JP2010135133A - Manufacturing method of cold cathode electron source, and field emission element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a cold cathode electron source that has a large volume of field emission current flow, under a constant voltage for manufacturing a field emission type flat panel display (FED), a field emission type lamp (FEL), or the like, of a high luminance. <P>SOLUTION: In the manufacturing method of a cold cathode electron source having an electron emission material constituted of a conductive substrate with a metal oxide, such as, titanium oxide on it, and a light containing at least ultraviolet beam is irradiated on the electron emission material. More specifically, a process for activating the electron emission material made of the metal oxide formed on the conductive substrate and a process for irradiating the light containing at least ultraviolet beam on the electron emission material are included. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a cold cathode electron source. The present invention also relates to a field emission device and a field emission light emitting device using a cold cathode electron source, and further relates to a field emission flat panel display (FED), a field emission lamp (FEL) and the like incorporating the field emission light emitting device. The present invention also relates to a method for processing a cold cathode electron source, a field emission method, and a light emission method using field emission.

The cold cathode electron source has an electron emission portion including a conductive substrate and an electron emission material formed on the conductive substrate, and forms an electric field when a voltage is applied between the conductive substrate of the counter electrode and the electron emission material. Releases an electron beam. When the electron beam emitted in this way collides with a phosphor disposed on the conductive substrate side of the counter electrode, the phosphor is excited and emits light, so that it is used for various applications as a light emitting element. Specifically, a field emission flat panel display (FED) is attracting attention as an image display device, and a field emission lamp (FEL) as an illumination device.
The FED is of the same electron beam excitation type as a cathode ray tube (CRT), and can reduce power consumption, be thin, and be miniaturized while maintaining its excellent characteristics. In addition, FEL is not inferior to LED in terms of power consumption, durability, and light emission efficiency, and is also suitable for surface light emission because it is easy to increase the area of the phosphor screen and the electron emission portion. Furthermore, with respect to the emission color, a good white color can be realized by combining many electron beam excited phosphors.

An electron emission material is disposed in the electron emission portion of the cold cathode electron source. As the electron emission material, in addition to carbon nanotubes (CNT), Patent Document 1 discloses a nano-sized inorganic material, specifically, an oxidation material. It has been proposed to use zinc nanotubes and the like. Patent Document 2 proposes to use acicular titanium oxide or the like as an electron emission material.
In order to ensure the characteristics of the electron-emitting material, Patent Document 1 discloses an activation process (including what is generally referred to as a raising process of the electron-emitting material) for peeling off the film formed on the surface of the electron-emitting part. It describes that the material is exposed on the surface of the electron emission portion or is vertically aligned. Patent Document 2 describes that a tape peeling process is performed to peel off the tape attached to the surface of the electron emission portion to form a sparse region and a dense region of the electron emission material, and a high electric field concentration effect is obtained at the boundary. is doing.

JP 2006-120636 A (Claim 1 etc., paragraph 0043) WO2008 / 069243 (claims, etc.)

  Although the electron emission characteristics can be improved by the activation treatment such as tape peeling described in Patent Documents 1 and 2, more field emission current can be produced when applied to a cold cathode electron source in order to produce a brighter light emitting device. (Emission current) is required.

  As a result of studying a method for obtaining a larger field emission current under a constant voltage applied to a cold cathode electron source, the present inventors irradiate a metal oxide used as an electron emission material with light containing at least ultraviolet light. As a result, it was found that a desired field emission current was obtained, and the present invention was completed.

That is, the present invention includes a step of irradiating the electron emitting material with light including at least ultraviolet light in a method of manufacturing a cold cathode electron source having an electron emitting material made of a metal oxide on a conductive substrate. It is a manufacturing method of the cold cathode electron source characterized.
Moreover, it is a field emission device using the cold cathode electron source obtained by the above method.
And a cold cathode electron source having at least an electron emitting material made of a conductive substrate and a metal oxide formed thereon, and a light source for irradiating the electron emitting material with light containing at least ultraviolet light. This is a field emission device.
The field emission light-emitting device includes at least the field emission device described above and a conductive substrate including a phosphor. Specifically, a field emission type using the field emission light-emitting device. Flat panel display, field emission lamp.
Further, at least ultraviolet light is applied to the electron-emitting material before and / or while applying a voltage to a cold cathode electron source having an electron-emitting material composed of a conductive substrate and a metal oxide formed thereon. And a light emitting method using field emission, further comprising: a cold cathode electron source processing method, a field emission method, and a field emission method.

In the present invention, more field emission current can be obtained under a constant voltage applied to the cold cathode electron source by irradiating the electron-emitting material made of metal oxide with light including at least ultraviolet light.
In addition, the present invention provides an electron emission material before and / or while applying a voltage to a cold cathode electron source having an electron emission material comprising a conductive substrate and a metal oxide formed thereon. By irradiating light including at least ultraviolet light, more field emission current can be obtained under a constant voltage. Moreover, sufficient stability and reliability of the electron emission characteristics can be secured.
For this reason, in the field emission light emitting device using the cold cathode electron source, more field emission current flows under a constant voltage, so that even higher brightness can be obtained, and further, the area can be increased. Can be easily applied, and can be applied to field emission flat panel displays, field emission lamps, and the like.

  The present invention relates to a method for manufacturing a cold cathode electron source having an electron emission material made of a metal oxide on a conductive substrate, and the light containing at least ultraviolet light in the metal oxide that becomes the electron emission material at any stage. A method of manufacturing a cold cathode electron source, comprising the step of irradiating

The step of irradiating the metal oxide serving as the electron-emitting material with light containing at least ultraviolet light can be performed, for example, in at least one of the following steps (1) to (3). From the viewpoint of light irradiation efficiency, (2) or (3) is preferable, and (3) is more preferable. The light to irradiate should just contain the ultraviolet light of wavelength 400nm or less, and may contain visible light, infrared light, etc. in addition to that. Light irradiation intensity, irradiation time, and the like can be set as appropriate. Specifically, the irradiation intensity is appropriately about 1 × 10 ⁻⁶ to 1 × 10 ³ W per 1 cm ^{2 of} the electron emission material. In the case of (1) and (2), the irradiation time is suitably about 1 minute to 10 hours. Furthermore, in the case of (3), it can be appropriately performed intermittently or continuously during one period of field emission or the entire time of field emission. The reason why a large amount of field emission current can be obtained under a constant voltage when the metal oxide is irradiated with light containing at least ultraviolet light is not clear, but the metal oxide itself has conductivity or the photocatalytic action of the metal oxide. It is thought that the effect of decomposing / removing the substances adhering to the surface due to the above is affected.
(1) A step of manufacturing a metal oxide to be an electron emission material (2) After a step of forming an electron emission portion including an electron emission material made of a metal oxide on a conductive substrate, the electron emission material is described later. Stage before activation treatment, stage of activation treatment, or stage after activation treatment (3) Electrons including an electron-emitting material composed of a conductive substrate and a metal oxide formed thereon After producing a cold cathode electron source having an emission part, before applying a voltage to the cold cathode electron source, or applying a voltage.

  The cold cathode electron source has an electron emission portion including a conductive substrate and an electron emission material formed thereon. In the present invention, a known metal oxide having electron emission characteristics can be used as the electron emission material, and for example, titanium oxide, tin oxide, zinc oxide, silicon oxide, and the like can be used. The metal oxide can be produced by a conventionally known method. When irradiation with light containing at least ultraviolet light is performed in the step (1), the metal oxide is produced or the metal oxide is produced. During the process, for example, at least one of the production reaction process, the drying process, the baking process, and the pulverization process can be irradiated with light containing at least ultraviolet light. Of the metal oxides, titanium oxide and tin oxide are preferable since they have excellent electron emission characteristics and can be manufactured at low cost. Titanium oxide is known in the form of rutile, anatase, or brookite as its crystal form, but any crystal form can be used. Tin oxide can also be used in any crystal form.

  The particle shape of the metal oxide is preferably an anisotropic shape such as a needle shape, a rod shape, a column shape, a plate shape, a nanotube, or a nanowire, and more preferably a needle shape, but a shape having a small anisotropy such as a granular shape. It doesn't matter. Moreover, there is no restriction | limiting in particular also in the magnitude | size of particle | grains, The thing of the range of several nm-30 micrometers can be used. Acicular titanium oxide and acicular tin oxide are preferable because they are excellent in electron emission characteristics and can be manufactured at low cost. As the acicular titanium oxide, known ones can be used, and the average minor axis diameter is 0.1 to 1.0 μm, the average major axis diameter is 1.0 to 15.0 μm, and the axial ratio (major axis diameter / short axis). (Axial diameter) is preferably in the range of 10-20. As the acicular tin oxide, known ones can be used, and the particle diameter thereof is an average minor axis diameter of 0.005 to 0.050 μm, an average major axis diameter of 0.1 to 5.0 μm, and an axial ratio (long (Axis diameter / minor axis diameter) is preferably in the range of 20-100. The acicular titanium oxide and acicular tin oxide include a shape called a rod shape or a column shape in addition to a needle shape.

  The metal oxide is preferably a conductive material, and more preferably acicular conductive titanium oxide and / or acicular conductive tin oxide. The needle-like conductive titanium oxide and needle-like conductive tin oxide include needle-like shapes as well as rod-like or columnar shapes. When volume resistance is used as the conductivity index, a range of at most 1000 Ωcm is preferable, and a range of 0.01 to 100 Ωcm is more preferable. Conductive titanium oxide is obtained by conducting a conductive treatment on titanium dioxide, for example, titanium oxide having a conductive coating layer such as low-order titanium oxide, titanium oxynitride, antimony-containing tin oxide, phosphorus-containing tin oxide, etc. The acicular conductive titanium oxide is obtained by subjecting acicular titanium dioxide to a conductive treatment. The particle diameter of the acicular conductive titanium oxide has an average minor axis diameter of 0.1 to 1.0 μm, an average major axis diameter of 1.0 to 15.0 μm, and an axial ratio (major axis diameter / minor axis diameter). A range of 10-20 is preferred. The conductive tin oxide may be a known one obtained by doping the above tin oxide with antimony, phosphorus or the like, and the acicular conductive tin oxide is obtained by using the above acicular tin oxide. The particle diameter of acicular conductive tin oxide is an average minor axis diameter of 0.005 to 0.050 μm, an average major axis diameter of 0.1 to 5.0 μm, and an axial ratio (major axis diameter / minor axis diameter) is 20. A range of ˜100 is preferred.

  Next, an electron emission portion including an electron emission material made of the metal oxide is formed on a conductive substrate, and an activation process is performed as necessary to form a cold cathode electron source. In order to form the electron emission portion, a flowable composition containing an electron emission material is applied on a conductive substrate, the electron emission material is dispersed in an arbitrary solution, and the substrate is submerged in the dispersion and left to stand. Thus, known methods such as a method of sedimentation by sedimentation on a substrate (precipitation method) and an electrophoretic deposition method can be used, but the method of applying the fluid composition is simple and preferable. As the conductive substrate, a known material such as ITO glass (indium-doped tin oxide-coated glass) or a metal Al plate can be used. Further, a conductive plastic substrate such as a conductive metal oxide such as conductive titanium oxide or conductive tin oxide or a metal such as aluminum, gold, silver, or copper is used as a conductive substrate. Such a plastic substrate is more preferable because it can be applied to flexible applications.

  In the method of applying the flowable composition, the flowable composition is prepared by dispersing the electron-emitting material in an arbitrary solvent. The flowable composition includes compositions in a paste state, an ink state, a paint state, a dispersed state, and the like, and can be adjusted to a suitable viscosity according to a coating method. The solvent is not particularly limited, and examples thereof include water, toluene, terpineol, butyl carbitol, butyl carbitol acetate, methyl isobutyl ketone, methyl ethyl ketone, cyclohexane, anisole, N-methyl-2-pyrrolidone, n-butanol, isopropanol, and acetonitrile. Used.

  In addition, a dispersant may be added to the fluid composition in order to disperse the electron emission material in a solvent, and a resin may be added to adjust the viscosity and improve the coating property. As such resins, known resins such as acrylic resins, cellulose resins, alkyd resins, melamine resins, and epoxy resins can be widely used. However, acrylic resins that decompose at a relatively low temperature because they need to be removed by heat treatment. It is more preferable to use a resin, a cellulose resin, or the like. The resin content is appropriately adjusted because the suitable viscosity varies depending on the coating method. Moreover, in order to improve the electroconductivity of a composition, you may mix electroconductive substances, such as a metal microparticle and electroconductive carbon. These additives are not particularly limited, and those used for preparing ordinary organic paints may be used, and the addition ratio can be appropriately set according to the type and amount of the electron-emitting material to be used.

In addition, by adding an immobilization substance to the fluid composition, a part of the electron emission material of the electron emission portion and the substrate are bound by the immobilization substance, and the electron emission portion is charged during operation. For example, it can be prevented from being peeled off, and a stable field emission current can be provided for a long time. Examples of the immobilizing substance include glass compositions such as glass powder, colloidal silica, and alkyl silicate, and nanoparticles, sols of metals, metal oxides, and complexes, and glass compositions are preferable. In particular, when a glass composition is used, the addition amount is preferably 1 to 500 parts by weight in terms of SiO ₂ with respect to 100 parts by weight of the electron emission material. When glass powder is used, those having a softening point of 300 to 600 ° C. and an average particle diameter of 0.1 to 5 μm can be used. The addition ratio of the electron emission material and the immobilization substance is not particularly limited, and is appropriately determined experimentally according to the type of the electron emission material and the immobilization substance.

  The application method of the fluid composition is not particularly limited, and any method such as screen printing, spray printing, dip method, spin coating method, doctor blade method, and applicator method may be used. When using screen printing, applicator method, etc., it can be used up to relatively high viscosity, so the total solid content in the flowable composition, that is, the total solid content of the electron emission material, the immobilizing substance, etc. The fluid composition preferably contains about 1 to 70% by weight. On the other hand, when spray printing or the like is used, one having a low viscosity can be applied, and the total solid content in the flowable composition is preferably about 1 to 30% by weight. By applying the fluid composition in this manner, a layer containing an electron-emitting material can be formed on the conductive substrate. However, the layer may be dried as needed after the application, and before the activation treatment In order to remove the resin or the like in advance, it may be fired as necessary. Although this baking temperature can be set suitably, for example, 100-1000 degreeC is preferable, More preferably, it is 200-600 degreeC. As the firing atmosphere, air, inert gas such as nitrogen gas, vacuum, or the like can be used.

  After forming the electron emission portion including the electron emission material, the electron emission material is preferably activated. This activation process is a process of forming a so-called electron emission site in the electron emission part, and in addition to forming a new part contributing to electron emission, a part not contributing to electron emission or a part adversely affected is removed. Including that. The part that does not contribute to electron emission here is, for example, impurities, electron emission materials arranged in a direction different from the direction of the applied electric field, even if arranged in the electric field direction, they are dense and hinder electric field concentration. It refers to the electron emission material. Specifically, by the activation treatment, the electron emission material can be exposed on the surface of the layer, or can be vertically aligned (also referred to as raising treatment), and a sparse region and a dense region of the electron emission material can be formed. As such an activation treatment, a treatment for peeling the polyimide film or the like formed on the surface of the layer, a tape peeling treatment for removing the tape attached to the surface of the layer, a treatment for mechanically polishing the layer, an electrode surface on the layer A process of applying a high electric field in a direction perpendicular to the direction, a process of irradiating a layer with laser light, and the like can be applied, and two or more of these processes may be combined.

  The film is formed and peeled by applying a paint containing a film-forming agent such as a polyimide polymer to the surface of the layer, heating to form a film on the layer surface, and then applying pressure as necessary, , Peel the film. In the tape peeling treatment, a polymer tape is applied to the surface of the layer, and then pressure is applied as necessary, and then the tape is peeled off. The mechanical polishing process is a process of polishing the layer surface with a polishing machine.

  In the high electric field application treatment, a conductive substrate is placed on the opposite side with a certain distance from the conductive substrate and vacuum-sealed, and then a high electric field is applied therebetween. The electric field application direction at this time is not particularly specified. The electric field strength is preferably 8 V / μm or more, more preferably a pulse high electric field having a pulse width of 5 to 2000 μs and a repetition frequency of 1 to 1000 Hz. When titanium oxide having a high dielectric constant is used as an electron emission material, it is preferable because interaction with an electric field can be further strengthened. Further, in a high electric field application process, a minute sparse region can be obtained by peeling off a part of the layer also by causing a weak discharge. The application time can be set as appropriate.

The irradiation process with laser light is a process of irradiating the layer with laser light, and the wavelength of the laser light used is preferably 248 nm KrF excimer laser. The energy density of the laser beam is 10 to 200 mJ / cm ² , the pulse width is 5 to 20 ns, the pulse repetition frequency is 1 to 100 Hz, and the power density at this time is 0.1 to 20 MW / cm ² , more preferably 0. 0.7 to 8.6 MW / cm ² , more preferably 3 to 7 MW / cm ² . The irradiation time can be set as appropriate.

In the case of performing irradiation of light including at least ultraviolet light in the step (2), after forming an electron emission portion including an electron emission material made of a metal oxide on a conductive substrate, the following Can be done in order.
(A) The activation treatment is performed after irradiation with light containing at least ultraviolet light.
(B) Irradiation of light including at least ultraviolet light is performed at the stage of performing the activation treatment.
(C) After performing the activation treatment, irradiation with light including at least ultraviolet light is performed.

  In the case of performing irradiation of light including at least ultraviolet light in the step (3), a cold cathode electron source having an electron emission material composed of a conductive substrate and a metal oxide formed thereon, and a counter electrode A conductive substrate is placed and vacuum sealed. Irradiation of light including at least ultraviolet light can be performed at a stage before applying a voltage and / or at a stage of applying a voltage, and is intermittently performed at one stage of applying the voltage or at the entire time of field emission. It is preferable to carry out appropriately or continuously.

  The cold cathode electron source of the present invention can be produced by irradiating the metal oxide serving as the electron emission material with light containing at least ultraviolet light in any one of steps (1) to (3). In addition, using the cold cathode electron source, a conductive substrate as a counter electrode can be disposed and vacuum sealed to obtain a field emission device. As the conductive substrate for the counter electrode, a known material such as ITO glass (indium-doped tin oxide-coated glass) or metal Al plate can be used as described above. In this field emission device, the cold cathode electron source side is a cathode electrode, the counter electrode side is an anode electrode, and an electron beam is emitted from the electron emission material when a voltage is applied between them. As the electron-emitting material used for the field emission device, the above metal oxide can be used, but an activated metal oxide is preferable, and titanium oxide is more preferable. Furthermore, the cold cathode electron source, the counter conductive substrate, and the phosphor formed thereon may be disposed and vacuum sealed to form a field emission light emitting device. As the phosphor, a known material such as ZnO can be used. Moreover, in order to ensure the electroconductivity of a fluorescent substance and to raise the reflectance of light, the fluorescent film surface may be equipped with electroconductive vapor deposition films, such as metal Al and metal Zn. Using the field emission light-emitting element, a field emission flat panel display (FED) or a field emission lamp (FEL) can be obtained. The FEL can easily perform dimming of the lamp by adjusting the driving voltage and the pulse width and, if necessary, forming a gate electrode between the electrodes.

  Furthermore, as another invention, at least a cold cathode electron source having an electron emission material comprising a conductive substrate and a metal oxide formed thereon, and a light source for irradiating the electron emission material with light containing at least ultraviolet light To provide a field emission device. Since this field emission device is provided with a light source, light containing at least ultraviolet light can be irradiated in the step (3). For this reason, at least one of the above-mentioned (1) and (2) may be irradiated with light containing at least ultraviolet light to the metal oxide serving as the electron-emitting material. It is not necessary to perform. As the electron-emitting material used for the field emission device, the above-described metal oxide can be used, but an activated metal oxide is preferable, and titanium oxide is more preferable. Further, the cold cathode electron source, the light source for irradiating the electron emission material with light including at least ultraviolet light, the conductive substrate of the counter electrode, and the phosphor formed thereon are vacuum-sealed and field emission is performed. It can also be set as a light emitting element. As the phosphor, a known material such as ZnO can be used. Moreover, in order to ensure the electroconductivity of a fluorescent substance and to raise the reflectance of light, the fluorescent film surface may be equipped with electroconductive vapor deposition films, such as metal Al and metal Zn. Using the field emission light-emitting element, a field emission flat panel display (FED) or a field emission lamp (FEL) can be obtained. The FEL can easily perform dimming of the lamp by adjusting the driving voltage and the pulse width and, if necessary, forming a gate electrode between the electrodes.

  Furthermore, as another invention, (A) a cold cathode electron source having an electron emission material composed of a conductive substrate and a metal oxide formed thereon, and / or while applying a voltage, By irradiating the electron-emitting material with light containing at least ultraviolet light, a process for increasing the field emission current of the electron-emitting material can be performed. Similarly, (B) electron emission before and / or while applying a voltage to a cold cathode electron source having an electron-emitting material made of a conductive substrate and a metal oxide formed thereon. By irradiating the material with light including at least ultraviolet light, a high field emission current can be obtained. Further, (C) before applying voltage to the cold cathode electron source having an electron emission material made of a conductive substrate and a metal oxide formed thereon, and a conductive substrate having a phosphor, and / or voltage By irradiating the electron-emitting material with light including at least ultraviolet light while applying a voltage, a high field emission current can be obtained and light can be emitted. In the above methods (A), (B), and (C), the time of irradiation with light including at least ultraviolet light is appropriately or intermittently performed at one time of field emission or the entire time of field emission. Is preferred.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

Example 1
A titanium oxide (FTL-100, manufactured by Ishihara Sangyo), which has an average major axis diameter of 1.68 μm and an average minor axis diameter of 0.13 μm, is mixed with an organic solvent and an organic resin to form a paste. It was applied to. Since the paste contains an organic solvent and an organic resin, the paste was baked at 500 ° C. for 1 hour in a nitrogen atmosphere to remove it.
An ITO glass substrate was placed in parallel with the obtained acicular titanium oxide layer at an interval of 125 μm. A power source was connected so that the acicular titanium oxide layer was a cathode electrode and the opposing ITO glass substrate was an anode electrode, and vacuum sealed to 10 ⁻⁵ Pa. An activation treatment was performed by applying a pulse high electric field of 3.5 kV, 60 Hz, 1/100 Duty Ratio between the obtained electrodes for 5 seconds. In this way, a cold cathode electron source (sample A) was obtained.

It was confirmed that electron emission started when voltage was applied to Sample A. When the current due to the emitted electrons was measured, it was 2 × 10 ⁻⁵ mA / cm ² at 1 kV. Next, when black light is used as a light source and 75 μW / cm ² of ultraviolet light is applied to the acicular titanium oxide layer from the top of the opposing ITO glass substrate, the current value reaches 1.8 × 10 ⁻⁴ mA / cm ^2. Rose. Moreover, it was found that the current value was maintained even when the irradiation with ultraviolet light was stopped (see FIG. 1). From this result, it was found that the field emission current of the cold cathode electron source can be improved in the field emission device by irradiating light including ultraviolet light.
Further, the opposing ITO glass substrate was replaced with an ITO glass substrate coated with ZnO phosphor, and vacuum-sealed in the same manner to obtain a field emission light emitting device (sample B). It was confirmed that when a voltage was applied to Sample B, the phosphor film emitted light and electron emission started. Next, when black light was used as a light source and 75 μW / cm ² of ultraviolet light was applied to the acicular titanium oxide layer from the top of the ITO glass substrate coated with ZnO phosphor, 1.8 × 10 ⁻⁴ mA / The current value increased to cm ² . In addition, it was found that the current value was maintained even when the irradiation with ultraviolet light was stopped. From this result, it was found that the field emission current of the cold cathode electron source can be improved in the field emission light emitting device by irradiating light including ultraviolet light.

  From this embodiment, since the field emission current of the cold cathode electron source of the present invention is improved, the cold cathode electron source of the present invention is a field emission flat panel display (FED), a field emission lamp (FEL), etc. It was found that it can be used for a light emitting element.

  Since the cold cathode electron source of the present invention can obtain a large amount of field emission current under a constant voltage, it is preferably used for a field emission device and a field emission light emitting device. Specifically, a field emission type flat panel display, It is suitably used for a field emission lamp.

FIG. 3 is a diagram showing a field emission current of Sample A obtained in Example 1.

Claims (14)

  A method for manufacturing a cold cathode electron source having an electron emission material made of a metal oxide on a conductive substrate, comprising the step of irradiating the electron emission material with light containing at least ultraviolet light. Source manufacturing method.   Forming an electron-emitting material made of a metal oxide on a conductive substrate, then activating the electron-emitting material, and irradiating the electron-emitting material with light containing at least ultraviolet light The manufacturing method of the cold cathode electron source of Claim 1 characterized by the above-mentioned.   Light containing at least ultraviolet light in the electron emission material before and / or while applying a voltage to a cold cathode electron source having an electron emission material comprising a conductive substrate and a metal oxide formed thereon. The manufacturing method of the cold cathode electron source of Claim 1 characterized by the above-mentioned.   The method for producing a cold cathode electron source according to any one of claims 1 to 3, wherein the metal oxide is titanium oxide.   A field emission device using a cold cathode electron source manufactured by the method according to claim 1.   A cold cathode electron source having at least an electroconductive substrate and an electron emission material made of a metal oxide formed thereon, and a light source for irradiating the electron emission material with light including at least ultraviolet light. Field emission device.   7. The field emission device according to claim 5, wherein the electron emission material is an activated metal oxide.   The field emission device according to any one of claims 5 to 7, wherein the metal oxide is titanium oxide.   A field emission light-emitting device comprising at least the field emission device according to claim 5 and a conductive substrate including a phosphor.   A field emission flat panel display using the field emission light emitting device according to claim 9.   A field emission lamp using the field emission light emitting device according to claim 9.   Light containing at least ultraviolet light in the electron emission material before and / or while applying a voltage to a cold cathode electron source having an electron emission material comprising a conductive substrate and a metal oxide formed thereon. The processing method of the cold cathode electron source characterized by irradiating.   Light containing at least ultraviolet light in the electron emission material before and / or while applying a voltage to a cold cathode electron source having an electron emission material comprising a conductive substrate and a metal oxide formed thereon. A method of field emission, characterized by irradiating.   Before and / or while applying a voltage to a cold cathode electron source having an electron emission material composed of a conductive substrate and a metal oxide formed thereon, and a conductive substrate with a phosphor, A light emission method by field emission, wherein the electron emission material is irradiated with light including at least ultraviolet light.

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