloy, wherein an oxide of the alloy has an electric conductivity higher than that of an oxide of the metal electrode material alone. 2. The electron-emitting device according to claim 1, wherein
The metal electrode is a Ni electrode, and the surface electrode layer is Ni.
An electron-emitting device characterized by being formed of an alloy containing 5 to 20 mol% of Ag or Li. 3. The electron-emitting device according to claim 1,
The metal electrode is a Cr electrode, and the surface electrode layer is Cr.
0.35 to 1.4 mol% Ti or 1.25 to 5 m
An electron-emitting device formed of an alloy containing ol% of Ni. 4. A low resistance portion made of an electron-emitting material, which is electrically connected across the step portion, and a pair of metal electrodes for energizing the low resistance portion are provided on an insulating substrate having the step portion. In the electron-emitting device in which the electron-emitting portion is formed near the upper surface of the step portion, the electron-emitting portion is formed at a position higher than at least the positive electrode side low resistance portion. 5. The electron-emitting device according to claim 4,
The metal electrode is a Ni electrode, and the surface electrode layer is Ni.
An electron-emitting device characterized by being formed of an alloy containing 5 to 20 mol% of Ag or Li. 6. The electron-emitting device according to claim 4,
The metal electrode is a Cr electrode, and the surface electrode layer is Cr.
0.35 to 1.4 mol% Ti or 1.25 to 5 m
An electron-emitting device formed of an alloy containing ol% of Ni. 7. An image display device, characterized in that a face plate is arranged opposite to an electron source in which a plurality of electron-emitting devices according to claim 1 are arranged. 8. In a light emitting device having at least one electron-emitting device arranged on a substrate, a phosphor irradiated with electrons emitted from the device, and a face plate, the phosphor is an electron of the electron-emitting device. A light emitting device, which is arranged so as to cover the emitting portion and has an electrical connection with any of the electrodes forming the electron emitting device. 9. The light emitting device according to claim 8, wherein the electron-emitting device has an opening, and an electron-emitting portion is formed in the opening, and the particle size of the phosphor is the opening. A light emitting device having a size larger than a size and having a space between an electron emitting portion and a phosphor. 10. An electron-emitting device is electrically driven,
The light emitting device according to claim 6 or 7, wherein a phosphor is arranged on the electron emitting device by an electrophoretic method. 11. The light emitting device according to claim 8 or 9, wherein the substrate and the face plate form a vacuum container, and a spacer in the form of beads or filler having a size equivalent to the thickness of the phosphor layer. A light-emitting element characterized in that the elements are dispersed in a vacuum container. 12. The light emitting device according to claim 8, wherein the substrate and the face plate form a vacuum container, and a part of a constituent member of the electron-emitting device is a spacer between the substrate and the face plate. A light-emitting element characterized in that a convex portion is formed. 13. The device according to claim 8, which has a plurality of electron-emitting devices.
Alternatively, in the light-emitting device according to item 9, the electron-emitting device includes an anode electrode having an opening on an electron-emitting portion, and plural kinds of phosphors are selectively arranged on the anode electrode of each electron-emitting device. The light-emitting element characterized in that the anode electrode on which the fluorescent substance is placed is electrically connected and is insulated from the anode electrode on which the different type of fluorescent substance is placed. 14. The light emitting device according to claim 8 or 9, wherein the substrate and the face plate form a vacuum container by heat adhesion, and the electrode having electrical connection with the phosphor is a metal electrode. At least the surface electrode layer of the metal electrode is made of an alloy of the metal electrode material, and the electrical conductivity of the oxide of the alloy is higher than the electrical conductivity of the oxide of the single metal electrode material. . 15. The light emitting device according to claim 14, wherein
The metal electrode is a Ni electrode, and the surface electrode layer is Ni.
A light-emitting element characterized by being formed of an alloy containing 5 to 20 mol% of Ag or Li. 16. The light emitting device according to claim 14, wherein
The metal electrode is a Cr electrode, and the surface electrode layer is Cr.
0.35 to 1.4 mol% Ti or 1.25 to 5 m
A light-emitting element, which is formed of an alloy containing ol% Ni. 17. An image display device for displaying an image using the light emitting device according to claim 8.