WO2005092505A1 - カーボンナノチューブ触媒の選択付与方法 - Google Patents
カーボンナノチューブ触媒の選択付与方法 Download PDFInfo
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- WO2005092505A1 WO2005092505A1 PCT/JP2005/006519 JP2005006519W WO2005092505A1 WO 2005092505 A1 WO2005092505 A1 WO 2005092505A1 JP 2005006519 W JP2005006519 W JP 2005006519W WO 2005092505 A1 WO2005092505 A1 WO 2005092505A1
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- Prior art keywords
- catalyst
- opening
- substrate
- measuring
- deposit
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 94
- 239000010410 layer Substances 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 41
- 230000008021 deposition Effects 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims description 36
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 2
- 230000005684 electric field Effects 0.000 description 12
- 238000012544 monitoring process Methods 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000007733 ion plating Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/347—Ionic or cathodic spraying; Electric discharge
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
Definitions
- the present invention relates to a method for applying a catalyst for producing carbon nanotubes.
- an electron source emitter for emitting electrons In a field emission display (FED: Field Emission Display) or an electron beam storage device, an electron source emitter for emitting electrons needs to be provided.
- the mechanism by which the electron emitter emits electrons is based on a field emission phenomenon that is different from thermionic emission found in conventional CRTs.
- Field emission is a phenomenon in which a strong electric field is applied to a solid surface, and the potential barrier on the surface becomes thinner and lower, so that electrons on the solid surface are emitted into a vacuum by a tunnel effect.
- the tip of the electron source emitter is a carbon nanotube (hereinafter referred to as CNT).
- CNT carbon nanotube
- Carbon nanotubes not only have excellent electrical conductivity, but also have a very large aspect ratio (aspect ratio), sharp tips, and are chemically stable and mechanically tough. It is advantageous to use as the tip of the electron source emitter.
- a single nanotube alone emits a small number of electrons and therefore a small current.
- a nanotube array is used, in which a large number of nanotubes are arranged at the tip of multiple emitters arranged in a sword mountain shape.
- Non-Patent Documents 1 and 2 disclose methods for selectively generating carbon nanotubes at the tips of a plurality of emitters.
- a catalyst is attached to the entire surface of an emitter chip, and CVD (Chemical Vapor Deposition) is performed while applying an electric field in a direction perpendicular to the substrate. It is going to be done. It is also effective to apply a catalyst for CNT growth to each of the tips of the emitter, and the method disclosed in Non-Patent Document 2 arranges Ni metal as a catalyst at a desired position by FIB (Focused Ion Beam). By doing so, it is possible to grow CNT selectively at that position.
- FIB Fluorused Ion Beam
- NPA Nickel Implanted Nanopyramids Array
- Non-Patent Document 1 since a catalyst thin film is provided on the entire surface of the substrate, the growth point of the CNT depends on the shape of the substrate that determines the electric field distribution. There is a title. Also, if there is contamination such as dust, electric field concentration occurs there as well.
- Non-Patent Document 2 has a problem that the FIB must be precisely positioned at the tip of the emitter chip because the CNT growth catalyst is directly applied by the FIB.
- An object of the present invention is to provide a method for applying a catalyst, which allows a growth position of a carbon nanotube to be selected accurately and easily.
- the catalyst applying method of the invention according to claim 1 is a method of applying a catalyst for growing carbon nanotubes to at least one predetermined position on a substrate surface of a substrate made of a conductive material, wherein a coating layer is formed on the substrate surface. Forming a hole in contact with the substrate surface in a coating layer at a position corresponding to each of the predetermined positions; and forming a conductive layer while rotating the substrate around an axis substantially perpendicular to the substrate surface. By obliquely irradiating the material particles with an upward force on the coating layer, a cone-shaped deposit is deposited on a portion of the substrate surface in contact with the hole, and an eave-shaped deposit extending to close the opening of the hole.
- a deposition step of depositing a layer a measurement step of measuring the size of the opening according to the elongation of the eaves-like deposition layer, and, if the size of the opening is measured to be a predetermined size, the opening of the opening
- the catalyst by irradiating the material particles of the catalyst through the And a catalyst providing step of providing the tip of the cone-shaped deposit.
- a field emission projection is formed at at least one predetermined position on a substrate surface of a substrate made of a conductive material, and the field emission projection is used for growing a carbon nanotube.
- a method of applying a catalyst comprising: preparing a coating layer having a hole in contact with the substrate surface at a position corresponding to each of the predetermined positions on the substrate; and providing the substrate with an axis substantially perpendicular to the substrate surface. While rotating around, conductive material particles are inclined from above the coating layer. Irradiation deposits a pyramidal deposit as the field emission projection on the surface of the substrate in contact with the hole, and deposits an eaves-like deposition layer extending so as to close the opening of the hole.
- FIG. 1A is a schematic cross-sectional view showing a cross section of a substrate in a preparation step according to the first embodiment of the present invention.
- FIG. 1B is a schematic sectional view showing a cross section of the substrate in the deposition step in the first example of the present invention.
- FIG. 1C is a schematic cross-sectional view showing a cross section of the substrate in the measurement step in the first example of the present invention.
- FIG. 1D is a schematic cross-sectional view showing a cross section of the substrate in the catalyst step in the first example of the present invention.
- FIG. 1E is a schematic cross-sectional view showing a cross section of the substrate in a final step in the first example of the present invention.
- FIG. 2 is a schematic cross-sectional view showing a cross section of a substrate in an initial step according to a second embodiment of the present invention.
- FIG. 3A is a schematic sectional view showing a cross section of a substrate in a deposition step according to a third embodiment of the present invention.
- FIG. 3B is a schematic cross-sectional view illustrating a substrate in a catalyst applying step according to a third embodiment of the present invention. It is a schematic sectional drawing.
- FIG. 4 is a schematic sectional view showing a cross section of a substrate according to a fourth embodiment of the present invention.
- FIG. 1A shows an apparatus for performing the catalyst applying method and a preparation step in which a substrate is prepared.
- the apparatus includes a conductive substrate 1 such as a Si substrate, a substrate rotating motor 5 for rotating the conductive substrate 1, a DC power supply 6, an ammeter 7, and a material source 8 for creating an emitter and an opening. including.
- a dielectric layer 2, a conductive layer 3, and a release layer 4 are sequentially laminated on both sides of the hole 11 in the cross section.
- the holes 11 are formed by a photolithography process in which a material corresponding to each of the dielectric layer 2, the conductive layer 3, and the release layer 4 is sequentially laminated, and then a circular etching is performed on the plane of the conductive substrate 1. It is formed in a cylindrical shape.
- a material of the dielectric layer 2, the conductive layer 3, and the release layer 4 for example, SiO2, A1, and a resin for resist can be used, respectively.
- one cylindrical hole 11 is shown for ease of explanation, but a large number of holes are formed in the conductive substrate 1 so as to be arranged in an array. May be.
- the rotation motor 5 rotates the conductive substrate 1 at a constant speed about an axis perpendicular to the plane.
- the DC power supply 6 has its positive side connected to the conductive substrate 1 and its negative side connected to the conductive layer 3 via the ammeter 7, and applies a voltage between the conductive substrate 1 and the conductive layer 3.
- Ammeter 7 Measures the field emission electron current flowing between the conductive substrate 1 and the conductive layer 3.
- the material source 8 for forming the minute opening forms an opening with an eave-like deposition layer near the top of the hole 11 and forms a conical deposit as an emitter at the bottom of the hole 11, that is, on the conductive substrate 1.
- It is a material source that can be used as a catalyst for conductive materials, for example, CNT such as Cr.
- the irradiation of the material from the material source 8 is performed from a certain direction obliquely above the conductive substrate 1 by deflecting the ion beam by an electric field.
- the angle of the oblique irradiation is an appropriate angle determined by the ratio between the height and the diameter of the cylindrical hole 11.
- the position of the material source 8 is laterally offset on the horizontal plane of the substrate according to the distance from the conductive substrate 1.
- the irradiation of the material from the material source 8 may use a vapor deposition device or a sputtering device as long as the deposited particles can be irradiated in a specific direction such as a slanting direction.
- FIG. 1B shows a state of a deposition process from a material source 8.
- a material source 8 For the state shown in FIG. 1A to the portion extending from the upper surface of the release layer 4 to the conductive layer 3 through the edge with the hole 11, an eave is formed in an eaves-like cross section.
- a conical deposit 9 is formed at the bottom of the hole 11. This is because the conductive substrate 1 is irradiated with the material obliquely from the material source 8 while the conductive substrate 1 is rotated by the rotation motor 5 as described above. It is deposited so as to extend toward the center of the hole 11 of the shape.
- a conical deposit 9 is formed at the bottom of the hole 11 opened by the photolithographic process.
- FIG. 1C shows a state of a measurement process for measuring a field emission electron current.
- the electric field intensity is sufficiently increased, electron emission starts from the tip of the conical deposit 9, and a current flows between the conductive substrate 1 and the conductive layer 3 via the eaves-like deposition layer 10. Flows.
- the ammeter 7 By monitoring this current with the ammeter 7, it is possible to know when the opening of the hole 11 has become sufficiently small (that is, a minute opening).
- the appropriate correspondence between the applied voltage, the aperture diameter, and the current value is empirically determined.
- FIG. 1D shows a state of a catalyst step for providing a catalyst.
- the catalyst material source 12 for CNT growth is positioned so that the offset with respect to the conductive substrate 1 is smaller than the material source 8 for the deposited layer.
- the catalyst material source 12 irradiates the conductive substrate 1 with the catalyst material particles through the hole 11 having a small opening.
- the catalyst 13 is selectively applied to the conical tip of the conical deposit 9 on the conductive substrate 1 in a region corresponding to the small opening diameter of the hole 11.
- FIG. 1E shows a state of a final step of removing the release layer.
- the release layer 4 together with the eaves-like deposited layer 10 adhered thereto is removed by a washing step using a suitable solvent.
- a state is obtained in which the catalyst 13 for CNT growth is applied only to an extremely narrow region, that is, only to the conical tip of the conical deposit 9.
- a configuration is provided in which the size of the conical deposit, that is, the area where the catalyst can be applied only to the tip of the emitter, that is, the size of the minute opening is electrically measured. This makes it possible to appropriately control the area to which the catalyst is applied to a minute area.
- the positional relationship between the deposition material source and the substrate is offset so that the deposition direction is oblique, and the positional relationship between the material sources when applying the catalyst
- reduce the offset amount and increase the angle of incidence on the substrate compared to when using a deposition material source reduce the size of the target, or increase the distance to the target to enter the small opening force This makes it possible to make the area to which the catalyst substance is applied smaller.
- FIG. 2 shows a configuration for realizing the catalyst application method in the second embodiment.
- a dielectric layer 2, a conductive layer 3, and a release layer 4 are laminated on a conductive substrate 1 in the same manner as in the first embodiment.
- a variable DC power supply 6 'capable of arbitrarily changing the supply voltage is connected with an appropriate polarity, and a voltmeter 19 and an ammeter 7 are connected. Have been.
- FIG. 1 shows a configuration for realizing the catalyst application method in the second embodiment.
- the eaves-like deposition layer 10 is formed and the conical deposit 9 is formed at the bottom of the hole 11 by the deposition process from the material source 8 in the same manner as in the first embodiment.
- the conductive substrate 1 is being rotated by the rotation motor 5.
- a DC voltage adjusted by the variable DC power supply 6 ′ is applied between the conductive substrate 1 and the conductive layer 3. In this case, electron emission occurs as the shape of the tip of the conical deposit 9 becomes sharper.
- the voltage at which the field emission starts by adjusting the voltage of the variable DC power supply 6 ′ is detected by monitoring the current value of the ammeter 7. That is, in the early stage when the deposition of the conical deposit 9 starts, the voltage required for emitting electrons is high. However, as the sharpness of the tip increases, the electric field concentration at the tip increases, and the applied voltage required for electron emission decreases. By monitoring the applied voltage necessary for electron emission in this manner, the angle of the tip of the conical deposit 9 on the substrate can be monitored, and the state of the opening diameter of the hole 11 can be monitored. I can figure it out. The relationship between the appropriate opening diameter and the field emission start voltage can be determined empirically. When an appropriate opening diameter is obtained, the catalyst 13 is applied to the conical deposit 9 in the same manner as in the first embodiment.
- the second embodiment is the same as the first embodiment in that the field emission electrons are monitored, but differs in that the applied voltage is adjusted so that the amount of the field emission electron current does not fluctuate. . Since the field emission start voltage can be accurately measured, the accuracy of the measurement of the opening diameter of the hole 11 is improved.
- 3A to 3B show a configuration for realizing the catalyst application method in the third embodiment.
- a configuration is shown in which deposited particles from the material source 8 are used as charged particles to monitor the amount of adhesion to the substrate side.
- the deposition particles from the material source 8 are deposited as an eaves-like deposition layer 10 and a conical deposit 9 on the conductive substrate 1.
- the amount of the deposited particles is detected by detecting the charge carried by the deposited particles as a current.
- FIG. 3A shows a configuration in a deposition step in the third embodiment.
- a dielectric layer 2, a conductive layer 3, and a release layer 4 are laminated on the conductive substrate 1 in the same manner as in the first embodiment.
- the conductive substrate 1 is further grounded via the ammeter 7, and the conductive layer 3 is grounded.
- the irradiation from the material source 8 is performed by ion plating, and the deposition is performed obliquely while the conductive substrate 1 is rotated by the rotation motor 5. At this time, the charge of the deposited particles deposited on the eaves-like deposited layer 10 flows to the ground plane.
- the charges carried by the sediment particles that reach the conical sediment 9 flow to the ground via the ammeter 7.
- the current flowing through the ammeter 7 reaches the conical sediment 9 by closing the opening as the eaves of the eaves-like layer 10 extend toward the center of the opening of the hole 11. It decreases as the number of deposited particles decreases.
- the state of the opening of the cylindrical hole 11 can be grasped.
- the relationship between the appropriate opening diameter and the current value due to the deposited particles can be determined empirically.
- the catalyst 13 is applied to the conical deposit 9 in the same manner as in the first embodiment.
- FIG. 3B is a modification of the third embodiment, and shows a configuration in a catalyst applying step.
- a DC power supply 6 and an ammeter 7 are connected in series between the conductive substrate 1 and the conductive layer 3.
- a potential difference is provided between the conductive substrate 1 and the conductive layer 3.
- an electric field is generated between the conductive substrate 1 and the conductive layer 3, and the isoelectric surface thereof becomes sharper as the shape of the conical deposit 9 becomes more advanced. .
- the accumulation of the sedimentary particles with the electric charge can be concentrated on the tip portion of the conical sediment 9. Further, the state of deposition can be monitored by monitoring the current value of the ammeter 7.
- the catalyst applying step by applying a voltage between the conductive substrate and the conductive layer, it is possible to apply the catalyst to a finer region at the tip of the conical deposit.
- FIG. 4 shows a configuration for realizing the catalyst application method in the fourth embodiment.
- the configuration is such that the state of the minute opening is grasped more directly by capturing the field emission electrons that have jumped out through the minute opening of the eaves-like deposited layer by the anode electrode.
- a dielectric layer 2 is formed on a conductive substrate 1 in the same manner as in the first embodiment.
- the conductive layer 3 and the release layer 4 are laminated.
- an anode electrode 14 is further provided on the conductive substrate 1 including the hole 11 formed by the dielectric layer 2, the conductive layer 3, and the release layer 4.
- An ammeter 7, a DC power supply 6a and a DC power supply 6b are connected to the anode electrode 14 in series and then grounded.
- the DC power supply 6a and the DC power supply 6b apply a positive voltage to the anode electrode 14.
- the positive electrode side of the DC power supply 6b is connected to the conductive layer 3, and applies a positive voltage to the conductive layer 3.
- a material source 8 is provided in the same manner as in the first and second embodiments.
- the material source 8 and the substrate are connected. It is necessary to provide a shirt 15 in between to prevent the deposited particles from being affected by the anode electrode 14 when measuring the current of the field emission electrons.
- a switch 16 for turning ON / OFF the irradiation from the material source 8 is provided between the material source 8 and the power supply 17, so that the current measurement process of the field emission electrons and the deposition process from the material source 8 are alternated. To be able to run.
- the irradiation from the material source 8 is performed by vapor deposition, sputtering or ion plating, and deposition is performed obliquely while the conductive substrate 1 is rotated by the rotation motor 5.
- the deposition is performed by vapor deposition or sputtering
- the field emission electron current is measured using the ammeter 7 at the same time.
- the shutter 15 of the material source 8 is closed and the switch 16 is turned off to measure the field emission electron current.
- the state of the opening of the cylindrical hole 11 can be grasped by monitoring the current caused by the electrons captured by the anode electrode 14.
- the relationship between the appropriate aperture size and the current value of the deposited particles can be determined empirically.
- the catalyst can be applied to the conical deposit 9 in the same manner as in the first embodiment.
- the state of the opening diameter can be directly grasped by measuring the amount of electrons that fly out through the minute opening.
- a catalyst can be selectively applied to a point where CNT is to be grown.
- the position where the catalyst is to be applied is precisely controlled, and the catalyst can be applied without being affected by contamination.
- the position of the hole where the minute opening is provided is formed by a mask at the level of photolithography, so that the catalyst can be applied to an arbitrary position. Further, since the catalyst can be applied to the entire surface of the substrate in the same manner as in the prior art, it is easy to carry out the application. Further, even when manufacturing a field emission array in which a large number of emitters are arrayed, it is possible to apply the catalyst to all the emitters in one process. Industrial availability
- a method and an apparatus for selectively applying a catalyst for growing carbon nanotubes to an arbitrary position on a substrate for a field emission source have been described. It can be applied to all fields where carbon nanotubes need to be selectively grown on a substrate, such as a field emission display (FED), a field emission imaging device, and other field emission sources. Applicable to the equipment used.
- FED field emission display
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Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006511610A JP4672653B2 (ja) | 2004-03-29 | 2005-03-28 | カーボンナノチューブ触媒の選択付与方法 |
US11/547,105 US20070265158A1 (en) | 2004-03-29 | 2005-03-28 | Method of Selectively Applying Carbon Nanotube Catalyst |
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JP2004-094960 | 2004-03-29 | ||
JP2004094960 | 2004-03-29 |
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WO2005092505A1 true WO2005092505A1 (ja) | 2005-10-06 |
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US (1) | US20070265158A1 (ja) |
JP (1) | JP4672653B2 (ja) |
WO (1) | WO2005092505A1 (ja) |
Cited By (1)
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RU2561267C2 (ru) * | 2009-11-25 | 2015-08-27 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Нанопористая полимерная пена, имеющая высокую пористость |
Families Citing this family (1)
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US7678672B2 (en) * | 2007-01-16 | 2010-03-16 | Northrop Grumman Space & Mission Systems Corp. | Carbon nanotube fabrication from crystallography oriented catalyst |
Citations (1)
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JP2003288833A (ja) * | 2001-03-27 | 2003-10-10 | Canon Inc | カーボンファイバーの形成に用いる触媒及びその製造方法、並びに電子放出素子、電子源、画像形成装置 |
Family Cites Families (11)
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US5007873A (en) * | 1990-02-09 | 1991-04-16 | Motorola, Inc. | Non-planar field emission device having an emitter formed with a substantially normal vapor deposition process |
JP3007654B2 (ja) * | 1990-05-31 | 2000-02-07 | 株式会社リコー | 電子放出素子の製造方法 |
JP3252545B2 (ja) * | 1993-07-21 | 2002-02-04 | ソニー株式会社 | 電界放出型カソードを用いたフラットディスプレイ |
US6033277A (en) * | 1995-02-13 | 2000-03-07 | Nec Corporation | Method for forming a field emission cold cathode |
US5702281A (en) * | 1995-04-20 | 1997-12-30 | Industrial Technology Research Institute | Fabrication of two-part emitter for gated field emission device |
US6020677A (en) * | 1996-11-13 | 2000-02-01 | E. I. Du Pont De Nemours And Company | Carbon cone and carbon whisker field emitters |
JP3139541B2 (ja) * | 1997-12-01 | 2001-03-05 | 日本電気株式会社 | 電界放出型冷陰極の製造方法 |
US6120857A (en) * | 1998-05-18 | 2000-09-19 | The Regents Of The University Of California | Low work function surface layers produced by laser ablation using short-wavelength photons |
JP2000021287A (ja) * | 1998-06-30 | 2000-01-21 | Sharp Corp | 電界放出型電子源及びその製造方法 |
KR100360470B1 (ko) * | 2000-03-15 | 2002-11-09 | 삼성에스디아이 주식회사 | 저압-dc-열화학증착법을 이용한 탄소나노튜브 수직배향증착 방법 |
US6864162B2 (en) * | 2002-08-23 | 2005-03-08 | Samsung Electronics Co., Ltd. | Article comprising gated field emission structures with centralized nanowires and method for making the same |
-
2005
- 2005-03-28 US US11/547,105 patent/US20070265158A1/en not_active Abandoned
- 2005-03-28 JP JP2006511610A patent/JP4672653B2/ja not_active Expired - Fee Related
- 2005-03-28 WO PCT/JP2005/006519 patent/WO2005092505A1/ja active Application Filing
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JP2003288833A (ja) * | 2001-03-27 | 2003-10-10 | Canon Inc | カーボンファイバーの形成に用いる触媒及びその製造方法、並びに電子放出素子、電子源、画像形成装置 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2561267C2 (ru) * | 2009-11-25 | 2015-08-27 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Нанопористая полимерная пена, имеющая высокую пористость |
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JPWO2005092505A1 (ja) | 2008-02-07 |
US20070265158A1 (en) | 2007-11-15 |
JP4672653B2 (ja) | 2011-04-20 |
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