JP2006209982A - Electron emitting element, its manufacturing method, and electro-optical device, and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electron emitting element of which the electron emitting part can be formed in a simple way and can miniaturize it and make it high definition, its manufacturing method, an electro-optical device, and electronic equipment. <P>SOLUTION: A first electrode 4 is formed on a wiring 17, a thin film 51 that is a monomolecular film of an organic matter (film of hydrocarbon molecule having thiol group) around the first electrode 14, a second electrode 5 is formed on a wiring 18 so as to overlap on a part of the first electrode 4, and an electron emitting part 13 having a nano gap between the first and second electrodes 4, 5 by removing the film 51 by performing UVO<SB>3</SB>cleaning. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electron-emitting device, a method for manufacturing the electron-emitting device, an electro-optical device, and an electronic apparatus.

  In recent years, display screens have become larger, and thinning and low power consumption are important technical issues. Therefore, attention is being focused on SED (Surface-Conduction Electron-Emitter Display) that can solve these technical problems. In the surface conduction electron-emitting device employed in this SED, a plurality of electron-emitting portions of the same number as the pixels are formed in a lattice shape on the cathode electrode, and electrons are emitted from this electron-emitting portion in a vacuum. Then, electrons collide with the phosphor formed on the anode electrode arranged to face the cathode electrode. When electrons collide with the phosphor, the phosphor emits light, and a predetermined color appears on the pixel. Various methods have been proposed as a method of forming a plurality of electron emission portions on a substrate in a lattice shape.

  For example, as disclosed in Patent Document 1, there is a manufacturing method in which a device is manufactured by forming a thin film on a flat surface using mercaptan or the like. As disclosed in Patent Document 2, there is a manufacturing method for forming a nanogap by performing energization forming on an electron emission portion of an electron emission element. As disclosed in Patent Document 3, a molecular integrated circuit device having a nano-order flat base capable of growing a self-organized structure without being affected by the base is formed using the tunnel effect. There was a manufacturing method.

JP 2000-133649 A JP 2002-313220 A JP 2003-203560 A

  However, since Patent Document 1 and Patent Document 3 are methods for forming a thin film on a flat surface, an electron-emitting portion having a nanogap is formed in the case of a complicated shape such as a surface conduction electron-emitting device. I couldn't. Moreover, although it was the method of forming an electron emission part in patent document 2, an electron emission part was not able to be formed unless many processes were passed. In other words, forming the required electron emission portion is complicated and complicated, and is inefficient.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an electron-emitting device in which an electron-emitting portion can be formed by a simple method and which can be made high definition and miniaturized, a method for manufacturing the electron-emitting device, an electro-optical device using these, and an electron Is to provide equipment.

  The method for forming an electron-emitting device according to the present invention is a method for forming an electron-emitting device having a first electrode, a second electrode, and an electron-emitting portion, the step of forming a first electrode on a substrate, A step of forming a thin film around the electrode; a step of forming a second electrode on the substrate; and a step of removing the thin film to form the electron emission portion.

  According to the present invention, an electron emission portion having a nanogap can be easily formed simply by forming a thin film around the first electrode and removing the formed thin film.

  In the method for forming an electron-emitting device according to the present invention, in the step of forming the thin film, the thin film is preferably an organic monomolecular film.

  According to this invention, since it is a monomolecular film, a thin film can be formed.

  In the method for forming an electron-emitting device according to the present invention, in the step of forming the thin film, the thin film is preferably a film formed of a hydrocarbon having a thiol group.

  According to the present invention, since a hydrocarbon monomolecular film is formed, a very thin film can be formed. Moreover, since the thiol group is bonded to the metal of the first electrode, a thin film can be formed on the entire surface of the first electrode without any gap.

  In the method for forming an electron-emitting device of the present invention, it is desirable that the hydrocarbon molecules forming the thin film contain 3 to 750 carbon atoms in the step of forming the thin film.

  According to the present invention, since the carbon atom diameter is 0.154 nm, the length of the carbon chain can be changed if the number of carbon atoms is 3 or more and 750 or less. Can be formed. In addition, by appropriately selecting the number of carbon atoms, the thickness of the hydrocarbon monomolecular film can be controlled, so that the thickness of the thin film can be arbitrarily changed. If the thickness of the thin film can be arbitrarily changed, it is possible to form electron emission portions having various nano gaps corresponding to the electron emission characteristics. This makes it possible to optimize the characteristics of the electron-emitting device.

In the method for forming an electron-emitting device according to the present invention, in the step of forming the nanogap, the thin film is preferably removed by UVO ₃ cleaning.

According to the present invention, since the thin film is easily removed by performing UVO ₃ cleaning, the nanogap can be easily formed. Therefore, it is suitable for mass production. In addition, since variations in the nanogap are reduced, an electron emission portion having stable electron emission characteristics can be formed, and an electron emitting device having stable electron emission characteristics can be obtained.

  In the method for forming an electron-emitting device according to the present invention, the step of forming the first electrode and the second electrode is preferably a droplet discharge method.

  According to the present invention, when the droplet for forming the first electrode is ejected, the formed first electrode is likely to have a convex curved surface shape. Therefore, when the second electrode is formed next, the first electrode is formed. Since the droplets easily flow along the convex curved surface shape, the droplets can be easily disposed in the vicinity of the first electrode, so that an electron emission portion having a nanogap can be easily formed. And if the quantity of the droplet for forming a 1st electrode is changed suitably, the magnitude | size of a 1st electrode can be changed. If the electrode shape of the first electrode can be reduced, the electron-emitting device can also be reduced, so that the density and size can be reduced. For example, the electro-optical device can be increased in definition and size.

  The electron-emitting device of the present invention is an electron-emitting device having a first electrode, a second electrode, and an electron-emitting portion, and extends in a direction intersecting the first wiring formed on the substrate and the first wiring. A second wiring formed as described above, a first electrode formed on the first wiring, and a second electrode formed on the second wiring, and a thin film is provided around the first electrode, It has the said electron emission part formed by removing the said thin film, It is characterized by the above-mentioned.

  According to the present invention, it is possible to provide an electron emission portion having a nanogap simply by removing the thin film formed around the first electrode. Moreover, since the electron emission portion is a nanogap, the electron emission characteristics of the electron emission portion are excellent.

  In the electron-emitting device of the present invention, it is preferable that the first electrode is formed in a convex curved shape.

  According to the present invention, the droplet for forming the second electrode flows along the convex curved surface shape of the first electrode, and the droplet is repelled by the thin film formed on the first electrode. Since the repelled droplets are arranged at positions separated by the thickness of the thin film, an electron emission portion having a nanogap is formed.

  The electro-optical device of the present invention includes the above-described electron-emitting device.

  According to the present invention, since the electron-emitting portion having a nanogap that can be formed by a simple method is provided with the electron-emitting device that can be miniaturized by increasing the density, the high-density, high-definition and miniaturization can be achieved. A possible electro-optical device can be provided.

  An electronic apparatus according to the present invention includes the above-described electro-optical device.

  According to this aspect of the invention, since the electro-optical device that can be miniaturized with high density is provided, it is possible to provide an electronic device that can achieve higher definition and smaller size.

  Embodiments of an electron-emitting device, an electron-emitting device manufacturing method, an electro-optical device, and an electronic apparatus according to the present invention will be described below in detail with reference to the accompanying drawings.

(Embodiment)
(Configuration of electron-emitting device)
The main part of embodiment of this invention is demonstrated in detail. FIG. 1 is a schematic perspective view of the electron-emitting device of this embodiment.

  The substrate 11 is electrically insulative, and various types such as glass, quartz glass, Si wafer, plastic film, and ceramic plate can be used.

As shown in FIG. 1, a wiring 17 as a first wiring is formed on the substrate 11 in the X direction. Similarly, a wiring 18 as a second wiring is formed in the Y direction. An insulating layer 15 is formed on part of the substrate 11 and part of the wiring 17, and wiring 18 is formed on the insulating layer 15. That is, the wiring 17 and the wiring 18 intersect on the substrate 11 so as not to be conducted through the insulating layer 15. On the substrate 11, a pair of the first electrode 4 and the second electrode 5 facing each other is provided, the first electrode 4 is formed on the wiring 17, and the second electrode 5 is formed on the wiring 18. Has been. An electron-emitting device 10 including an electron-emitting portion 13 having a nanogap formed between the first electrode 4 and the second electrode 5 is formed on the substrate 11.
(Method for forming electron-emitting device)

  Next, a method for forming the electron-emitting device of this embodiment will be described. 2A to 2G are schematic cross-sectional views illustrating an example of the procedure of the method for forming the electron-emitting device according to the present embodiment.

  As shown in FIGS. 2A to 2G, a schematic manufacturing process of the electron-emitting device includes a process of forming a wiring 17 as a first wiring, a process of forming an insulating layer 15 as an insulating film, The step of forming the wiring 18 as the second wiring, the step of forming the first electrode 4 on the wiring 17, the step of forming the thin film 51 on the first electrode 4, and the step of forming the second electrode 5 on the wiring 18 And the process of forming the electron emission portion 13. Hereinafter, each step will be described in detail.

  The substrate 11 is sufficiently cleaned using a detergent, pure water, an organic solvent, or the like, and a pretreatment for removing contaminants adhering to the substrate 11 is performed. Thereafter, a mask (not shown) is placed on the substrate 11, and a wiring 17 as a first wiring is formed by a thin film forming method such as a vacuum evaporation method or a sputtering method, as shown in FIG. You may form by the droplet discharge using a droplet discharge method.

As a material of the wiring 17, a general conductive material can be used. For example, metals or alloys such as Ni, Cr, Au, Mo, W, Pt, Ti, Al, Cu, Pd, metals such as Pd, Ag, Au, RuO ₂ , Pd—Ag, or metal oxides and glass It can be suitably selected from a printed conductor composed of a transparent conductor such as In ₂ O ₃ —SnO ₂ , a semiconductor material such as polysilicon, and the like. The width of the wiring 17 is in the range of 10 μm to 300 μm. A preferable film thickness of the wiring 17 is in the range of 10 nm to 3 μm. In addition, the wiring 17 formed on the substrate 11 can be formed in any shape because the width and length of the wiring 17 can be changed if the shape of the mask is changed as necessary. It can be changed within a range where the electron-emitting device 10 can be arranged.

  Next, as shown in FIG. 2B, an insulating layer 15 as an insulating film is formed on the substrate 11, and the insulating layer 15 is also formed on the wiring 17 (see FIG. 1). The insulating layer 15 is formed by a thin film forming method such as a vacuum evaporation method or a sputtering method. You may form by the droplet discharge using a droplet discharge method.

As a material of the insulating layer 15, a material used in a semiconductor process or the like can be used. For example, it is possible to use SiO ₂ and, SiN, or the like Al ₂ O _3. The width of the insulating layer 15 is in the range of 10 μm to 300 μm. The film thickness of the insulating layer 15 is in the range of 2 μm to 200 μm, preferably in the range of 2 μm to 20 μm.

  Next, as shown in FIG. 2C, a wiring 18 as a second wiring is formed on the insulating layer 15 and the substrate 11 (see FIG. 1). The wiring 18 is formed by the same thin film forming method as the wiring 17 described above, and the material, width, film thickness, etc. of the wiring 18 are the same as those of the wiring 17 described above.

  Next, as shown in FIG. 2D, the droplet L is dropped by the droplet discharge method so that the wiring 17 partially overlaps. Thereafter, the first electrode 4 is formed by drying the droplet L to form a thin film, or further baking (heating treatment) as necessary after drying.

  The droplet L for forming the first electrode 4 is made of a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium. In the present embodiment, as the conductive fine particles, for example, metal fine particles containing any of gold, silver, copper, iron, chromium, manganese, molybdenum, titanium, palladium, tungsten, and nickel, as well as oxidation of these As well as fine particles of conductive polymers and superconductors. These conductive fine particles can be used by coating the surface with an organic substance or the like in order to improve dispersibility. The particle diameter of the conductive fine particles is preferably 1 nm or more and 0.1 μm or less. If it is larger than 0.1 μm, there is a risk of clogging in the discharge nozzle of the droplet discharge head described later. On the other hand, if it is smaller than 1 nm, the volume ratio of the coating agent to the conductive fine particles becomes large, and the ratio of the organic matter in the obtained film becomes excessive.

  The dispersion medium is not particularly limited as long as it can disperse the conductive fine particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol, butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydro Hydrocarbon compounds such as naphthalene and cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2- Methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Of these, water, alcohols, hydrocarbon compounds, and ether compounds are preferable and more preferable dispersion media in terms of fine particle dispersibility, dispersion stability, and ease of application to the droplet discharge method. Examples thereof include water and hydrocarbon compounds.

  The surface tension of the conductive fine particle dispersion is preferably in the range of 0.02 N / m to 0.07 N / m. When the liquid is discharged by the droplet discharge method, if the surface tension is less than 0.02 N / m, the wettability of the composition of the functional liquid for the wiring pattern with respect to the discharge nozzle surface increases, and thus flight bending tends to occur. If it exceeds 0.07 N / m, the shape of the meniscus at the tip of the discharge nozzle is not stable, and it becomes difficult to control the discharge amount and the discharge timing. In order to adjust the surface tension, a small amount of a surface tension regulator such as a fluorine-based, silicone-based, or nonionic-based material may be added to the dispersion within a range that does not significantly reduce the contact angle with the substrate. The nonionic surface tension modifier improves the wettability of the liquid to the substrate, improves the leveling property of the film, and helps prevent the occurrence of fine irregularities in the film. The surface tension modifier may contain an organic compound such as alcohol, ether, ester, or ketone, if necessary.

  The viscosity of the dispersion is preferably 1 mPa · s to 50 mPa · s. When the liquid material is discharged as a droplet L using the droplet discharge method, if the viscosity is less than 1 mPa · s, the periphery of the discharge nozzle is easily contaminated by the outflow of the functional liquid for the wiring pattern, and the viscosity is 50 mPa · When it is larger than s, the flow resistance at the discharge nozzle hole becomes high, and it becomes difficult to smoothly discharge the droplet L.

Examples of the discharge technique of the droplet discharge method for dropping the droplet L include a charge control method, a pressure vibration method, an electromechanical conversion method, an electrothermal conversion method, and an electrostatic suction method. Here, in the charge control method, a charge is applied to a material by a charging electrode, and the flight direction of the material is controlled by a deflection electrode and discharged from a discharge nozzle. In addition, the pressure vibration method is a method in which an ultra-high pressure of about 30 kg / cm ² is applied to the material to discharge the material to the nozzle tip side, and when the control voltage is not applied, the material moves straight from the discharge nozzle. When discharged and a control voltage is applied, electrostatic repulsion occurs between the materials, and the materials are scattered and are not discharged from the discharge nozzle. The electromechanical conversion method utilizes the property that a piezoelectric element (piezoelectric element) is deformed by receiving a pulse-like electric signal. The piezoelectric element is deformed through a flexible substance in a space where material is stored. Pressure is applied, and the material is extruded from this space and discharged from the discharge nozzle.

  In the electrothermal conversion method, a material is rapidly vaporized by a heater provided in a space where the material is stored to generate bubbles, and the material in the space is discharged by the pressure of the bubbles. In the electrostatic attraction method, a minute pressure is applied to a space in which a material is stored, a meniscus of material is formed on the discharge nozzle, and an electrostatic attractive force is applied in this state before the material is drawn out. In addition to this, techniques such as a system that uses a change in the viscosity of a fluid due to an electric field and a system that uses a discharge spark are also applicable. The droplet discharge method has an advantage that the use of the material is less wasteful and a desired amount of the material can be accurately disposed at a desired position. In addition, the amount of one drop of the liquid material discharged by the droplet discharge method is 1 to 300 nanograms, for example.

  The dropped droplet L is dried as necessary to remove the dispersion medium and secure the film thickness. The drying method can be performed by lamp annealing, for example, in addition to a process using a normal hot plate or an electric furnace for heating the substrate 11. The light source used for lamp annealing is not particularly limited, but excimer lasers such as infrared lamps, xenon lamps, YAG lasers, argon lasers, carbon dioxide lasers, XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, etc. It can be used as a light source. In general, these light sources have an output in the range of 10 W to 5000 W, but in the present embodiment, a range of 100 W to 1000 W is sufficient.

  Since the dried film after discharging the droplets L needs to be subjected to heat treatment to obtain conductivity and to remove organic components and leave metal particles, the substrate 11 after discharging the droplets L is subjected to heat treatment and light treatment. Applied.

  The heat treatment and the light treatment are usually performed in the air, but can be performed in an inert gas atmosphere such as nitrogen, argon, or helium, or in a reducing atmosphere such as hydrogen, if necessary. The heat treatment and light treatment temperatures include the boiling point (vapor pressure) of the dispersion medium, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the fine particles, the presence and amount of coating material, and the heat resistance temperature of the substrate. It is determined appropriately in consideration of the above. In the present embodiment, the discharged droplets L are baked at 200 to 400 ° C. for 300 minutes in a clean oven in the atmosphere. This is because it is necessary to bake at about 200 ° C. or higher in order to remove the organic component of the organic silver compound. However, when a substrate such as plastic is used, it is preferably performed at a temperature between room temperature and 250 ° C. As described above, the dry film ensures electrical contact between the fine particles and is converted into the first electrode 4.

  Next, as shown in FIG. 2E, a hydrocarbon monomolecular thin film 51 (a hydrocarbon film having a thiol group) is formed on the surface of the first electrode 4. Generally, when a metal is immersed in a solution containing a hydrocarbon having a thiol group (including at least a hydrocarbon solvent), the thiol group enters the gap between the metal atom and an atom adjacent to the atom, The thiol groups are uniformly bonded to the metal surface, and the hydrocarbon covers the surface of the metal part. When the solvent is removed, a hydrocarbon film can be formed.

  In this embodiment, hydrocarbon having a thiol group is used as a solute, and toluene is used as a solvent. Therefore, a solution in which a hydrocarbon having a thiol group is dissolved is prepared by setting the solute concentration to 1% and the solvent concentration to 99%. Next, the first electrode 4 formed on the substrate 11 is left in the solution for about 24 hours. And the board | substrate 11 is pulled up from a solution and the solvent adhering to the 1st electrode 4 is skipped. The temperature at which the solvent is blown is room temperature and is in the range of 20 ° C to 30 ° C. Then, a thin film 51 is formed on the surface of the first electrode 4. The wiring 18 is covered with a mask (not shown) so that the thin film 51 is not formed on the wiring 18. The solvent used here is toluene, but is not limited thereto. For example, a solvent obtained by adding chloroform, alcohol, ether, low-molecular hydrocarbon, or the like to toluene may be used. The concentration of toluene used as a solvent is not limited to 99%. For example, if the amount of toluene is reduced and the amount of hydrocarbon having thiol groups is increased, the concentration of hydrocarbon having thiol groups is relatively increased, so that the thin film 51 can be formed relatively quickly.

  Here, if the carbon molecular weight contained in the solution in which the hydrocarbon having a thiol group is dissolved is changed, the length of the carbon chain is changed, and the thickness of the thin film 51 can be changed. For example, since the diameter of the carbon atom is 0.154 nm, when the carbon molecular weight is 3, the thin film 51 is about 0.5 nm. Similarly, when the carbon molecular weight is 750, the thin film 51 is about 115 nm. That is, the nanogap can be varied in the range of about 0.5 nm to about 115 nm. In this embodiment, the carbon molecular weight is set to 3 so that the nanogap is about 0.5 nm.

  Next, as shown in FIG. 2 (f), the second electrode 5 is formed at a position adjacent to the first electrode 4. As a method of forming the second electrode 5, the droplet L is dropped so as to partially overlap the wiring 18 by a droplet discharge method. Thereafter, the second electrode 5 is formed by drying the droplet L to form a thin film, or further baking (heat treatment) as necessary after drying. Note that the second electrode 5 can be formed by using the same droplet discharge method as the first electrode 4, and the same material and dispersion medium may be used. Then, when the droplet L for forming the second electrode is dropped on the wiring 18, it is dropped so as to come into contact with the first electrode 4 to form a nanogap. In order to drop the droplet L near the first electrode 4, for example, when the droplet L is dropped on the first electrode 4, the droplet L is repelled by the thin film 51 provided on the first electrode 4, and the thin film The droplet L is disposed at a position separated by the thickness of 51. In the case of this embodiment, the second electrode 5 is formed at a position about 0.5 nm apart.

Next, as shown in FIG. 2G, the electron emission portion 13 is formed. When the thin film 51 (hydrocarbon film having a thiol group) formed on the first electrode 4 is removed, an electron emission portion 13 having a nanogap between the first electrode 4 and the second electrode 5 can be formed. . The electron emission portion 13 has a nano gap of about 0.5 nm. The removal of the thin film 51 can be realized by performing UVO ₃ cleaning described later. Note that FIG. 2G is a schematic cross-sectional view showing a CC cross section of FIG.

In UVO ₃ cleaning, a low-pressure mercury lamp is often used. This cleaning method is a dry cleaning method for decontamination of organic compounds and surface modification by the action of ultraviolet rays and ozone (O ₃ ) generated from a low-pressure mercury lamp, including organic solvents, water, cleaning agents, etc. Do not use. In general, UVO ₃ cleaning has a cleaning action on materials such as glass and ceramics, and both cleaning and surface modification actions on materials such as plastic and metal. Since the thin film 51 formed on the first electrode 4 is organic, it can be easily removed by performing UVO ₃ cleaning.

The low-pressure mercury lamp can generate two types of ultraviolet light (ultraviolet light) of 185 nm and 254 nm. The output of the low-pressure mercury lamp is 200W. The standard UVO ₃ cleaning conditions are such that the distance between the object to be cleaned and the low-pressure mercury lamp is in the range of 5 to 20 mm, and the irradiation time of the low-pressure mercury lamp is in the range of 30 seconds to 2 minutes. In the present embodiment, the cleaning conditions for removing the thin film 51 formed on the first electrode 4 were an irradiation distance of about 10 mm and an irradiation time of 1 minute. Even when the thickness of the thin film 51 is changed, the thin film 51 can be removed if the cleaning conditions for the irradiation time and the irradiation distance are set to an appropriate range. In addition, since it is only necessary to determine the irradiation time and irradiation distance in advance, the removal work of the thin film 51 is simplified and suitable for mass production. Then, in the step of forming the thin film 51, since the thin film forming method, can little variation in film 51 is formed, in the step of removing the thin film 51, since the batch processing with UVO ₃ washed as described above, the variation The electron emission portion 13 having a small nanogap can be formed. Moreover, it can be done easily. Therefore, the electron-emitting device 10 and the electro-optical device 70 having excellent electron emission characteristics can be formed. Compared with the method of forming the nano gap by the energization forming method, the method is a combination of the thin film formation method and the UVO ₃ cleaning method, so that the nano gap can be easily formed and the process is simplified. , Less complex work. Note that, as long as a nanogap can be formed, a part of the thin film 51 may remain.

In the UVO ₃ cleaning described above, a xenon excimer lamp can be used in addition to a method using a low-pressure mercury lamp. This xenon excimer lamp generates 172 nm ultraviolet light (ultraviolet light). However, since the wavelength of this xenon excimer lamp is shorter than that of the low-pressure mercury lamp, the distance from the object to be cleaned is in the range of 1 to 3 mm. Even if this xenon excimer lamp is used, since the thin film 51 is removed, the electron emission portion 13 having a nanogap can be formed.

The thin film 51 can be removed by heating and baking in an oxygen atmosphere in addition to the UVO ₃ cleaning method using these lamps that generate ultraviolet light. By heating and baking the thin film 51, the thin film 51 is oxidized or decomposed and removed, so that the electron emission portion 13 having a nanogap can be formed. The first electrode 4 and the second electrode 5 are formed after the wiring is formed to form the electron emission portion 13 having a nanogap. For example, the electron emission portion 13 having the nanogap is formed in the reverse order. Then, even if connected to the wiring, the electron emission portion 13 having a nanogap between the first electrode 4 and the second electrode 5 can be formed.
(Configuration of electro-optical device)

  FIG. 3 is a diagram showing a schematic configuration of the electro-optical device, and FIG. 3A is a schematic sectional view showing a sectional structure along the line CC in FIG. b) is a schematic plan view.

As shown in FIG. 3A, the electro-optical device 70 includes a substrate 11 on which the electron-emitting devices 10 are arranged, and a display substrate 71 that faces the substrate 11. The substrate 11 and the display substrate 71 are kept at a fixed interval via an outer frame member (not shown), and a space 72 is provided between the substrate 11 and the display substrate 71. The space 72 is 10 ⁻ Sealed in a vacuum state of about ⁷ Torr (Newton / m ² ). A wiring 17, a wiring 18, and an insulating layer 15 are formed on the substrate 11. An electron-emitting portion 13 having a nanogap is formed between the first electrode 4 formed on the wiring 17 and the second electrode 5 formed on the wiring 18, and constitutes the electron-emitting device 10.

  The display substrate 71 includes a counter electrode 73, a fluorescent film 74, and a light shielding film 75. The light shielding film 75 is formed in accordance with the arrangement of the electron-emitting devices 10 so as to partition the pixels, and plays a role of reducing crosstalk between pixels and reflection of external light by the fluorescent film 74. As the material, a material having conductivity and light shielding properties such as graphite is used. The phosphor film 74 contains a phosphor, and plays a role of lighting a pixel when the phosphor emits light by collision of emitted electrons from the electron-emitting device 10. The electron-emitting devices 10 arranged on the substrate 11 include an electron-emitting portion 13 having a nanogap. And the electron emission part 13 which has this nano gap is arrange | positioned in the position facing the fluorescent film 74. FIG.

  Here, when the electro-optical device 70 is a color display type, the fluorescent film 74 is formed by being divided for each pixel by phosphors corresponding to the three primary colors. An acceleration voltage (for example, about 10 kV) is applied to the counter electrode 73 and plays a role of accelerating the emitted electrons in order to give sufficient energy to excite the phosphor of the phosphor film 74. For the counter electrode 73, for example, a transparent conductor such as ITO is used.

  As shown in FIG. 3B, the wiring 17 and the wiring 18 are formed on the substrate 11 so as to intersect each other. A so-called simple matrix type in which an electron-emitting device 10 corresponding to each pixel is provided by a first electrode 4 formed extending from the wiring 17 and a second electrode 5 formed extending from the wiring 18. An element array is provided. An insulating layer 15 is formed at the intersection of the wiring 17 extending in the X-axis direction and the wiring 18 extending in the Y-axis direction. A scanning signal for sequentially driving the electron-emitting devices 10 row by row (alignment in the X-axis direction in the figure) is applied to the wiring 17, and the wiring 18 has a row selected by the scanning signal. A gradation signal for controlling the electron emission of the electron-emitting device 10 is applied to control the electron emission for each pixel.

  The configuration of the electro-optical device 70 is as described above. The scanning signal applied to the wiring 17 and the gradation signal applied to the wiring 18 are controlled to emit electrons from the electron-emitting device 10, and the counter electrode 73 The accelerated emitted electrons collide with the fluorescent film 74, so that the pixels are turned on and a desired image is displayed.

  In the embodiment as described above, the following effects are obtained.

(1) The first electrode 4 is formed on the wiring 17 as the first wiring, and the thin film 51 (the film of hydrocarbon molecules having a thiol group) is formed on the first electrode 4. After forming the two electrodes 5, UVO ₃ cleaning is performed to remove the monomolecular thin film 51, thereby forming the electron emission portion 13 having a nanogap between the first electrode 4 and the second electrode 5. it can. Since the method for removing the thin film 51 is UVO ₃ wash, because the nanogap easily formed, is efficient, a mass production direction. Since the electron emission portion 13 has a nano gap, the electron emission device 10 having excellent electron emission characteristics can be obtained.
(2) When the thin film 51 of monomolecular film is formed, if the carbon molecular weight of the thin film 51 (solution in which a hydrocarbon having a thiol group is dissolved) is appropriately selected, the length of the carbon chain depends on the carbon molecular weight. The thickness of the thin film 51 can be arbitrarily changed. If the thickness of the thin film 51 can be changed, the electron-emitting portion 13 having a nanogap can be arbitrarily changed and set, so that various electron-emitting devices 10 that match the required electron-emitting characteristics can be formed.
(3) Since the first electrode 4 is formed by the droplet discharge method, the shape of the first electrode 4 can be reduced by appropriately changing the amount of the droplet L. And since the electron emission part 13 which has a nanogap can also be made small, since the electron emission element 10 provided with the electron emission part 13 can also be made small, the electro-optical apparatus 70 which can be densified and reduced in size can be provided.
(Electronics)

  Next, an electronic apparatus including the electro-optical device 70 according to the present invention will be described.

  4 and 5 are schematic perspective views illustrating examples of the electronic apparatus.

  A specific example of the electronic apparatus according to the present embodiment will be described with reference to FIG.

  As shown in FIG. 4, a portable information processing device 700 as an electronic device includes a keyboard 701, an information processing body 703, and an electro-optical display device 702 including the electro-optical device 70. A more specific example of such a portable information processing apparatus 700 is a personal computer or the like. Since the portable information processing apparatus 700 includes the electron-emitting device 10 having excellent electron-emitting characteristics, high definition can be achieved. In addition, since the electron-emitting device 10 capable of increasing the density is provided, the electro-optic display device 702 including the electro-optic device 70 can be made high definition and downsized.

  Next, a specific example of the electronic device according to the present embodiment will be described with reference to FIG.

  As shown in FIG. 5, an electron beam exposure apparatus 800 as an electronic apparatus includes an electron gun 810 in an exposure unit 850. Further, the electron gun 810 is provided with the electron-emitting device 10 having excellent electron emission characteristics. Since the electron beam exposure apparatus 800 is equipped with the electron gun 810 including the electron-emitting device 10 capable of increasing the density, the nanometer level high-precision that requires a fine pattern is provided. Can draw. In addition, since the electron-emitting device 10 capable of increasing the density is provided, the electron-emitting device 10 can be made small, and the electron beam exposure apparatus 800 can be downsized.

  Another example of an electronic device including the electron-emitting device 10 is characterized by controlling the number of electron beams emitted from a solid, the emission direction, the electron density distribution, and the luminance using the wave nature of electrons. Coherent electron source, coherent electron beam converging device, electron beam holography device, monochromatic electron gun, electron microscope, multiple coherent electron beam generating device, electrophotographic printer drawing device, etc. It is also possible to provide an electronic apparatus including the electro-optical device.

  The present invention has been described above with reference to preferred embodiments. However, the present invention is not limited to the above-described embodiments, and includes modifications as described below, as long as the object of the present invention can be achieved. Any other specific structure and shape can be set.

  (Modification 1) In the above-described embodiment, the electron emission portion 13 having a nanogap is formed between the first electrode 4 and the second electrode 5 by a distance corresponding to the thickness of the thin film 51. This is not restrictive (see FIG. 2 (g)). For example, as shown in FIG. 6, the first electrode 4 and the second electrode 5 may be overlapped to form an electron emission portion 13 having a nanogap. Even in this case, since the thin film 51 can be formed on the first electrode 4, the electron emission portion 13 having a nanogap can be formed between the first electrode 4 and the second electrode 5. Effects can be obtained. The electron emission portion 13 having the nanogap is different only in that the second electrode 5 is formed so as to cover the first electrode 4. An electron emission portion 13 having a gap is formed. Even if the first electrode 4 is covered with the second electrode 5, the same effect can be obtained.

  (Modification 2) In the above-described embodiment, the first electrode 4 is formed by the droplet discharge method, but is not limited thereto. For example, the first electrode 4 may be formed by a thin film forming method such as a vacuum evaporation method or a sputtering method. Even in this case, since the thin film 51 can be formed on the first electrode 4, the electron emission portion 13 having a nanogap can be formed between the first electrode 4 and the second electrode 5. Effects can be obtained.

  (Modification 3) In the above-described embodiment, the shape of the first electrode 4 is a convex curved surface, but this is not restrictive. For example, the first electrode 4 may be formed in a rectangular shape. Even in this case, since the thin film 51 can be formed on the first electrode 4, the electron emission portion 13 having a nanogap can be formed between the first electrode 4 and the second electrode 5. Effects can be obtained.

1 is a schematic perspective view of an electron-emitting device according to an embodiment. (A)-(g) is a schematic sectional drawing which shows the manufacturing process of an electron emission element. It is the figure which showed schematic structure of the electro-optical apparatus, (a) is schematic sectional drawing. (B) is a schematic plan view. The schematic perspective view which shows the portable information processing apparatus as an electronic device. The schematic perspective view which shows the electron beam exposure apparatus as an electronic device. 6 is a schematic cross-sectional view of an electron-emitting device as Modification 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 4 ... 1st electrode, 5 ... 2nd electrode, 10 ... Electron emission element, 11 ... Substrate, 13 ... Electron emission part which has nanogap, 15 ... Insulating layer as insulating film, 17 ... Wiring as 1st wiring, 18 ... wiring as second wiring, 51 ... thin film (hydrocarbon film having thiol group), 70 ... display device as electro-optical device, 71 ... display substrate, 72 ... space, 73 ... counter electrode, 74 ... Fluorescent film, 75 ... light-shielding film, 700 ... portable information processing apparatus as electronic equipment, 800 ... electron beam exposure apparatus as electronic equipment, L ... droplet, X ... X direction, Y ... Y direction, Z ... Z direction .

Claims (10)

A method for forming an electron-emitting device having a first electrode, a second electrode, and an electron-emitting portion,
Forming a first electrode on a substrate;
Forming a thin film around the first electrode;
Forming a second electrode on the substrate;
Removing the thin film to form the electron emission portion;
A method for forming an electron-emitting device, comprising: The method for forming an electron-emitting device according to claim 1,
In the step of forming the thin film,
The method for forming an electron-emitting device, wherein the thin film is an organic monomolecular film. The method for forming an electron-emitting device according to claim 2,
In the step of forming the thin film,
The method for forming an electron-emitting device, wherein the thin film is a film formed of a hydrocarbon molecule having a thiol group. In the formation method of the electron emission element of Claim 2 or Claim 3,
In the step of forming the thin film,
The method for forming an electron-emitting device, wherein the hydrocarbon molecules constituting the thin film contain 3 to 750 carbon atoms. In the formation method of the electron-emitting device as described in any one of Claims 2-4,
In the step of forming the electron emission portion,
A method for forming an electron-emitting device, wherein the thin film is removed by UVO ₃ cleaning. The method for forming an electron-emitting device according to claim 1,
The step of forming the first electrode and the second electrode includes:
A method for forming an electron-emitting device, which is a droplet discharge method. An electron-emitting device having a first electrode, a second electrode, and an electron-emitting portion,
A first wiring formed on the substrate;
A second wiring formed to extend in a direction crossing the first wiring;
A first electrode formed on the first wiring;
A second electrode formed on the second wiring,
An electron-emitting device having the electron-emitting portion formed by providing a thin film around the first electrode and removing the thin film. The electron-emitting device according to claim 7,
The electron-emitting device, wherein the first electrode has a convex curved surface shape.   An electro-optical device comprising the electron-emitting device according to claim 7. An electronic apparatus comprising the electro-optical device according to claim 9.

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