JP4917121B2 - Electron-emitting device, electron-emitting device, self-luminous device, image display device, cooling device, and charging device - Google Patents

Description

  The present invention relates to an electron-emitting device that emits electrons by applying a voltage.

  As a conventional electron-emitting device, a Spindt type electrode, a carbon nanotube (CNT) type electrode, and the like are known. Such an electron-emitting device has been studied for application in the field of FED (Field Emission Display), for example. In such an electron-emitting device, a voltage is applied to the sharp portion to form a strong electric field of about 1 GV / m, and electrons are emitted by the tunnel effect.

  However, since these two types of electron-emitting devices have a strong electric field in the vicinity of the surface of the electron-emitting region, the emitted electrons easily obtain a large energy by the electric field and easily ionize gas molecules. There is a problem that cations generated by ionization of gas molecules are accelerated and collided in the direction of the surface of the device by a strong electric field, and device destruction occurs due to sputtering. In addition, since oxygen in the atmosphere has lower dissociation energy than ionization energy, ozone is generated prior to the generation of ions. Since ozone is harmful to the human body and oxidizes various things with its strong oxidizing power, there is a problem of damaging members around the element. To avoid this, the surrounding members are ozone resistant. There is a restriction that high material must be used.

  Therefore, MIM (Metal Insulator Metal) type and MIS (Metal Insulator Semiconductor) type electron emitting devices are known as other types of electron emitting devices. These are surface emission type electron-emitting devices that use the quantum size effect and strong electric field inside the device to accelerate electrons and emit electrons from the planar device surface. Since these emit electrons accelerated inside the device, a strong electric field is not required outside the device. Therefore, the MIM type and MIS type electron-emitting devices have a problem that they are destroyed by sputtering due to ionization of gas molecules, and ozone is generated, like the Spindt-type, CNT-type, and BN-type electron-emitting devices. Can be overcome.

  For example, in Patent Document 1, an insulator film in which fine particles such as metal are dispersed between two electrodes is provided as an electron acceleration layer, electrons are injected from one electrode into the electron acceleration layer, and the injected electrons are injected. An MIM type electron-emitting device that is accelerated by an electron acceleration layer and emits electrons through the other electrode is disclosed. In Patent Document 1, this thickness is set to several tens to 1000 mm.

JP-A-1-298623 (published on December 1, 1991)

  In general, it is difficult to uniformly disperse fine particles of several nm to several hundred nm in a solvent and a solid. Therefore, in the conventional MIM type electron-emitting device in which the insulator film includes metal fine particles as the electron acceleration layer, the dispersion state of the metal fine particles is not uniform. The uneven distribution of the metal fine particles is a cause of shortening the lifetime of the element. If the dispersion state of the metal fine particles is not uniform, aggregates of the metal fine particles are likely to be present in the insulator film, and if the metal fine particle aggregates are present in the insulator film, they are electrically conductive when a voltage is applied to the element. This is because a path is easily formed and dielectric breakdown is likely to occur. Therefore, the lifetime of the device using the conventional electron-emitting device is shortened. Further, for example, when a conventional electron-emitting device is applied to a display, if the dispersion state of the metal fine particles is not uniform, luminance unevenness occurs.

  The present invention has been made in view of the above problems, and an object thereof is to provide an electron-emitting device in which conductive fine particles are uniformly dispersed in an electron acceleration layer and can stably emit electrons for a long period of time.

  In order to solve the above problems, an electron-emitting device of the present invention has an electrode substrate, a thin film electrode, the electrode substrate, and an electron acceleration layer sandwiched between the thin film electrode, the electrode substrate, the thin film electrode, When the voltage is applied between them, the electron accelerating layer accelerates the electrons and emits the electrons from the thin film electrode. The electron accelerating layer includes conductive fine particles and the conductive fine particles. Insulating fine particles having a primary average particle size larger than the primary average particle size are included, and the average particle size of the aggregates of the conductive fine particles in the electron acceleration layer is 0.35 μm or less. It is said.

  According to the above configuration, the electron acceleration layer including the conductive fine particles and the insulating fine particles having a primary average particle size larger than the primary average particle size of the conductive fine particles is provided between the electrode substrate and the thin film electrode. This electron acceleration layer is a layer in which insulator fine particles and conductive fine particles are densely assembled, and has semiconductivity. When a voltage is applied to the semiconductive electron acceleration layer, a current flows in the electron acceleration layer, and a part thereof is emitted as ballistic electrons by the strong electric field formed by the applied voltage. Here, the average particle diameter of the aggregate of the conductive fine particles in the electron acceleration layer is 0.35 μm or less. The average particle diameter of the aggregate of the conductive fine particles is larger than the primary average particle diameter of the conductive fine particles, but when it is 0.35 μm or less, as will be understood from the examples described later, the electron acceleration layer In this case, a large aggregate that causes breakdown is not formed, and it can be said that the conductive fine particles are uniformly dispersed in the electron acceleration layer.

  Conventionally, the conductive fine particles could not be uniformly dispersed in the electron acceleration layer. However, in the electron-emitting device according to the present invention, as described above, the conductive fine particles are uniformly dispersed in the electron acceleration layer, so that the device can have a long life and can stably emit electrons for a long time. .

  In the electron-emitting device of the present invention, in addition to the above configuration, the conductive fine particles may be a conductor having high anti-oxidation power.

  Here, the high antioxidant power mentioned here indicates that the oxide formation reaction is low. In general, the larger the negative value ΔG [kJ / mol] value of the oxide formation free energy obtained by thermodynamic calculation, the easier the oxide formation reaction occurs. In the present invention, a metal element corresponding to ΔG> −450 [kJ / mol] or more corresponds to conductive fine particles having a high antioxidant power. In addition, the conductive fine particles in a state in which the formation reaction of oxides is less likely to occur by attaching or covering an insulating material smaller than the particle size of the conductive fine particles around the corresponding conductive fine particles also have an antioxidant power. Is contained in highly conductive fine particles.

  According to the above configuration, since the conductive material having high antioxidation power is used as the conductive fine particles, it is difficult for the device to deteriorate due to oxidation by oxygen in the atmosphere, so that the electron-emitting device can be operated stably even at atmospheric pressure. it can. Therefore, the lifetime can be extended and continuous operation can be performed for a long time even in the atmosphere.

  In the electron-emitting device of the present invention, in addition to the above configuration, the conductive fine particles may be a noble metal. As described above, since the conductive fine particles are precious metals, it is possible to prevent element deterioration such as oxidation of the conductive fine particles by oxygen in the atmosphere. Therefore, the lifetime of the electron-emitting device can be extended.

  In the electron-emitting device of the present invention, in addition to the above-described configuration, the conductive fine particles must be smaller than the size of the insulator material because of the need to control conductivity, and the primary average particle size of the conductive fine particles is 3 It is preferably 10 nm. Thus, by setting the primary average particle size of the conductive fine particles to be smaller than that of the insulator material, preferably 3 to 10 nm, a conductive path by the conductive fine particles is not formed in the electron acceleration layer, and electron acceleration is performed. Dielectric breakdown is less likely to occur in the layer. Although there are many unclear points in principle, ballistic electrons are efficiently generated by using conductive fine particles having a particle diameter within the above range.

  Here, the insulating fine particles preferably have an average particle diameter of 10 to 1000 nm, and more preferably 12 to 110 nm. In this case, the dispersion state of the particle size may be broad with respect to the average particle size. For example, fine particles having an average particle size of 50 nm may have a particle size distribution in the region of 20 to 100 nm. By making the average particle size of the insulating material, which is the fine particles, preferably 10 to 1000 nm, more preferably 12 to 110 nm, heat can be efficiently transferred from the inside of the conductive fine particles smaller than the size of the insulating material to the outside. By conducting, Joule heat generated when a current flows in the device can be efficiently released, and the electron-emitting device can be prevented from being destroyed by heat. Furthermore, the resistance value in the electron acceleration layer can be easily adjusted.

  In order to solve the above problems, the method for manufacturing an electron-emitting device according to the present invention includes an electrode substrate, a thin film electrode, and the conductive fine particles and the primary average particle diameter of the conductive fine particles sandwiched between the electrode substrate and the thin film electrode. An electron acceleration layer including insulator fine particles having a large primary average particle diameter, and when a voltage is applied between the electrode substrate and the thin film electrode, electrons are accelerated in the electron acceleration layer, A method of manufacturing an electron-emitting device that emits the electrons from the thin film electrode, wherein the electron acceleration layer is formed on the electrode substrate using the nanocolloid liquid of the conductive fine particles in a liquid state. It is characterized by including steps.

  According to the above method, the electron acceleration layer is formed using a nano colloid liquid of conductive fine particles in a liquid state. Here, in the device manufacturing process, when dry-up conductive fine particles are used, since they are aggregated, it is difficult to re-disperse in the solvent to near the primary particle size. Even when conductive fine particles existing in a dispersed state in a solvent are used, mixing with another solvent generally degrades the dispersion stability and causes aggregation. Accordingly, the aggregated conductive fine particles having a large particle diameter are dispersed in the electron acceleration layer, and dielectric breakdown is likely to occur.

  However, in the above method according to the present invention, since the nanocolloid liquid is used in a liquid state, an electron acceleration layer in which conductive fine particles are uniformly dispersed can be formed. Therefore, in the above method according to the present invention, the device can have a long lifetime, electrons can be stably emitted for a long period of time, and the electron emission current can be increased.

  Here, the conductive fine particles preferably have an average particle size in a colloidal state of 0.35 μm or less. By using conductive fine particles having an average particle size of 0.35 μm or less in a colloidal state, the dispersibility of the conductive fine particles in the electron acceleration layer can be enhanced.

  In the method for manufacturing an electron-emitting device according to the present invention, in addition to the above method, in the electron acceleration layer forming step, a nanocolloid liquid of the conductive fine particles and a solvent in which the insulating fine particles are dispersed are mixed, You may apply to.

  According to the above method, the electron acceleration layer in which the conductive fine particles are uniformly dispersed can be easily formed by mixing the nano colloid liquid of the conductive fine particles and the solvent in which the insulator fine particles are dispersed.

  In order to solve the above-described problems, an electron-emitting device of the present invention includes any one of the above-described electron-emitting devices and a power supply unit that applies a voltage between the electrode substrate and the thin-film electrode. It is a feature.

  According to the above configuration, the conductive fine particles are uniformly dispersed in the electron acceleration layer, and the electron emission device can stably emit electrons for a long period of time.

  Furthermore, by using the electron-emitting device of the present invention for a self-luminous device and an image display apparatus equipped with the self-luminous device, surface emission with a long life that can stably emit electrons with reduced luminance unevenness is realized. A self-luminous device and an image display device can be provided.

  Further, by using the electron-emitting device of the present invention in which the conductive fine particles are made of a metal having high anti-oxidation power for a cooling device, electrons can be stably emitted for a long period of time in the atmosphere and cooling can be performed with high efficiency.

  In addition, by using the electron-emitting device of the present invention using a metal having high anti-oxidation power for the conductive fine particles in a charging device, it is possible to stably discharge electrons in the air for a long period of time to charge a charged object.

  In the electron-emitting device of the present invention, as described above, the electron acceleration layer includes conductive fine particles and an insulating material larger than the primary average particle diameter of the conductive fine particles. When fine particle aggregates are included, the average particle size of the aggregates is 0.35 μm or less.

  According to the above configuration, the electron acceleration layer including the conductive fine particles and the insulating material larger than the primary average particle diameter of the conductive fine particles is provided between the electrode substrate and the thin film electrode. It is a layer in which insulator fine particles and conductive fine particles are densely gathered and has semiconductivity. When a voltage is applied to the semiconductive electron acceleration layer, a current flows in the electron acceleration layer, and a part thereof is emitted as ballistic electrons by the strong electric field formed by the applied voltage. Here, the average particle diameter of the aggregate of the conductive fine particles in the electron acceleration layer is 0.35 μm or less. The average particle diameter of the aggregate of the conductive fine particles is larger than the primary average particle diameter of the conductive fine particles, but when it is 0.35 μm or less, as will be understood from the examples described later, the electron acceleration layer It cannot be said that a large agglomerate enough to cause dielectric breakdown is formed, and the conductive fine particles are uniformly dispersed.

  Conventionally, the conductive fine particles could not be uniformly dispersed in the electron acceleration layer. However, in the electron-emitting device according to the present invention, as described above, the conductive fine particles are uniformly dispersed in the electron acceleration layer, so that the device can have a long life and stably emit electrons for a long time. It becomes possible.

It is a schematic diagram which shows the structure of the electron-emitting element of one Embodiment of this invention. FIG. 2 is an enlarged view of a cross section in the vicinity of a fine particle layer in the electron-emitting device of FIG. 1. It is a TEM photograph of an electron-emitting device and shows that conductive fine particles are uniformly dispersed. It is a TEM photograph of an electron-emitting device and is a diagram showing that conductive fine particles are dispersed unevenly. It is a figure which shows the measurement system of an electron emission experiment. It is a figure which shows the light emission experimental device of an electron emission element. It is a figure which shows the upper surface photograph of the light emission experimental apparatus of an electron emission element. It is a figure which shows the result of the light emission experiment with the fluorescent substance of the electron-emitting element of an Example. It is a figure which shows the distribution measurement result of the particle size in the electroconductive fine particles of the electron-emitting element of an Example. It is a figure which shows the result of the light emission experiment with the fluorescent substance of the electron-emitting element of another Example. It is a figure which shows the distribution measurement result of the particle size in the electroconductive fine particles of the electron-emitting element of another Example. It is a figure which shows the distribution measurement result of the particle size in the electroconductive fine particles of the electron-emitting element of a comparative example. It is a figure which shows an example of the charging device using the electron-emitting element of this invention. It is a figure which shows an example of the self-light-emitting device using the electron-emitting element of this invention. It is a figure which shows another example of the self-light-emitting device using the electron-emitting element of this invention. It is a figure which shows another example of the self-light-emitting device using the electron-emitting element of this invention. It is a figure which shows another example of the image forming apparatus which comprises the self-light-emitting device using the electron-emitting element of this invention. It is a figure which shows an example of the air blower using the electron-emitting element which concerns on this invention, and a cooling device provided with the same. It is a figure which shows another example of the air blower using the electron-emitting element of this invention, and a cooling device provided with the same.

  Hereinafter, embodiments and examples of the electron-emitting device of the present invention will be specifically described with reference to FIGS. Note that the embodiments and examples described below are merely specific examples of the present invention, and the present invention is not limited thereto.

[Embodiment 1]
FIG. 1 is a schematic diagram showing the configuration of an embodiment of an electron-emitting device of the present invention. As shown in FIG. 1, an electron-emitting device 1 of this embodiment includes a substrate (electrode substrate) 2 that serves as a lower electrode, an upper electrode (thin film electrode) 3, and an electron acceleration layer 4 that is sandwiched therebetween. Consists of. In addition, the substrate 2 and the upper electrode 3 are connected to a power source 7 so that a voltage can be applied between the substrate 2 and the upper electrode 3 arranged to face each other. The electron-emitting device 1 applies a voltage between the substrate 2 and the upper electrode 3, thereby causing a current to flow between the substrate 2 and the upper electrode 3, that is, the electron acceleration layer 4. The upper electrode 3 is transmitted or emitted from the gap between the upper electrodes 3 as ballistic electrons by the strong electric field formed by The electron emission device 10 is composed of the electron emission element 1 and the power source 7.

  The substrate 2 serving as the lower electrode serves as a support for the electron-emitting device. Therefore, any material can be used without particular limitation as long as it has a certain degree of strength, has good adhesion to a directly contacting substance, and has appropriate conductivity. Examples thereof include metal substrates such as SUS, Ti, and Cu, semiconductor substrates such as Si, Ge, and GaAs, insulator substrates such as glass substrates, and plastic substrates. For example, if an insulating substrate such as a glass substrate is used, a conductive material such as a metal is attached to the interface with the electron acceleration layer 4 as an electrode, so that the substrate 2 can be used as a lower electrode. . The conductive material is not particularly limited as long as a noble metal material excellent in conductivity can be formed into a thin film using magnetron sputtering or the like. An ITO thin film widely used for transparent electrodes is also useful as an oxide conductive material. In addition, for example, a metal thin film in which a Ti film is formed to 200 nm on a glass substrate surface and a Cu film is further formed to a 1000 nm thickness may be used in that a tough thin film can be formed. Never happen.

  The upper electrode 3 applies a voltage in the electron acceleration layer 4. Therefore, any material that can be applied with voltage can be used without particular limitation. However, from the standpoint that electrons accelerated and become high energy in the electron acceleration layer 4 are transmitted with as little energy loss as possible and emitted, a material having a low work function and capable of forming a thin film is higher. The effect can be expected. Examples of such a material include gold, silver, carbon, tungsten, titanium, aluminum, palladium, and the like whose work function corresponds to 4 to 5 eV. In particular, assuming operation at atmospheric pressure, gold without oxide and sulfide formation reaction is the best material. In addition, silver, palladium, tungsten, and the like, which have a relatively small oxide formation reaction, are materials that can withstand actual use without problems. The film thickness of the upper electrode 3 is important as a condition for efficiently emitting electrons from the electron-emitting device 1 to the outside, and is preferably in the range of 10 to 55 nm. The minimum film thickness for causing the upper electrode 3 to function as a planar electrode is 10 nm. If the film thickness is less than this, electrical conduction cannot be ensured. On the other hand, the maximum film thickness for emitting electrons from the electron-emitting device 1 to the outside is 55 nm. If the film thickness exceeds this, no ballistic electrons are transmitted, and the upper electrode 3 accelerates electrons by absorbing or reflecting ballistic electrons. Recapture into layer 4 will occur. Therefore, when the film thickness of the upper electrode 3 is in the range of 10 to 55 nm, the electron-emitting device 1 ensures electrical continuity and allows a sufficient current in the device to flow, and stably emits ballistic electrons from the upper electrode 3. It becomes possible to make it.

  The electron acceleration layer 4 includes conductive fine particles 6 and insulating fine particles 5 having a primary average particle size larger than the primary average particle size of the conductive fine particles. In the electron acceleration layer 4, the conductive fine particles are uniformly dispersed, and the particle diameter of the aggregate of the conductive fine particles is 0.35 μm or less. In the present embodiment, since the electron acceleration layer 4 includes the insulating fine particles 5 and the conductive fine particles 6, the electron acceleration layer 4 is hereinafter referred to as a fine particle layer 4.

  As the conductive fine particles 6, any type of conductor can be used on the principle of operation of generating ballistic electrons. However, if a conductor having a high anti-oxidation power is used, oxidative deterioration when operating at atmospheric pressure can be avoided. Examples of the conductor having a high anti-oxidation power include noble metals, specifically, materials such as gold, silver, platinum, palladium, and nickel, and the conductive fine particles may be metal fine particles. Such conductive fine particles 6 can be prepared using a known fine particle production technique such as sputtering or spray heating, and also use commercially available metal fine particle powders such as silver nanoparticles produced and sold by Applied Nano Laboratory. Is possible. The principle of ballistic electron generation will be described later.

  Here, the primary average particle diameter of the conductive fine particles 6 must be smaller than the size of the insulating fine particles 5 described below, and more preferably 3 to 10 nm, because it is necessary to control the conductivity. Thus, by setting the primary average particle diameter of the conductive fine particles 6 to be smaller than the particle diameter of the insulating fine particles 5, preferably 3 to 10 nm, a conductive path by the conductive fine particles 6 is formed in the fine particle layer 4. Therefore, dielectric breakdown in the fine particle layer 4 is less likely to occur. Although there are many unclear points in principle, ballistic electrons are efficiently generated by using the conductive fine particles 6 having a particle diameter in the above range. The average particle size of the conductive fine particles 6 can be measured using, for example, Microtrac 9340-UPA (manufactured by Nikkiso Co., Ltd.) after dispersing the conductive fine particles in an appropriate concentration in a dispersion medium.

  Further, as shown in FIG. 3, the conductive fine particles 6 are uniformly dispersed in the fine particle layer 4. Here, uniformly dispersed means that the average particle diameter of the aggregates of the conductive fine particles 6 in the fine particle layer 4 is 0.35 μm or less, as can be seen from the examples described later. The average particle diameter of the aggregate of the conductive fine particles 6 is larger than the primary average particle diameter of the conductive fine particles 6, but when it is 0.35 μm or less, as will be understood from the examples described later, the electron acceleration layer It can be said that the large aggregates that cause dielectric breakdown are not formed, and the conductive fine particles 6 are uniformly dispersed.

  Here, as shown in FIG. 4, when the dispersion state of the conductive fine particles in the electron acceleration layer (fine particle layer) is non-uniform and aggregation of the conductive fine particles exists in the fine particle layer, when a voltage is applied to the element, Conductive paths are easily formed, and dielectric breakdown tends to occur. However, as described above, since the conductive fine particles 6 are uniformly dispersed in the electron acceleration layer (in the fine particle layer 4), the electron-emitting device 1 can achieve a long life of the device, and the electrons can be used for a long time. It can be released stably. 3 and 4 are diagrams showing TEM photographs. In the TEM observation, the upper part of the fine particle layer 4 is embedded with a resin and peeled off from the substrate 2 for observation. Therefore, in FIGS. 3 and 4, the substrate 2 is not included, and the region where the substrate 2 was present is shown as the substrate region.

  An insulating material smaller than the primary average particle diameter of the conductive fine particles 6 may be present around the conductive fine particles 6, and the insulating material smaller than the primary average particle diameter of the conductive fine particles 6 The attached substance may adhere to the surface, and the attached substance may be an insulating film that coats the surface of the conductive fine particle 6 as an aggregate having a shape smaller than the primary average particle diameter of the conductive fine particle 6. As the insulator material smaller than the primary average particle diameter of the conductive fine particles 6, any insulator material can be used on the operation principle of generating ballistic electrons. However, when the insulating material smaller than the primary average particle diameter of the conductive fine particles 6 is an insulating film that coats the conductive fine particles 6, and the insulating film is covered by the oxide film of the conductive fine particles 6, the oxide film is caused by oxidative degradation in the atmosphere. In order to avoid oxidative deterioration when operated at atmospheric pressure, an insulating film made of an organic material is preferable. For example, alcoholate, fatty acid, alkanethiol, etc. Materials. It can be said that the thinner the insulating coating, the more advantageous.

  As for the insulating fine particles 5, any material can be used without particular limitation as long as it has insulating properties. However, the weight ratio of the insulating fine particles 5 to the whole fine particles constituting the fine particle layer 4 is preferably 80 to 95%. By setting the weight ratio of the conductive fine particles 6 in the fine particle layer (electron acceleration layer) 4 to 30% or less, a high resistance and thin film semiconductive layer can be formed, and the fine particle layer (electron acceleration layer) in which dielectric breakdown does not occur. ) 4 can be realized.

The size of the insulating fine particles 5 is preferably larger than the primary average particle size of the conductive fine particles 6 in order to obtain a heat radiation effect superior to that of the conductive fine particles 6, and the diameter of the insulating fine particles 5 (primary average particle size). ) Is preferably 10 to 1000 nm, more preferably 12 to 110 nm. Therefore, the material of the insulator fine particles 5 is practically SiO ₂ , Al ₂ O ₃ , TiO ₂ . However, using small-sized silica particles with surface treatment increases the surface area of the silica particles in the solvent and increases the solution viscosity compared to using spherical silica particles with a larger particle diameter. Therefore, the film thickness of the fine particle layer 4 tends to increase slightly. The material of the insulating fine particles 5 may be fine particles made of an organic polymer. For example, highly crosslinked fine particles (SX8743) made of styrene / divinylbenzene manufactured and sold by JSR Corporation, or manufactured by Nippon Paint Corporation. The fine sphere series of styrene / acrylic fine particles to be sold is available. Here, the insulating fine particles 5 may use two or more kinds of different particles, may use particles having different particle size peaks, or have a single particle and a broad distribution of particle sizes. May be used.

  The thinner the fine particle layer 4 is, the stronger the electric field is applied, so that electrons can be accelerated by applying a low voltage, but the layer thickness can be made uniform, and the resistance of the electron acceleration layer in the layer thickness direction can be adjusted. The layer thickness of the fine particle layer 4 is preferably 0.5 to 3 μm because electrons can be emitted even if the aggregate of the conductive fine particles 6 (average particle size 0.35 μm or less) is included.

  Next, the principle of electron emission will be described. FIG. 2 is an enlarged schematic view of the cross section in the vicinity of the fine particle layer 4 of the electron-emitting device 1. As shown in FIG. 2, most of the fine particle layer 4 is composed of insulating fine particles 5, and conductive fine particles 6 are scattered in the gaps. The ratio between the insulating fine particles 5 and the conductive fine particles 6 in FIG. 2 is such that the weight ratio of the insulating fine particles 5 to the total weight of the insulating fine particles 5 and the conductive fine particles 6 corresponds to 80%. The conductive fine particles 6 adhering to the hit are about six particles.

  Since the fine particle layer 4 is composed of the insulating fine particles 5 and a small number of conductive fine particles 6, it has semiconductivity. Therefore, when a voltage is applied to the fine particle layer 4, a very weak current flows. The voltage-current characteristics of the fine particle layer 4 show so-called varistor characteristics, and the current value is rapidly increased as the applied voltage increases. A part of this current becomes ballistic electrons due to the strong electric field in the fine particle layer 4 formed by the applied voltage, and is transmitted through the upper electrode 3 or passes through the gap and emitted to the outside of the electron-emitting device 1. The formation process of ballistic electrons is thought to be due to electrons tunneling while being accelerated in the direction of the electric field, but it has not been determined.

  Next, an embodiment of a manufacturing method of the electron-emitting device 1 will be described. First, a dispersion liquid in which the insulating fine particles 5 and the conductive fine particles 6 are dispersed is applied on the substrate 2 by using, for example, a spin coating method to form the fine particle layer 4. Here, the dispersion is prepared by mixing and dispersing the solvent in which the insulating fine particles 5 are dispersed and the nanocolloid liquid of the conductive fine particles 6. The nano colloid liquid of the conductive fine particles 6 is mixed in a liquid state.

  Thus, when the nano colloid liquid of the conductive fine particles 6 is used in a liquid state, the fine particle layer 4 in which the conductive fine particles 6 are uniformly dispersed can be formed. The conductive fine particles 6 preferably have an average particle size in a colloidal state of 0.35 μm or less. By using conductive fine particles having an average particle size in the colloidal state of 0.35 μm or less, the dispersibility in the fine particle layer 4 can be enhanced as described in Examples described later.

  Examples of the nano colloid liquid of the conductive fine particles 6 include gold nano particle colloid liquid manufactured and sold by Harima Kasei Co., Ltd., silver nano particles manufactured and sold by Applied Nano Laboratory, and platinum nano manufactured and sold by Tokuru Chemical Laboratory Co., Ltd. Examples thereof include a particle colloid solution and a palladium nanoparticle colloid solution, and a nickel nanoparticle paste manufactured and sold by IOX Co., Ltd.

  In addition, the solvent of the nano colloid liquid of the conductive fine particles 6 can be used without particular limitation as long as the insulating fine particles 5 can be dispersed and dried after coating. For example, toluene, benzene, xylene, hexane, tetradecane, etc. are used. be able to. Similarly, the solvent in which the insulating fine particles 5 are dispersed can be used without particular limitation as long as the conductive fine particles 6 can be dispersed and dried after coating. For example, toluene, benzene, xylene, hexane, tetradecane, and the like can be used. .

  The fine particle layer 4 can be made to have a predetermined film thickness by repeating the film formation by the spin coating method and drying a plurality of times. The fine particle layer 4 can be formed by a method such as a dropping method or a spray coating method in addition to the spin coating method.

  Further, the fine particle layer 4 may be formed as follows. A solvent in which the insulating fine particles 5 are dispersed is applied onto the substrate 2 by using, for example, a spin coating method to form an insulating fine particle layer. Thereafter, the nano colloid liquid of the conductive fine particles 6 may be added to the insulator fine particle layer in a liquid state to form the fine particle layer 4. When formed in this manner, the nano colloid liquid of the conductive fine particles 6 penetrates into the insulating fine particle layer, and the conductive fine particles 6 are uniformly dispersed. Therefore, the conductive fine particles can be prevented from aggregating with the solvent in which the insulating fine particles are dispersed, and the fine particle layer 4 in which the conductive fine particles 6 are uniformly dispersed can be formed. In addition to the spin coating method, for example, a method such as an electrostatic spraying method or an ink jet method can be used as a method for adding the nanocolloid liquid.

  After forming the fine particle layer 4, the upper electrode 3 is formed on the fine particle layer 4. For example, magnetron sputtering may be used to form the upper electrode 3. Further, the upper electrode 3 may be formed by using, for example, an inkjet method, a spin coating method, a vapor deposition method, or the like.

(Example)
In this example, an electron emission experiment, a light emission experiment, and a particle size distribution measurement using the electron-emitting device according to the present invention will be described with reference to FIGS. These experiments and the like are examples of implementation and do not limit the contents of the present invention. First, the electron-emitting devices of Examples 1 and 2 and the electron-emitting device of Comparative Example 1 were produced as follows. First, a method for manufacturing the electron-emitting devices of Examples 1 and 2 will be described.

Example 1
The electron-emitting device of Example 1 was manufactured as follows. First, 3 mL of hexane solvent is put into a 10 mL reagent bottle, and 0.5 g of spherical silica particles having an average particle diameter of 110 nm are placed therein as insulator fine particles 5, and the reagent bottle is placed in an ultrasonic disperser to disperse the silica particles. went. Next, silver nanoparticle colloid liquid manufactured by Applied Nanoparticles Laboratory as conductive fine particles 6 (primary average particle diameter of silver nanoparticles 4.5 nm (manufacturer measurement data at the time of delivery), hexane dispersion solution with a solid content concentration of 37%) Was added in an amount of 0.125 g (solid content weight) in the liquid state, and ultrasonic dispersion treatment was similarly performed to obtain a fine particle dispersion A. The weight ratio of the insulating fine particles 5 to the total mass of the insulating fine particles 5 and the conductive fine particles 6 in the fine particle dispersion A was 80%.

Then, the fine particle dispersion A was deposited on a 30 mm square SUS substrate as the substrate 2 by using a spin coating method to form the fine particle layer 4. The film forming condition by the spin coating method was that after the dispersion solution A was dropped onto the substrate 2, the substrate 2 was rotated at 500 RPM for 5 seconds, and subsequently at 3000 rpm for 10 seconds. This film forming condition was performed once, and a single layer was deposited on the substrate 2 and then naturally dried at room temperature. The film thickness of the fine particle layer 4 was about 1000 nm. The upper electrode 3 was formed on the surface of the fine particle layer 4 by using a magnetron sputtering apparatus, whereby the electron-emitting device of Example 1 was obtained. Gold was used as the film forming material for the upper electrode 3, and the layer thickness (surface electrode film thickness) of the upper electrode 3 was 40 nm. Moreover, the area was set to 0.07 cm < ² > by using the mask of a circular hole with a diameter of 3 mm.

(Example 2)
The electron-emitting device of Example 2 was manufactured in the same manner as the electron-emitting device of Example 1. However, Example 2 is different from Example 1 in that Ag nanoparticle aggregated in a silver nanoparticle colloid liquid is used. First, the same silver nanoparticle colloidal solution as in Example 1 is a hexane with a fine particle solid content concentration of 37%, which is initially well dispersed with a primary average particle size of 4.5 nm (manufacturer measurement data upon delivery). Dispersion solution. However, if this is left as it is, silver nanoparticles will aggregate and precipitate over time. In Example 2, silver nanoparticles containing aggregates / precipitates after standing for about 1 month were used. The result of measuring the particle size of the silver nanoparticles containing the aggregates / precipitates was 348 nm as described later. In addition, the silver nanoparticle colloid liquid of Example 1 is not an aggregate as described later.

(Comparative Example 1)
The electron-emitting device of Comparative Example 1 was manufactured as follows. First, 3 mL of a toluene solvent is placed in a 10 mL reagent bottle, and 0.5 g of silica particles having an average particle diameter of 110 nm are charged as insulator fine particles 5 therein, and the reagent bottle is placed in an ultrasonic dispersing device. The particles were dispersed. Next, 0.055 g of silver nanoparticles (primary average particle diameter of 10 nm, of which the insulating coating alcoholate is 1 nm thick, dry-up product) is additionally charged into the reagent bottle as conductive fine particles 6 having an insulator substance attached to the surface, Similarly, ultrasonic dispersion processing is performed. Thus, Dispersion Solution B in which the blending ratio (weight ratio) of insulating fine particles (silica particles) was 90% was obtained.

  Then, the dispersion solution B was deposited on a 30 mm square SUS substrate as the substrate 2 by using a spin coating method to form the fine particle layer 4. The upper electrode 3 was formed on the surface of the fine particle layer 4 using a magnetron sputtering apparatus, whereby the electron-emitting device of Comparative Example 1 was obtained. The film forming condition by the spin coating method was that after the dispersion solution B was dropped onto the substrate 2, the substrate 2 was rotated at 500 rpm for 5 seconds and then at 3000 RPM for 10 seconds. This film forming condition was repeated three times, three layers were deposited on the substrate 2, and then naturally dried at room temperature. The film thickness of the fine particle layer 4 was about 1500 nm.

After the fine particle layer 4 was formed on the surface of the substrate 2, the upper electrode 3 was formed using a magnetron sputtering apparatus. Gold was used as a film forming material, the layer thickness of the upper electrode 3 was 12 nm, and the area was 0.28 cm ² .

(Measurement of electron emission current of electron-emitting device)
For the electron-emitting devices of Examples 1 and 2 and Comparative Example 1 manufactured as described above, an experiment for measuring the electron emission current per unit area was performed using the experimental system shown in FIG. In the experimental system shown in FIG. 5, the counter electrode 8 is disposed on the upper electrode 3 side of the electron-emitting device 1 with the insulator spacer 9 interposed therebetween. The electron-emitting device 1 and the counter electrode 8 are each connected to a power source 7, and a voltage V1 is applied to the electron-emitting device 1 and a voltage V2 is applied to the counter electrode 8. An electron emission experiment was conducted by placing such an experimental system in a vacuum of 1 × 10 ⁻⁸ ATM. In the electron emission experiment, V2 = 100V. The distance between the electron-emitting device and the counter electrode was 5000 μm across the insulator spacer 9. In the measurement in a vacuum, V2 = 50 to 200V is not so different from the result.

The electron-emitting device of Example 1 was confirmed to have an electron-emitting current of 1.27E-4 A / cm ² at V1 = 19.3V. The electron-emitting device of Example 2 was confirmed to have an electron-emitting current of 5.35E-5 A / cm ² at V1 = 18.3V. The electron-emitting device of Comparative Example 1 was confirmed to have an electron-emitting current of 4.92E-5 A / cm ² at V1 = 28.1V.

Here, electrons are emitted in a vacuum of 1 × 10 ⁻⁸ ATM. However, since conductive fine particles of noble metal (silver in the examples) are used, electrons can be emitted in the atmosphere.

(Measurement of light emission from electron-emitting devices)
Furthermore, using the light emission experiment apparatus shown in FIGS. 6 and 7, a light emission experiment with fluorescence was performed on the electron-emitting devices of Examples 1 and 2 and Comparative Example 1. In the light emission experimental apparatus shown in FIG. 6, a glass substrate 15 with ITO is disposed on the upper electrode 3 side of the electron-emitting device 1. On the glass substrate 15 with ITO, a phosphor 16 is applied on the surface facing the electron-emitting device 1. And the glass substrate 15 with ITO was connected with the power supply, and the applied voltage to the glass substrate 15 with ITO was 2000V. Further, a voltage of 15 V was applied to the electron-emitting device 1 from a bias electrode connected to the bias power source 17. FIG. 7 is a top view (photograph) of the luminescence experimental apparatus. An electron emission experiment was conducted by placing such a light emission experimental apparatus in a vacuum of 1 × 10 ⁻⁸ ATM.

  The result of the light emission experiment of the electron-emitting device of Example 1 is shown in FIG. FIG. 8 is a photograph of light emission from the top of the glass substrate 15 with ITO. FIG. 8 shows that uniform surface electrons are emitted. Furthermore, the measurement result of the particle size distribution of the hexane dispersion colloid of the silver nanoparticle used in Example 1 is shown in FIG. From FIG. 9, it was found that the median diameter of the number particle size distribution was 4.9 nm (0.0049 μm), that is, the colloid of silver nanoparticles was present with a substantially primary particle size.

  The result of the light emission experiment of the electron-emitting device of Example 2 is shown in FIG. FIG. 10 is a photograph of light emission from the top of the glass substrate 15 with ITO. FIG. 10 shows that nonuniform surface electrons are emitted. Furthermore, the measurement result of the particle size distribution of the hexane dispersion colloid aggregate of the silver nanoparticle used in Example 2 is shown in FIG. From FIG. 11, it was found that the median diameter of the number particle size distribution was 0.348 μm.

  In addition, as a result of the light emission experiment of the electron-emitting device of Comparative Example 1, there were many devices in which the substrate (lower electrode) 2 and the upper electrode 3 leaked and did not emit electrons. There was also.) The measurement result of the particle size distribution of the toluene dispersion of the silver nanoparticles of the dry-up product used in Comparative Example 1 is shown in FIG. From FIG. 12, it was found that the median diameter of the number particle size distribution was 2.768 μm.

  From the above light emission experiment, it can be seen that when the nanocolloid liquid of the conductive fine particles 6 is used in a liquid state, the fine particle layer 4 in which the conductive fine particles 6 are uniformly dispersed can be formed. Furthermore, it can be seen that it is preferable that the conductive fine particles 6 have a colloidal average particle size of 0.35 μm or less because dispersibility in the fine particle layer (electron acceleration layer) 4 can be improved.

  Furthermore, a fine particle dispersion using a dispersion of hydrophilic silica particles in a solvent and a colloidal solution of platinum fine particles (an aqueous dispersion having a primary average particle diameter of 10 nm and a solid content concentration of 0.5%). From C, an electron emission experiment was performed on the electron-emitting device in which the fine particle layer 4 was formed in the same manner as described above, and electron emission was confirmed. Further, a fine particle dispersion using a dispersion of hydrophilic silica particles in a solvent and a colloidal solution of palladium fine particles (aqueous dispersion solution having a primary average particle diameter of 12 nm of palladium fine particles and a solid content concentration of 0.5%). From D, an electron emission experiment was performed on the electron-emitting device in which the fine particle layer 4 was formed in the same manner as described above, and electron emission was confirmed.

(Example 3)
The electron-emitting device of Example 3 was manufactured as follows. First, 2.0 g of ethanol solvent and 0.5 g of methyltrimethoxysilane KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.) are placed in a 10 mL reagent bottle, and spherical silica particles AEROSIL R8200 having an average particle size of 12 nm are formed as the insulating fine particles 5. Ebonic Exa Japan Co., Ltd.) was introduced in an amount of 0.5 g, and the reagent bottle was put on an ultrasonic dispersing device to prepare an insulating substance-containing resin binder dispersion C. The content of the insulating fine particles 5 in the dispersion C was 17% by weight.

  Then, after the dispersion C obtained above was dropped onto a 30 mm square SUS substrate as the substrate 2, an insulator substance-containing resin binder layer I was formed at 3000 rpm for 10 s using a spin coating method. Since this insulating material-containing resin binder layer I was dried at room temperature and did not change with time, it proceeded to the next step.

  Next, as a solution of the conductive fine particles 6, a gold nanoparticle-containing naphthene dispersion solution (manufactured by Harima Kasei Co., Ltd., average particle diameter of gold nanoparticles 5.0 nm (measurement data described in the catalog), gold nanoparticle solid content concentration 52% ) Was dropped onto the insulator substance-containing resin binder layer I, and then the substrate 2 was rotated at 6000 rpm and 10 s using a spin coating method to form the fine particle layer 4. The gold nanoparticle-containing naphthene dispersion solution is a colloidal solution of gold nanoparticles.

Thereafter, the upper electrode 3 was formed on the surface of the fine particle layer 4 using a magnetron sputtering apparatus, and the electron-emitting device of Example 3 was obtained. Gold was used as the film forming material, the layer thickness of the upper electrode 3 was 40 nm, and the area was 0.014 cm ² .

The electron-emitting device of this Example 3 has an electron emission current per unit area of 0.461 mA / cm ² at a voltage of V1 = 29.6 V applied to the thin film electrode in a vacuum of 1 × 10 ⁻⁸ ATM. It was confirmed that the current in the device was 115 mA / cm ² and the electron emission efficiency was 0.40%.

  In Example 3, although the above-described light emission experiment was not performed, it is expected that the same result as that of the silver colloid of Example 1 is obtained.

[Embodiment 2]
FIG. 13 shows an example of a charging device 90 according to the present invention using the electron-emitting device 1 according to the present invention described in the first embodiment. The charging device 90 includes the electron-emitting device 1 and a power source 7 that applies a voltage to the electron-emitting device 1, and charges the photoconductor 11. The image forming apparatus according to the present invention includes the charging device 90. In the image forming apparatus according to the present invention, the electron-emitting device 1 constituting the charging device 90 is installed facing the photosensitive member 11 that is a member to be charged, and emits electrons by applying a voltage to the photosensitive member 11. Is charged. In the image forming apparatus according to the present invention, conventionally known members may be used other than the charging device 90. Here, it is preferable that the electron-emitting device 1 used as the charging device 90 is disposed 3 to 5 mm away from the photoreceptor 11, for example. The applied voltage to the electron-emitting device 1 is preferably about 25V, and the electron acceleration layer of the electron-emitting device 1 is configured such that, for example, 1 μA / cm ² of electrons is emitted per unit time when a voltage of 25V is applied. It only has to be.

  The electron-emitting device 1 used as the charging device 90 does not cause discharge even when operated in the atmosphere if the conductive fine particles 6 are a conductor having a high anti-oxidation power. Therefore, no ozone is generated from the charging device 90. . Ozone is harmful to the human body and regulated by various environmental standards, and even if it is not released outside the machine, it oxidizes and degrades organic materials such as the photoreceptor 11 and the belt. Such a problem can be solved by using the electron-emitting device 1 according to the present invention for the charging device 90 and having the charging device 90 in the image forming apparatus.

  Further, since the electron-emitting device 1 used as the charging device 90 is configured as a surface electron source, it can be charged with a width in the rotation direction of the photoconductor 11 and there are many opportunities for charging to a certain place of the photoconductor 11. You can earn. Therefore, the charging device 90 can be uniformly charged as compared with a wire charger that charges in a linear manner. Further, the charging device 90 has an advantage that the applied voltage can be remarkably reduced to about 10 V as compared with a corona discharger that requires voltage application of several kV.

[Embodiment 3]
FIGS. 14 to 16 show examples of the self-luminous device according to the present invention using the electron-emitting device 1 according to the present invention described in the first embodiment.

  A self-emitting device 31 shown in FIG. 14 includes an electron-emitting device 1, a power source 7 that applies a voltage to the electron-emitting device 1, and a glass substrate 34 and an ITO film 33 that are base materials at positions facing and away from the electron-emitting device 1. The phosphor 32 includes a light emitting unit 36 having a laminated structure.

As the phosphor 32, an electron excitation type material corresponding to red, green, and blue light emission is suitable, for example, Y ₂ O ₃ : Eu for red, (Y, Gd) BO ₃ : Eu, and Zn ₂ SiO for green. ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, blue, BaMgAl ₁₀ O ₁₇ : Eu ^{2+ and the} like can be used. A phosphor 32 is formed on the surface of the glass substrate 34 on which the ITO film 33 is formed. The thickness of the phosphor 32 is preferably about 1 μm. In addition, the thickness of the ITO film 33 is 150 nm in the present embodiment, as long as the film thickness can ensure conductivity.

  In forming the phosphor 32, it is preferable to prepare a kneaded product of an epoxy resin serving as a binder and finely divided phosphor particles and form the film by a known method such as a bar coater method or a dropping method.

  Here, in order to increase the emission luminance of the phosphor 32, it is necessary to accelerate the electrons emitted from the electron-emitting device 1 toward the phosphor. In this case, the substrate 2 and the light-emitting portion 36 of the electron-emitting device 1 are accelerated. A power source 35 may be provided between the ITO films 33 in order to apply a voltage for forming an electric field for accelerating electrons. At this time, the distance between the phosphor 32 and the electron-emitting device 1 is preferably 0.3 to 1 mm, the applied voltage from the power source 7 is preferably 18 V, and the applied voltage from the power source 35 is preferably 500 to 2000 V.

  A self-luminous device 31 ′ shown in FIG. 15 includes an electron-emitting device 1, a power supply 7 that applies a voltage to the electron-emitting device 1, and a phosphor 32. In the self-luminous device 31 ′, the phosphor 32 has a planar shape, and the phosphor 32 is disposed on the surface of the electron-emitting device 1. Here, the phosphor 32 layer formed on the surface of the electron-emitting device 1 is prepared as a coating liquid composed of a kneaded material with the phosphor particles finely divided as described above, and is formed on the surface of the electron-emitting device 1. To do. However, since the electron-emitting device 1 itself has a structure that is weak against external force, there is a risk that the device may be damaged if film forming means by the bar coater method is used. Therefore, a method such as a dropping method or a spin coating method may be used.

  A self-luminous device 31 ″ shown in FIG. 16 includes an electron-emitting device 1 and a power source 7 that applies a voltage to the electron-emitting device 1, and further, fluorescent particles 32 ′ are mixed in the particle layer 4 of the electron-emitting device 1 as a phosphor 32 ′. In this case, the fine particles of the phosphor 32 'may be used also as the insulator fine particles 5. However, the above-mentioned phosphor fine particles generally have a low electric resistance and are clearly more in comparison with the insulator fine particles 5. Therefore, when the phosphor fine particles are mixed with the insulator fine particles 5, the amount of the phosphor fine particles must be reduced to a small amount, for example, as the insulator fine particles 5, spherical silica particles ( When ZnS: Mg (average diameter: 500 nm) is used as the phosphor fine particles, an appropriate weight mixing ratio of about 3: 1 is appropriate.

  In the self-light-emitting devices 31, 31 ', 31 ", the electrons emitted from the electron-emitting device 1 collide with the phosphors 32, 32 to emit light. The self-light-emitting devices 31, 31', 31" When the conductive fine particles 6 of the emitting element 1 are a conductor having a high anti-oxidation power, electrons can be emitted in the atmosphere, so that the operation in the atmosphere is possible. In addition, whatever the conductive fine particles 6 are, if they are vacuum-sealed, the electron emission current increases and light can be emitted more efficiently.

Further, FIG. 17 shows an example of an image display device according to the present invention provided with the self-luminous device according to the present invention. An image display device 140 shown in FIG. 17 includes the self-luminous device 31 ″ shown in FIG. 16 and a liquid crystal panel 330. In the image display device 140, the self-luminous device 31 ″ is installed behind the liquid crystal panel 330. And used as a backlight. When used in the image display device 140, the applied voltage to the self-luminous device 31 ″ is preferably 20 to 35 V, and for example, 10 μA / cm ² of electrons are emitted per unit time at this voltage. The distance between the self-light emitting device 31 ″ and the liquid crystal panel 330 is preferably about 0.1 mm.

Further, when the self-luminous device 31 shown in FIG. 14 is used as the image display apparatus according to the present invention, the self-luminous devices 31 are arranged in a matrix, and an image is formed and displayed as an FED by the self-luminous device 31 itself. It can also be a shape. In this case, the applied voltage to the self-luminous device 31 is preferably 20 to 35 V, and it is sufficient that, for example, 10 μA / cm ² of electrons are emitted per unit time at this voltage.

[Embodiment 4]
18 and 19 show examples of the cooling device according to the present invention using the electron-emitting device 1 according to the present invention described in the first embodiment. In addition, you may utilize a cooling device as an air blower.

A cooling device 150 shown in FIG. 18 includes an electron-emitting device 1 and a power source 7 that applies a voltage to the electron-emitting device 1. In the cooling device 150, the electron-emitting device 1 emits electrons toward the object 41 to be cooled which is electrically grounded, thereby generating ion wind and cooling the object 41 to be cooled. In the case of cooling, the voltage applied to the electron-emitting device 1 is preferably about 18 V, and it is preferable to emit, for example, 1 μA / cm ² of electrons per unit time at this voltage in the atmosphere.

The cooling device 160 shown in FIG. 19 is further combined with the cooling device 150 shown in FIG. The cooling device 160 shown in FIG. 19 emits electrons toward the cooled object 41 in which the electron-emitting device 1 is electrically grounded, and further, the blower fan 42 blows air toward the cooled object 41 to generate electrons. Electrons emitted from the emitter 1 are sent toward the cooled object 41 to generate an ion wind to cool the cooled object 41. In this case, the air volume by the blower fan 42 is preferably 0.9 to ² L / min / cm ² .

  Here, when the object to be cooled 41 is to be cooled by air blowing, the flow velocity on the surface of the object to be cooled 41 becomes 0 only by air blowing by a fan or the like as in a conventional cooling device, and the portion of the portion where heat is most desired to be released Air is not replaced and cooling efficiency is poor. However, when charged particles such as electrons and ions are contained in the air to be blown, when the vicinity of the object to be cooled 41 is approached, it is attracted to the surface of the object to be cooled 41 by electric force. The atmosphere can be changed. Here, in the cooling devices 150 and 160 according to the present invention, since the charged air such as electrons and ions is included in the blown air, the cooling efficiency is remarkably increased.

  The electron-emitting device 1 used in the cooling devices 150 and 160 can be operated in the atmosphere when the conductive fine particles 6 are conductors having high antioxidation power.

  The above-described embodiments and implementations are examples, and the electron-emitting device 1 can be used in, for example, an electron beam curing apparatus. The electron beam curing device includes an electron-emitting device, a power source that applies a voltage to the electron-emitting device, and an acceleration electrode that further accelerates electrons.

  That is, the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope shown in the claims. That is, embodiments obtained by combining technical means appropriately modified within the scope of the claims are also included in the technical scope of the present invention.

  The electron-emitting device according to the present invention can ensure electrical continuity, flow a sufficient current in the device, and emit ballistic electrons from the thin film electrode. Therefore, for example, an image display device by combining with an image forming apparatus such as an electrophotographic copying machine, a printer, a facsimile, an electron beam curing device, or a light emitter, or an ion wind generated by emitted electrons. Can be suitably applied to a cooling device or the like.

1 Electron emitting device 2 Substrate (electrode substrate)
3 Upper electrode (thin film electrode)
4 Fine particle layer (electron acceleration layer)
5 Insulator fine particles 6 Conductive fine particles 7 Power supply (power supply unit)
8 Counter electrode 9 Insulator spacer 10 Electron emitter 11 Photoreceptor 21 Accelerating electrode 22 Resist 31, 31 ′, 31 ″ Self-luminous device 32, 32 ′ Phosphor 33 ITO film 34 Glass substrate 35 Power source 36 Light emitting unit 41 Cooled object 41 42 Blower Fan 51 Opening 90 Charging Device 100 Electron Beam Curing Device 140 Image Display Device 150 Cooling Device 160 Cooling Device 330 Liquid Crystal Panel

Claims (11)

An electrode substrate, a thin film electrode, and an electrode acceleration layer sandwiched between the electrode substrate and the thin film electrode. When a voltage is applied between the electrode substrate and the thin film electrode, electrons are transmitted through the electron acceleration layer. An electron-emitting device that accelerates and emits the electrons from the thin film electrode,
The electron acceleration layer includes conductive fine particles and insulating fine particles having a primary average particle size larger than the primary average particle size of the conductive fine particles,
In the electron acceleration layer, an average particle diameter of the aggregate of the conductive fine particles is 0.35 μm or less.    The electron-emitting device according to claim 1, wherein the conductive fine particles are a conductor having high anti-oxidation power. The electron-emitting device according to claim 2, wherein the conductive fine particles are gold, silver, platinum, palladium, or nickel .    4. The electron-emitting device according to claim 1, wherein the conductive fine particles have a primary average particle diameter of 3 to 10 nm. An electrode substrate, a thin film electrode, and an electron acceleration layer that is sandwiched between the electrode substrate and the thin film electrode and includes conductive fine particles and insulator fine particles having a primary average particle size larger than the primary average particle size of the conductive fine particles. When a voltage is applied between the electrode substrate and the thin film electrode, the electron accelerating layer accelerates electrons to emit the electrons from the thin film electrode.
An electron acceleration layer forming step of forming the electron acceleration layer on the electrode substrate using the nano colloid liquid of the conductive fine particles in a liquid state;
The method for producing an electron-emitting device, wherein the conductive fine particles have an average particle size in a colloidal state of 0.35 μm or less . 6. The electron emission according to claim 5 , wherein, in the electron acceleration layer forming step, a nano colloid liquid of the conductive fine particles and a solvent in which the insulating fine particles are dispersed are mixed and coated on the electrode substrate. Device manufacturing method.    An electron-emitting device comprising: the electron-emitting device according to claim 1; and a power supply unit that applies a voltage between the electrode substrate and the thin-film electrode. A self-luminous device comprising the electron-emitting device according to claim 7 and a light emitter. An image display device comprising the self-luminous device according to claim 8 .    An electron-emitting device comprising: the electron-emitting device according to claim 2; and a power supply unit that applies a voltage between the electrode substrate and the thin-film electrode. The electron-emitting device emits electrons from the electron-emitting device to be cooled. A cooling device characterized by cooling the body.    A photoconductor comprising: an electron-emitting device comprising: the electron-emitting device according to claim 2; and a power supply unit that applies a voltage between the electrode substrate and the thin-film electrode, and emitting electrons from the electron-emitting device. A charging device characterized by charging the battery.