WO2005055266A1 - 電子放出源の製造方法 - Google Patents
電子放出源の製造方法 Download PDFInfo
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- WO2005055266A1 WO2005055266A1 PCT/JP2004/017977 JP2004017977W WO2005055266A1 WO 2005055266 A1 WO2005055266 A1 WO 2005055266A1 JP 2004017977 W JP2004017977 W JP 2004017977W WO 2005055266 A1 WO2005055266 A1 WO 2005055266A1
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- gas
- electron emission
- emission source
- carbon material
- atmospheric pressure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/10—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes
- H01J31/12—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen
- H01J31/123—Flat display tubes
- H01J31/125—Flat display tubes provided with control means permitting the electron beam to reach selected parts of the screen, e.g. digital selection
- H01J31/127—Flat display tubes provided with control means permitting the electron beam to reach selected parts of the screen, e.g. digital selection using large area or array sources, i.e. essentially a source for each pixel group
Definitions
- the present invention relates to an electron emission source and a method for manufacturing the same, and more particularly, to a method for easily forming an electron emission source that can be used for a field emission display (hereinafter, referred to as FED), an electron beam source, a micro vacuum tube, and the like.
- FED field emission display
- the present invention relates to an electron emission source and a method for manufacturing the same, and more particularly, to a method for easily forming an electron emission source that can be used for a field emission display (hereinafter, referred to as FED), an electron beam source, a micro vacuum tube, and the like.
- FED field emission display
- the carbon nanotube has a structure in which a daraphen sheet having a network structure in which six-membered carbon rings are connected on a plane is wound in a cylindrical shape and is connected seamlessly.
- a structure composed of one graphene 'sheet is called a single-walled nanotube, and a structure formed by nesting a plurality of graphon' sheets in a nested structure is called a multi-walled nanotube.
- Daraite nanofibers also have a columnar structure in which graphene sheets are stacked in the shape of an ice cream cone with a truncated tip, or a shape that conforms to the surface shape of the catalyst metal used for formation. It is a material having a structure in which small pieces of graphite sheets are stacked.
- FED field 'emission' display
- Nanostructured carbon materials are excellent in performance such as electron emission characteristics, heat resistance, and chemical stability, and in recent years, are expected to be applied to electron emission sources that apply the above-mentioned field emission principle to image display. Have been. In addition, they are expected to be applied to electronic and electrical devices because they have the properties of being able to be used as semiconductors and conductors.
- Patent Document 1 discloses a method in which a substrate on which a catalytic metal thin film is formed is heat-treated under vacuum and then heat-treated. The ability to selectively form a graphite nanofipper thin film at a predetermined location on a substrate by the CVD method
- Patent Document 2 discloses that the output of microwaves for generating plasma in a vacuum deposition chamber is modulated over time. The force S generated by orienting the carbon nanotubes on the substrate in the vertical direction is described, respectively.
- Patent Document 3 discloses a manufacturing method as described above. It is described that the manufactured nanostructured carbon material is putt für photolithography technology.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2001-64775
- the arc discharge method and vacuum plasma method conventionally used in the production of nanostructured carbon materials require equipment to evacuate the equipment, making the production equipment complicated. And equipment and manufacturing costs are large. Furthermore, it is difficult for the arc discharge method to produce and grow a nanostructured carbon material directly on a substrate having a flat surface, and even if possible, it is limited to a local area, and it is not possible to form it directly and uniformly on a large-area substrate. Near impossible.
- the substrate is manufactured at a very high temperature of 600 ° C. or more, so if the nanostructured carbon material is formed directly on the substrate, the substrate can withstand the high temperature. Ceramics are limited to materials such as quartz glass, and are commonly used as substrate materials, for example, common glass such as soda glass or plastic.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for easily forming a nanostructured carbon material on various substrates to obtain an electron emission source. Disclosure of the invention
- the object of the present invention can be achieved by the following configurations.
- a method for manufacturing an electron emission source comprising: a conductive layer forming step of forming a conductive layer on at least a substrate; an insulating layer forming step of forming an insulating layer on the conductive layer; and a gate on the insulating layer.
- a method of manufacturing an electron emission source wherein at least one of an insulating layer forming step and the gate layer forming step is performed by an atmospheric pressure plasma method.
- the step of forming a nanostructured carbon material layer includes a step of depositing metal fine particles on the conductive layer, and the step of forming a nanostructured carbon material layer includes the step of depositing the metal particles on the conductive layer. 3.
- a gas containing at least a discharge gas is introduced between opposing electrodes under an atmospheric pressure or a pressure close to the atmospheric pressure, and a high-frequency voltage is applied between the electrodes to discharge the gas.
- a high-frequency voltage is applied between the electrodes to discharge the gas.
- FIG. 1 is a schematic cross-sectional view illustrating a configuration of an FED, which is an example of a planar image device using an electron emission source according to an embodiment of the present invention as a field emission cold cathode.
- FIGS. 2 (a) to 2 (k) are schematic cross-sectional views for explaining a patterning step of patterning a nanostructured carbon material by lithography on a substrate according to an embodiment of the present invention. It is.
- FIG. 3 is a cross-sectional view showing an example of a gas introduction section and an electrode section in a plasma jet type apparatus of the atmospheric pressure plasma discharge processing apparatus used in the present invention.
- FIG. 4 is a cross-sectional view showing an example of a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in the present invention.
- FIG. 5 is a schematic sectional view of a manufacturing apparatus for forming metal fine particles in an atmospheric pressure plasma discharge treatment apparatus used in the present invention.
- FIG. 6 is a cross-sectional view showing another example of a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in this effort.
- FIG. 7 is a cross-sectional view showing one example of an apparatus in which a cleaning film is provided in a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in the present invention.
- the present invention provides an atmospheric pressure plasma method for generating a discharge plasma by introducing a mixed gas containing a discharge gas and a raw material gas between opposed electrodes under an atmospheric pressure or a pressure close to the atmospheric pressure and applying a high-frequency voltage.
- the method is characterized in that a nanostructured carbon material is formed on a substrate on which a conductive layer is formed to manufacture an electron emission source.
- Nanostructured carbon materials include carbon nanotubes, carbon nanofibers, and graphite nanofibers.
- the pressure at or near atmospheric pressure is about 20 kPa to 110 kPa, preferably 93 kPa to 104 kPa.
- the term “high frequency” refers to one having a frequency of at least 0.5 kHz. Preferably it is 5 to 10 OMHz, more preferably 50 kHz to 5 OMHz. Further, as described in JP-A-2003-96569, different frequencies may be applied to each of the opposing electrodes.
- the discharge processing apparatus used in the atmospheric pressure plasma method according to the present invention applies a high-frequency voltage between at least one pair of opposed electrodes having at least one coated with a dielectric to discharge between the opposed electrodes. At least the discharge gas introduced between the electrodes and the source gas for forming a desired thin film or structure are activated, and the substrate to be left or transferred between the counter electrodes is activated. A thin film or structure is formed on the substrate by exposing it to the raw gas in a state (hereinafter, this method is referred to as a direct method).
- a base material is placed in the vicinity of the counter electrode as described above, a discharge is caused between the electrodes, and a discharge gas introduced between the counter electrodes is excited or activated, and a jet is jetted out of the counter electrode.
- the raw material gas is blown out, mixed and mixed near the base material, and exposed on the base material (which may be left standing or transferred) near the counter electrode, thereby forming a nanostructure on the base material.
- a jet type device for forming carbon material hereinafter, this type Plasma jet method.
- the above-mentioned atmospheric pressure plasma discharge treatment apparatus has, between the opposing electrodes, a power having gas supply means for supplying a discharge gas and a source gas, and further has an electrode temperature control means for controlling the temperature of the electrodes.
- the gas supplied between the counter electrodes includes at least a discharge gas excited by an electric field and a gas that receives the energy to be in a plasma state or an excitation state to form a nanostructured carbon material.
- a discharge gas excited by an electric field includes at least a gas that receives the energy to be in a plasma state or an excitation state to form a nanostructured carbon material.
- the gas that forms the nanostructured carbon material is a material that receives energy from the discharge gas, excites itself and becomes active, and is chemically deposited on the substrate to form the nanostructured carbon material. It is gas.
- an additional gas for promoting the reaction may be further added.
- the raw material gas including the hydrocarbon gas such as methane, fluorine-based hydrocarbon compounds of carbon oxides such C_ ⁇ 2 and CO, alcohols, ketones, amides, Suruhoki Sid, ethers, esters And the like, and preferred are a hydrocarbon-based gas and a fluorine-based carbonized compound.
- An additional gas may be contained depending on the type of the source gas.
- the additive gas include hydrogen gas, water vapor, hydrogen peroxide gas, carbon monoxide gas, and gases such as carbon fluoride and fluorocarbon. Among them, hydrogen gas, carbon fluoride, and fluorocarbon Steam is preferred.
- the discharge gas is a gas capable of causing a uniform discharge within a discharge surface, in which the material forming gas can be deposited on a base material, and itself serves as a medium for transferring energy.
- the discharge gas include a nitrogen gas, a rare gas, and a hydrogen gas, and these may be used alone as the discharge gas or may be used as a mixture.
- Noble gases include helium, neon, anoregon, krypton, xenon, and rad, elements of Group 18 of the periodic table. And the like.
- argon and nitrogen are preferable as the discharge gas from the viewpoint of mass production cost, and the gas introduced into the discharge space has a volume of 50/0 .
- the above is preferably argon gas and nitrogen or nitrogen gas.
- the amount of the discharge gas is preferably 90 to 99.9% by volume based on the total amount of gas supplied to the discharge space.
- the content in the mixed gas is preferably 0.01 to 10% by volume, and more preferably 0 to 10% by volume. 0 1 to 1% by volume. Further, it is preferable to supply the discharge gas to the discharge space at 0.01 to 50% by volume.
- the temperature at the time of forming the nanostructured carbon material on the substrate using the atmospheric pressure plasma method is preferably 400 ° C. or lower, more preferably 300 ° C. or lower. In this way, by suppressing the rise in temperature when the nanostructured carbon material is formed on the base material, it is possible to use the base material even if the heat resistance is small, such as glass or plastic. I can do it.
- FIG. 1 is a schematic cross-sectional view for explaining the configuration of an FED, which is an example of a planar image device using an electron emission source according to an embodiment of the present invention as a field emission cold cathode.
- the planar imaging device shown in FIG. 1 includes an anode substrate 41 provided with an electron emission source 1 and a phosphor 42, and the electron emission source 1 includes a conductive layer 3 and an insulating layer 4 formed on a base material 2. , A gate layer 5 formed on the insulating layer 4, and a nanostructured carbon material layer 8 formed on the conductive layer 3.
- a negative potential of up to several tens V is applied (a positive potential of several V to several tens V is applied to the anode substrate 41 side, and a positive potential is applied to the gate layer 5).
- the tip radius is as small as 5 nm or less, strong electric field concentration occurs at the tip, and electrons in the nanostructured carbon material layer 8 are emitted toward the anode substrate 41.
- the emitted electrons collide with the phosphor 42 provided on the anode substrate 41 side, causing the phosphor 42 to emit light.
- the substrate 2 may be any of insulating, conductive, and semiconductive materials, such as quartz glass, sapphire, crystallized transparent glass, Pyrek, (R) glass, soda lime glass, low soda glass, lead alkali silicate glass, Inorganic materials such as glass materials such as acid glass, ceramic materials such as alumina, zirconia, titania, silicon nitride, silicon carbide, gadolinium, gallium, and garnet may be used, and the following resin materials (organic materials) May be.
- the resin material various materials can be used as long as the material has heat resistance.Examples of the material having a heat resistance temperature of 250 ° C or less include polyimide, fluororesin, polyetheretherketone (PEEK), and the like. Polyethersulfone (PES), polyparapanoic acid resin, polyphenylene oxide, polyarylate resin, and even epoxy resin can be used. Among them, polyimide can be preferably used.
- ABS resin polycarbonate, polypropylene, acrylic resin, styrene resin, polyarylate, polysulfone, polyethersulfone, epoxy resin, poly-1-methinolepentene-1, fluorinated polyimide, phenoxy resin, polyolefin Resin, nylon resin, polyamide resin, polyamide-imide resin, Polytetrafluoroethylene resin (PTFE), Polytetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), Polytetrafluoroethylene-hexafluoropropylene copolymer (FEP), High temperature nylon resin, Polyphen Diene sulfide resin (PPS), trifluorinated ethylene resin (CTFP), modified phenol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyetheretherketone (PEEK) Fillers such as glass fiber, glass beads, graphite, carbon fiber, fluororesin, molyb
- polyimide resin containing graphite polyimide resin containing graphite, nylon resin containing graphite, acetal resin containing PTFE, phenol resin containing PTFE, and the like.
- Materials having a heat resistance temperature of 250 ° C or higher include glass fibers, glass beads, graphite, carbon fibers, fluororesins, and molybdenum disulfide in base resins such as polyimide resin, polyamide resin, and polyamideimide resin.
- a heat-resistant resin to which a filler such as titanium oxide is added is suitable, and a heat-resistant resin to which the above-mentioned filler is added to a fluorine resin is also suitable as a material having a continuous use temperature of 250 ° C. or higher.
- These resin substrates and composite substrates are used as plate-shaped or film-shaped substrates.
- FIGS. 2 (a) to 2 (k) are schematic cross-sectional views for explaining a patterning step of patterning a nanostructured carbon material by lithography according to an embodiment of the present invention.
- FIGS. 2 (a) to 2 (k) show a substrate cleaning step, a conductive layer forming step, an insulating layer forming step, a gate layer forming step, an opening forming step, and a sacrificial layer coating step, respectively.
- the process represents an exposure process, a development process, a metal particle attachment process, a nanostructure carbon material application process, and a sacrificial layer removal process.
- FIG. 3 shows a plasma jet in the atmospheric pressure plasma discharge treatment apparatus used in the present invention.
- FIG. 4 is a cross-sectional view showing an example of a gas introduction part and an electrode part in a mold type device. Processes that can be processed using the processing apparatus shown in FIG. 3 are the base material cleaning process and the insulating layer film forming process shown in FIGS. 2 (a) to 2 (k).
- a pair of electrodes 21a and 21b connected to a first power supply 11 are provided in parallel. At least one of the electrodes is covered with a dielectric 22, and a high-frequency voltage is applied by a first power supply 11 to a space 23 formed between the electrodes.
- the electrodes 21a and 21b have a hollow structure 24 inside. While discharging, heat generated by the discharge is discharged by water, oil, etc., and heat exchange is performed to maintain a stable temperature. You can do it.
- the metal base material is preferably stainless steel or titanium from the viewpoints of the power and processing of metals such as silver, platinum, stainless steel, aluminum, and iron.
- the dielectric is preferably an inorganic compound having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, silicate glass, and borate. There are glass lining materials such as system glass. Among them, a dielectric material provided by spraying alumina is preferable.
- the distance between the opposing electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the thickness of the base material, the magnitude of the applied voltage, the purpose of using plasma, etc.
- the minimum distance between the surface of the dielectric and the surface of the conductive metal base material when a dielectric is provided on one of the electrodes, and the distance between the surfaces of the dielectric when the dielectric is provided on both of the electrodes is preferably from 0.1 to 20 mm, particularly preferably from 0.5 to 2 mm, from the viewpoint of uniform discharge.
- a gas 31 containing a discharge gas is supplied to the space 23 through the flow path 34 by a gas supply means (not shown), and when a high frequency is applied to the space 23, a discharge is performed and the gas is discharged. 31 1 is turned into plasma. The gas 31 converted into plasma is ejected into a mixed space 25 with the raw material gas.
- the mixed gas 32 containing the raw material gas supplied by the gas supply means passes through the flow path 35 and is similarly conveyed to the mixing space 25, where it is mixed with the discharge gas converted into plasma and mixed therewith. Is sprayed onto the substrate 2.
- the source gas that has come into contact with the plasma-mixed gas is activated by the energy of the plasma and causes a chemical reaction, whereby a desired thin film or structure is formed on the substrate 2.
- the apparatus of this example has a structure in which a mixed gas 32 containing a source gas is sandwiched or surrounded by an activated discharge gas.
- the moving stage 27 has a structure capable of reciprocating or continuous scanning, and, if necessary, has a structure capable of performing the same heat exchange as that of the electrodes so that the temperature of the base material can be maintained. I have. Further, a mechanism 70 for exhausting the gas blown onto the base material can be provided as necessary. This makes it possible to quickly remove unnecessary duplicates ⁇ generated in the space from the discharge space and the substrate.
- the base material used is not limited to a plate-shaped flat base material, and a three-dimensional object or a film-shaped base material can be adopted by changing the structure of the moving stage.
- FIG. 4 is a cross-sectional view showing an example of a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in the present invention.
- Processes that can be processed using the processing apparatus shown in FIG. 4 are the conductive layer forming process, the gut layer forming process, and the nanostructure carbon material applying process shown in FIGS. 2 (a) to 20.
- the moving stage 27 constitutes one of the electrodes facing each other, and the two electrodes 21a and 21b connected to the power supply 11 are provided side by side so as to be parallel to the moving stage 27. I have.
- Each or at least one of the electrodes 21 a and 21 b and the moving stage 27 is coated with a dielectric 22, and between the electrodes 21 a and 27 and between the electrodes 21 b and 27.
- a high frequency voltage is applied to the space 23 formed between the electrodes 11 by the electrode 11.
- the electrodes 21a, 21b and 27 have a hollow structure 24 inside, and during the discharge, waste heat of the heat generated by the discharge is generated by water, oil, etc., and stable. Heat exchange can be performed to maintain the temperature.
- the gas 31 containing the discharge gas flows through the flow path 34 and the mixed gas 32 containing the raw material gas flows through the flow path 35 and is mixed and mixed into the mixing space 25 by a gas supply means (not shown). Is done.
- the mixed gas passes between the electrodes 21 a and 21 b and is supplied to the space 23 between the electrodes 21 a and 27 and the electrodes 21 b and 27, and a high frequency is supplied to the space 23.
- FIG. 5 is a schematic sectional view of a manufacturing apparatus for forming metal fine particles in an atmospheric pressure plasma discharge treatment apparatus used in the present invention.
- the electrodes 21a and 21b in FIG. 4 By changing the electrodes 21a and 21b in FIG. 4 to sputter targets such as iron, chromium, and nickel, the production apparatus shown in FIG. 5 can be obtained.
- Other configurations are the same as those of the manufacturing apparatus of FIG. 4, and the description is omitted. In the manufacturing apparatus shown in FIG.
- the electrode 27 requires the dielectric 22, and the gap D 1 between the electrodes 21 a and 21 b and the base material 2 is preferably 5 mm or less.
- the particle size of the metal fine particles produced by the production apparatus is 10 to 100 nm. Further, it is preferable to use a metal fine particle layer having a thickness of 10 nm to 1 zm obtained in the metal fine particle attaching step.
- FIG. 6 is a view showing another example of a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in the present invention. It is preferable to use an inexpensive gas such as argon gas or nitrogen gas as the discharge gas because the cost of forming a nanostructured carbon material can be reduced.
- An inexpensive gas such as argon gas or nitrogen gas
- One method for generating high-energy plasma with such a gas is as follows. As in the atmospheric pressure plasma discharge device shown in FIG. 6, there is a method in which different frequencies are applied to opposing electrodes.
- the frequency of the first power supply 11 is preferably 200 kHz or less, and the lower limit is preferably about 1 kHz.
- the frequency of the second power source 12 is 800 kHz or more. Is preferably used. The higher the frequency of the second power supply 12, the higher the plasma density.
- the upper limit is preferably about 20 OMHz.
- the electric field waveform may be a sign wave or a pulse wave, but is preferably a sine wave.
- the discharge output of the voltage introduced between the electrodes (discharge space) is preferably 1 W / cm 2 or more, more preferably 1 to 5 OW / cm 2 .
- a mixed gas 32 containing a source gas indicated by a white arrow and a gas 31 containing a discharge gas indicated by a black arrow are mixed and flown into the base material 2.
- the mixed gas that has collided with the base material 2 moves in the discharge space 25 along the surface of the base material 2 and is then discharged to the outside.
- the first filter 18a is provided between the electrodes 21a and 21b and the first power supply 11 so that the current from the first power supply 11 flows toward the electrodes 21a and 21b. It is installed and designed to make it difficult for the current from the first power supply 11 to pass, and to make it easy for the current from the second power supply 12 to pass. Also, a second filter 18 b is provided between the moving stage electrode 27 and the second power source 12 so that the current from the second power source 12 flows toward the moving stage electrode 27. It is designed so that the current from the second power supply 12 is difficult to pass and the current from the first power supply 11 is easy to pass.
- the first filter 18a a capacitor of several tens to tens of thousands of pF or a coil of several ⁇ ⁇ can be used depending on the frequency of the second power supply.
- a coil of 10 ⁇ m or more according to the frequency of the first power supply can be used, and these coils or capacitors can be used as a filter by grounding to ground.
- FIG. 7 is a cross-sectional view showing an example of an apparatus in which a cleaning film is provided in a direct type apparatus in the atmospheric pressure plasma discharge processing apparatus used in the present invention.
- Processes that can be processed using the processing apparatus shown in FIG. 7 are a gate layer and insulating layer etching process and a metal fine particle attaching process shown in FIGS. 2 (a) to 2 (k).
- a pair of electrodes 21a and 2lb facing each other are arranged at an interval D2.
- a gas supply unit 60 that ejects gas toward the gap between the pair of electrodes 21a and 21b is arranged at a position facing the gap.
- the gas supply section 60 has a nozzle main body 61 having a gas flow path formed therein, and projects from the nozzle main body 61 toward a flow path 29 to eject gas in communication with the gas flow path.
- a gas jetting part 62 is a gas jetting part 62.
- the cleaning film 53 for preventing the pair of electrodes 21a and 21b from being stained is continuously or intermittently driven by the film transport mechanism 50 while being in close contact with the electrodes 21a and 21b. It is provided to be transported.
- the film transport mechanism 50 is provided with a film guide roller 51 for guiding the clear film 53 near the gas supply unit 60. On the upstream side of the film guide roller 51, an unillustrated unwinding roller or an original winding of the cleaning film 53 is provided. Further, a take-up unit (not shown) that winds the cleaning film 53 through the other film guide roller 32 farther than the film guide roller 51 with respect to the gas supply unit 60. Is provided.
- the width dimension of the cleaning film 53 be set so that both ends protrude by 1 to 100 mm from both ends of the electrodes 21a and 21b.
- the cleaning film 53 becomes larger than the discharge space, so that the electrodes 21a and 21b can be prevented from being stained without being exposed to the discharge plasma. Since the cleaning film 53 and the nozzle body 61 are in contact with each other as described above, the space from the gas supply unit 60 to the flow path 29 is partitioned by the cleaning film 53. Therefore, the gas can be prevented from flowing out of the flow path 29.
- 5 volumes are applied to the surface of the substrate 2 using the apparatus shown in FIG.
- a nitrogen gas mixed with / 0 oxygen gas is blown, and a high frequency (sine wave or pulse wave) of 50 kHz (l kHz to 10 OMHz is applied) is applied under a high pressure of 5 kV for 10 seconds.
- An inert gas such as helium or argon may be used instead of nitrogen gas, and hydrogen, a fluorine-based compound, or water may be used instead of oxygen gas.
- the conductive layer forming step shown in FIG. 2 (b) 0.1% by volume of aluminum acetyl acetonate gas and 4% by volume of An argon gas mixed with hydrogen gas was blown, and a high frequency of 13.56 MHz and 10 W / cm 2 was applied for 300 seconds to form an aluminum film having a thickness of 300 nm as the conductive layer 3.
- Helium instead of argon gas, it may be inactivated I 1 raw gas such as nitrogen gas, the frequency of the high frequency wave may be l kHz ⁇ 100MHz.
- the conductive layer 3 may be made of a material having conductivity, and besides aluminum, molybdenum, tantalum, tungsten, chromium, nickel, copper, or the like can be used.
- iron, cobalt, rhodium, palladium, platinum, lanthanum, cerium, etc. which are used as catalyst materials for nanostructured carbon materials, can also be used.
- nitrogen gas an inert gas such as helium gas or argon gas may be used, and the high frequency may be 1 kHz to 10 OMHz.
- the material used for the insulating layer 4 is preferably a thermally stable substance, such as metal or It consists of metalloid oxides, nitrides, chalcogenides, fluorides, carbides and mixtures thereof.
- S I_ ⁇ 2 specifically, S i O, A 1 2 0 3, Ge 0 2, I n 2 ⁇ 3, T a 2 ⁇ 5, T E_ ⁇ 2, T i 0 2, Mo0 3, W0 3 , Z r 0 2, S i 3 N 4, A l N, BN, T i N, ZnS, Cd S, Cd S e, Zn S e, ZnTe, Ag F, Pb F 2, M nF 2, N i Use a simple substance such as F 2 or SiC or a mixture thereof.
- the thickness of the insulating layer 4 should be in the range of 0.2 to: L 0 / m, preferably 1 to 2 ⁇ m.
- L 0 / m preferably 1 to 2 ⁇ m.
- Argon gas mixed with hydrogen gas
- An inert gas such as a helium gas or a nitrogen gas may be used instead of the argon gas, and the high frequency may be 1 kHz to 100 MHz.
- the CVD material may be an organic metal compound having another conductive metal element, a chloride, or the like.
- the material of the gate layer 5 the same material as that of the conductive layer 3 can be used.
- the gate layer is first etched by a lithography technique to etch the gate layer, and then nitrogen gas is applied by using an apparatus shown in FIG.
- a mixture gas containing 0.1% by volume of chlorine gas was introduced into the mixture, and the mixture was applied at 80 kH and 7 kV.
- the substrate was washed with pure water to remove residual chlorine.
- patterning the insulating layer by lithography using the apparatus shown in FIG. 7, by introducing a mixed gas containing a fluorocarbon gas 41 volume 0/0 Argon gas It was applied at 80 kHz and etched for 150 seconds.
- the opening 81 was formed in the insulating layer 4 and the gate layer 5 to expose the conductive layer 3.
- Inactivation of helium, argon gas, etc. instead of nitrogen gas Gas may be used, and the frequency of the high frequency may be 1 kHz to 100 MHz.
- the etching material may be another material, for example, a chlorine compound in the case of aluminum, a bromine gas, a bromine compound, or the like.
- a fluorine-based gas, an oxygen gas, a hydrogen gas, or the like may be used as needed.
- a wet etching method can be used for the etching step.
- a mask layer 6 is formed by photolithography on the conductive layer 3 exposed on the bottom surface of the formed opening 81. Therefore, the mask layer 6 covers the surface of the gate layer 5, the cross section of the gate layer 5 and the insulating layer 4 (side surface of the opening), and the exposed surface of the conductive layer 3 (bottom surface of the opening).
- a commercially available resist, polyimide, or the like may be applied to the surface and cross-section of the gate layer 5, the cross-section of the insulating layer 4, and the surface of the conductive layer 3, and deposited by spin coating, dip, extrusion coating, or the like. be able to.
- the film thickness of the mask material 6 along the opening is set to be 0.1 m or more and 5 m or less. If the thickness of the mask material is 0.1 m or less, the mask material is too thin, so that the etching solution does not easily penetrate the entire substrate, and the emitter material deposited on the upper layer is removed by lift-off described later. It becomes difficult. When the thickness of the mask material is 5 im or more, the electron emission characteristics are significantly deteriorated as described later. For these reasons, here, the thickness of the mask material 6 deposited on the surface of the opening was set to 1 ⁇ .
- the mask layer 6 is exposed by photolithography.
- a baking step may be appropriately provided to cure the mask material.
- the exposed portion of the mask layer 6 is dissolved by photolithography to form an opening 91 and expose the conductive layer 3.
- the substrate 2 is coated using the apparatus shown in FIG.
- the electrode (described later) opposite to the electrode was replaced with an iron electrode (not shown), the gap between the electrode and the substrate 2 was set to l mm, and argon gas was introduced between the electrode and the substrate 2. 5 6 MH z, and 6 0 seconds casting in 4WZ c ni 2 applied.
- iron fine particles having a particle size of about 50 nm are deposited on the exposed aluminum film of the conductive layer 3 and the mask layer 6, and a metal fine particle layer (iron fine particle layer) having a thickness of about 0.1 ⁇ m is formed. 7 was formed.
- the electrode facing the substrate 2 is replaced with an electrode (not shown) using an alumina dielectric using the apparatus shown in FIG.
- the gap between the electrode 2 and the substrate 2 was set to 1 mm, and an argon gas containing 0.1% by volume of methane gas and 3% by volume of hydrogen gas was introduced between the electrode and the substrate 2.
- the film was formed for 600 seconds by applying MHz.
- the nanofiber-shaped nanostructured carbon material was grown on the iron fine particle layer 7 in the form of catalyst fine particles, and the nanostructured carbon material layer 8 was formed.
- the nanostructured carbon material can be controlled-grown into a graphite structure by changing the plasma application conditions, gas conditions, and pressure conditions in the chamber, in addition to nanofibers.
- the mask layer 6 is removed by lift-off together with unnecessary portions of the iron fine particle layer 7 and the nanostructured carbon material layer 8 to remove the nanostructured carbon which is a field emission type electron emission source.
- the material layer 8 could be formed.
- the fabricated field emission type electron emission source is provided with a phosphor layer of three colors of RGB on a glass support, and an anode electrode coated on the ITO layer is sandwiched by a spacer of 500 im thickness. Glued. Thereafter, the vacuum evacuation hole provided in advance was evacuated to about 10 Pa to 6 Pa to close the opening.
- the vacuum evacuation hole provided in advance was evacuated to about 10 Pa to 6 Pa to close the opening.
- a metal fine particle attaching step of previously attaching metal fine particles to the base material is performed, and then the metal fine particles are attached to the base material.
- a nanostructured carbon material is formed.
- various metals having a catalytic action in the formation of graphite and the vapor phase decomposition growth of carbon nanotubes can be used. Specifically, for example, iron groups such as Ni, Fe, and Co; platinum groups such as Pd, Pt, and Rh; rare earth metals such as La and Y; or Mo and Mn And transition metals such as these, any one of these metal compounds, or a mixture of two or more of these.
- any method may be used as long as the metal fine particles can be deposited on the base material, but it is preferable to use the atmospheric pressure plasma method. In this case, it is preferable to use a simple apparatus configuration. Fine metal particles can be attached to the material.
- the method of attaching metal fine particles to a substrate using an atmospheric pressure plasma method is roughly classified into a CVD method and a sputtering method.
- the sputtering method may use a target of each metal as described above.
- a volatile organometallic compound such as a metal complex such as an alkoxide / beta-diketone can be used as a raw material.
- a nano-structured carbon material and an electron emission source formed on the substrate at a lower substrate temperature (around 400 ° C.) as compared with the conventional technology can be used on a large-area substrate.
- the nanostructured carbon material and the electron emission source can be manufactured efficiently and uniformly using simple equipment that does not require a vacuum facility or a high-temperature generator.
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JP2009170281A (ja) * | 2008-01-17 | 2009-07-30 | Sony Corp | スペーサの製造方法 |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09102269A (ja) * | 1995-06-12 | 1997-04-15 | Korea Inf & Commun Co Ltd | フィールドエミッタアレイ(fea)の製造方法 |
JP2000315453A (ja) * | 1999-04-30 | 2000-11-14 | Fujitsu Ltd | 電界放出陰極のエミッタ及びその製造方法 |
JP2001043789A (ja) * | 1999-07-30 | 2001-02-16 | Sony Corp | 冷陰極電界電子放出素子及びその製造方法、並びに、冷陰極電界電子放出表示装置 |
JP2001176431A (ja) * | 1999-11-05 | 2001-06-29 | Cheol Jin Lee | 電界放出表示素子及びその製造方法 |
JP2002143795A (ja) * | 2000-11-14 | 2002-05-21 | Sekisui Chem Co Ltd | 液晶用ガラス基板の洗浄方法 |
JP2002282807A (ja) * | 2001-03-28 | 2002-10-02 | Toray Ind Inc | 基板の洗浄方法および洗浄装置 |
JP2003303699A (ja) * | 2002-04-08 | 2003-10-24 | Sekisui Chem Co Ltd | 放電プラズマ処理方法及びその装置 |
JP2003317998A (ja) * | 2002-04-22 | 2003-11-07 | Sekisui Chem Co Ltd | 放電プラズマ処理方法及びその装置 |
JP2004362919A (ja) * | 2003-06-04 | 2004-12-24 | Hitachi Zosen Corp | カーボンナノチューブを用いた電子放出素子の製造方法 |
-
2004
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- 2004-11-26 WO PCT/JP2004/017977 patent/WO2005055266A1/ja active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09102269A (ja) * | 1995-06-12 | 1997-04-15 | Korea Inf & Commun Co Ltd | フィールドエミッタアレイ(fea)の製造方法 |
JP2000315453A (ja) * | 1999-04-30 | 2000-11-14 | Fujitsu Ltd | 電界放出陰極のエミッタ及びその製造方法 |
JP2001043789A (ja) * | 1999-07-30 | 2001-02-16 | Sony Corp | 冷陰極電界電子放出素子及びその製造方法、並びに、冷陰極電界電子放出表示装置 |
JP2001176431A (ja) * | 1999-11-05 | 2001-06-29 | Cheol Jin Lee | 電界放出表示素子及びその製造方法 |
JP2002143795A (ja) * | 2000-11-14 | 2002-05-21 | Sekisui Chem Co Ltd | 液晶用ガラス基板の洗浄方法 |
JP2002282807A (ja) * | 2001-03-28 | 2002-10-02 | Toray Ind Inc | 基板の洗浄方法および洗浄装置 |
JP2003303699A (ja) * | 2002-04-08 | 2003-10-24 | Sekisui Chem Co Ltd | 放電プラズマ処理方法及びその装置 |
JP2003317998A (ja) * | 2002-04-22 | 2003-11-07 | Sekisui Chem Co Ltd | 放電プラズマ処理方法及びその装置 |
JP2004362919A (ja) * | 2003-06-04 | 2004-12-24 | Hitachi Zosen Corp | カーボンナノチューブを用いた電子放出素子の製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009170281A (ja) * | 2008-01-17 | 2009-07-30 | Sony Corp | スペーサの製造方法 |
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