WO2007139086A1 - カーボンナノチューブ成長用基板、カーボンナノチューブ成長方法、カーボンナノチューブ成長用触媒の粒径制御方法、及びカーボンナノチューブ径の制御方法 - Google Patents
カーボンナノチューブ成長用基板、カーボンナノチューブ成長方法、カーボンナノチューブ成長用触媒の粒径制御方法、及びカーボンナノチューブ径の制御方法 Download PDFInfo
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- WO2007139086A1 WO2007139086A1 PCT/JP2007/060859 JP2007060859W WO2007139086A1 WO 2007139086 A1 WO2007139086 A1 WO 2007139086A1 JP 2007060859 W JP2007060859 W JP 2007060859W WO 2007139086 A1 WO2007139086 A1 WO 2007139086A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0004—Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
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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
- 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
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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
- B01J37/349—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 flames, plasmas or lasers
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12063—Nonparticulate metal component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a carbon nanotube (hereinafter referred to as CNT) growth substrate, a CNT growth method, a particle size control method for a CNT growth catalyst, and a CNT diameter control method.
- CNT carbon nanotube
- the catalyst is usually formed as a thin film on the substrate by sputtering or EB evaporation, and the catalyst formed on the surface of the thin film is heated.
- the substrate is made into fine particles before and during the CNT growth process, etc., and this finely divided catalyst is used.
- the catalyst particle size is difficult to control because it is affected by various conditions such as the underlying buffer layer, process conditions, and catalyst film thickness.
- the particle size tends to be large because the particles are formed by aggregation of the catalyst.
- the smaller the diameter of the catalyst particles the easier it is to grow CNT. This particle size varies depending on the catalyst film thickness, pretreatment process conditions, reaction conditions, etc. Therefore, it is difficult to control easily.
- Patent Document 1 Japanese Patent Laid-Open No. 2001-48512 (Claims)
- Patent Document 1 Japanese Patent Application Laid-Open No. 2005-350342 (Claims)
- the problem is that CNTs cannot be grown sufficiently efficiently and at the lowest possible temperature so that they can be used in various fields including the semiconductor device manufacturing field.
- the particle diameter of the CNT growth catalyst and the inner diameter and Z or inner diameter of the CNT cannot be controlled. Therefore, a desired catalyst fine particle, for example, a catalyst fine particle having a controlled particle diameter, can be easily produced at the time of forming the catalyst layer, and the desired CNT, for example, the diameter is controlled on the catalyst layer. There is a need for a method that can grow CNTs efficiently.
- an object of the present invention is to solve the above-mentioned problems of the prior art, and a substrate for efficiently growing CNT, and a method for efficiently growing desired CNT on the substrate.
- Another object of the present invention is to provide a method for controlling the particle diameter of a CNT catalyst, and a method for controlling the CNT diameter when growing CNTs on a catalyst having a controlled particle diameter.
- the carbon nanotube (CNT) growth substrate of the present invention is characterized by having a catalyst layer formed on the surface using a coaxial vacuum arc deposition source (hereinafter referred to as an arc plasma gun).
- a coaxial vacuum arc deposition source hereinafter referred to as an arc plasma gun.
- the catalyst layer on the substrate also has a catalytic force whose particle size is controlled according to the number of shots of the arc plasma gun.
- the CNT growth substrate of the present invention preferably further comprises a buffer layer as an underlayer, and a catalyst layer formed by using an arc plasma gun on the buffer layer. In this case as well, it is preferable that the catalyst layer has a catalytic force whose particle size is controlled according to the number of shots of the arc plasma gun! /.
- the buffer layer is preferably a metal film selected from Ti, Ta, Sn, Mo, and A1, a nitride film of these metals, or an oxide film of these metals.
- a metal film selected from Ti, Ta, Sn, Mo, and A1
- a nitride film of these metals or an oxide film of these metals.
- Each of the metal, nitride and oxide may be a mixture of at least two.
- the catalyst layer may be used as an arc plasma gun target as an alloy or a compound containing at least one of Fe, Co and Ni, or at least one of these metals, or a metal, an alloy and an alloy thereof. Physical strength It is preferable that it is formed using a target that has at least two types of mixture strength.
- the catalyst layer is further activated with hydrogen radicals after formation, and further has a catalyst protective layer made of metal or nitride on the surface thereof.
- the metal used as the catalyst protective layer is a metal selected from Ti, Ta, Sn, Mo, and A1, and the nitride is preferably a nitride of these metals.
- Each of the above metal and nitride may be a mixture of at least two kinds.
- the CNT growth method of the present invention is characterized in that a catalyst layer is formed on a substrate using an arc plasma gun, and CNT is grown on the catalyst layer by a thermal CVD method or a remote plasma CVD method. . This achieves finer catalyst and enables CNT growth at lower temperatures.
- a substrate having a buffer layer as an underlayer for the catalyst layer.
- the buffer layer is made of Ti, Ta, Sn, Mo, and A1 force. These films, nitride films of these metals, or oxide films of these metals are preferable.
- the metal film, nitride film, and oxide film may each be a film of at least two kinds of mixtures.
- As an arc plasma gun target any one of Fe, Co and Ni, or an alloy or compound containing at least one of these metals, or these metals, Alloy and composite forces It is preferable to use a target with at least two selected mixture forces.
- the catalyst layer After the formation of the catalyst layer, it is preferable to activate the catalyst using hydrogen radicals, and then grow CNTs on the activated catalyst layer. Further, after the formation of the catalyst layer, it is preferable to form a catalyst protective layer having a metal or nitride force on the surface of the catalyst layer. This is to prevent the catalyst layer from being deactivated by exposure to an atmosphere such as air, and to prevent amorphous carbon from being formed on the catalyst during CNT growth.
- the metal used as the catalyst protective layer is a metal selected from Ti, Ta, Sn, Mo and Al, and the nitride is a nitride of these metals. Each of the above metal and nitride may be a mixture of at least two kinds.
- the catalyst particle size control method of the present invention controls the particle size of the catalyst by changing the number of shots of the arc plasma gun when the catalyst layer is formed on the substrate using the arc plasma gun. It is characterized by. As a result, the catalyst particle size can be appropriately selected according to the target diameter of the CNT grown on the catalyst layer.
- a substrate having a nota layer as the substrate is selected from Ti, Ta, Sn, Mo and Al forces. It is preferably a metal film, a nitride film of these metals, or an oxide film of these metals, and as an arc plasma gun target, any one of Fe, Co and Ni, Alternatively, it is preferable to use a target composed of an alloy or compound containing at least one of these metals, or a mixture of at least two selected from these metals, alloys and compounds.
- the method for controlling the CNT diameter of the present invention provides a catalyst layer having a particle diameter controlled according to the above-described catalyst particle diameter control method when the catalyst layer is formed on the substrate using an arc plasma gun. It is characterized by growing and growing CNTs on this catalyst layer by thermal CVD or remote plasma CVD, and controlling the diameter of the grown CNTs, that is, the inner diameter and Z or outer diameter. By virtue of this, it is possible to grow appropriately according to the target CNT diameter. [0022] According to the method for controlling the CNT diameter, it is preferable to activate the catalyst using hydrogen radicals after the formation of the catalyst layer, and then grow carbon nanotubes on the catalyst layer.
- the metal used as the catalyst protective layer is a metal selected from Ti, Ta, Sn, Mo, and A1 force, and the nitride is preferably a nitride of these metals! /.
- CNTs are grown by a thermal CVD method or a remote plasma CVD method using a substrate having a finely divided catalyst formed using an arc plasma gun, so that the CNTs can be efficiently produced at a predetermined temperature. It is possible to grow CNTs, and this brings about an effect that CNTs can be grown as wiring materials, for example, in a semiconductor device manufacturing process.
- the catalyst can be formed with fine particles having a controlled particle size from the beginning, so that the inner diameter and Z or outer diameter of the grown CNTs can be controlled. If you can!
- the catalyst fine particles formed by the arc plasma gun are incident on the substrate with high energy and formed, the catalyst fine particles are less likely to aggregate even when the temperature is applied.
- the catalyst layer is formed by atomizing on the substrate using an arc plasma gun, the radical species of the CNT growth source gas is used as a raw material, and the thermal CV D method or remote control is used.
- the thermal CV D method or remote control is used.
- high energy to the source atoms (molecules) according to the plasma CVD method, it becomes possible to grow CNTs efficiently at a predetermined wide range of growth temperatures, preferably at low temperatures.
- hydrogen radical treatment is performed on the catalyst layer to activate the catalyst, and a protective layer is formed on the surface of the catalyst layer, thereby further reducing the growth temperature and increasing the efficiency. It is possible to grow CNTs.
- a combination of the formation of a fine particle catalyst on a substrate by an arc plasma gun and a thermal CVD method or a remote plasma CVD method enables the CNT formation.
- Long-term low temperature 400 ° C or less, preferably 350 ° C or less, more preferably 300 ° C or less is acceptable.
- the formation of the fine particle catalyst by the arc plasma gun can be performed using a known arc plasma gun, for example, a coaxial arc plasma gun shown in FIG.
- the arc plasma gun shown in FIG. 1 includes a cylindrical anode 11 having one end closed and the other end opened, a force sword 12, and a trigger electrode (for example, a ring-shaped trigger electrode) 13.
- the cathode 12 is concentrically arranged inside the anode 11 and is separated from the anode wall surface by a certain distance.
- the tip of the force sword 12 (corresponding to the end of the anode 11 in the opening direction) is attached with a catalyst material 14 as a target of the arc plasma gun, and the trigger electrode 13 is interposed between the catalyst electrode 13 and the catalyst material 14.
- the cathode 12 may also be composed entirely of a catalyst material.
- An insulator 15 is attached to insulate the cathode 12, and a trigger electrode 13 is attached to the force sword through an insulator 16.
- the anode 11, the force sword 12, and the trigger electrode 13 are electrically insulated by the insulator 15 and the insulator 16.
- the insulator 15 and the insulator 16 may be configured integrally or separately.
- a trigger power source 17 that also has a pulse transformer force is connected between the force sword 12 and the trigger electrode 13, and an arc power source 18 is connected between the force sword 12 and the anode 11.
- the arc power source 18 includes a DC voltage source 19 and a capacitor unit 20. Both ends of the capacitor unit are connected to the anode 11 and the force sword 12, and the capacitor unit 20 and the DC voltage source 19 are connected in parallel. Yes.
- the capacitor unit 20 is charged at any time by the DC voltage source 19.
- the catalyst material 14 and the trigger electrode 13 attached to the force sword 12 by applying a pulse voltage from the trigger power source 17 to the trigger electrode 13.
- Trigger discharge (creeping discharge) between By this trigger discharge, an arc discharge is induced between the catalyst material 14 and the anode 11, and the discharge is stopped by the discharge of the electric charge stored in the capacitor unit 20.
- fine particles plasma ions and electrons generated by melting of the catalyst material are formed. These ion and electron fine particles are evacuated to the vacuum opening shown in FIG. It is discharged into the chamber and supplied onto the substrate to be processed placed in the vacuum chamber to form a layer of catalyst fine particles. It is preferable to repeat this trigger discharge a plurality of times and induce arc discharge for each trigger discharge.
- the wiring length of the capacitor unit 20 is set to 50 mm or less and the capacitance of the capacitor unit connected to the force sword 12 so that the peak current of arc discharge in the above case is 1800 A or more.
- this trigger discharge is preferably generated about 1 to 10 times per second.
- the catalyst particle diameter can be controlled by the number of shots of the arc plasma gun. Therefore, by changing the number of shots and appropriately controlling the catalyst particle diameter according to the target diameter of the grown CNT, it is possible to grow by appropriately controlling the inner diameter and Z or outer diameter of the growing CNT. It becomes.
- the force sword (target) of the arc plasma gun is any one of Fe, Co and Ni as a catalyst material, or an alloy or compound containing at least one of these metals, or at least two of these It is made of a mixture of! Only the tip of the force sword (which functions as a target) may have these catalyst material forces.
- the catalyst particle diameter In order to control the catalyst particle diameter by the number of shots, it depends on the film forming conditions, but it is preferably 1 A or more and 5 nm or less in terms of film thickness. If it is less than 1 A, the particles of the arc plasma gun force will be too far apart from each other when they reach the substrate, so the catalyst particle size will not reflect the number of shots. Particles are stacked to form a film The number of shots is not reflected and the same particle size is obtained. As a result, it becomes difficult to control the CNT diameter to grow.
- 1 A in terms of film thickness depends on the setting conditions of the arc plasma gun, when the above-mentioned catalyst layer is formed using an arc plasma gun manufactured by ULVAC, Inc., for example, 60V, 8800 F And if the substrate target interval is 80 mm and the conditions are set to 0.1 A per shot (shot), the film thickness is 10 shots, and 5 nm in terms of film thickness is 500 shots Become film thickness. In this case, if the voltage is about 80V and about 100V, it will be 0.5A and 1A per shot, respectively.
- the catalyst particle diameter can be controlled in accordance with the number of shots based on the film thickness per shot that is set depending on the film formation conditions by the arc plasma gun as described above. For example, if 0.1 A per shot is set, a catalyst layer with a desired film thickness can be formed with 10 to 500 shots, and if set to 0.5 A per shot, 2 to: LOO shots Thus, a catalyst layer having a desired film thickness can be formed.
- the catalyst particle size can be controlled according to the number of shots of the arc plasma gun. As the number of shots increases, among the particles that reach the substrate, nearby particles agglomerate and the particle size increases, so the desired number of shots in relation to the diameter of the CNT grown on the catalyst particles
- the particle size of the catalyst may be controlled by selecting as appropriate.
- the film forming conditions are about 0.5A or less per shot.
- the diameter of CNT grown on the catalyst layer can also be controlled.
- the inner diameter distribution of the grown CNTs varies depending on the film thickness.
- the inner diameter is close to the catalyst particle diameter.
- CNT when CNT is applied to a device such as a semiconductor, a plurality of CNTs are bundled. CNT diameter and the accompanying CNT density greatly affect CNT characteristics. Therefore, it is extremely important to be able to appropriately control the inner diameter and Z or outer diameter of the CNT.
- the relationship between the catalyst particle diameter and the inner diameter and Z or outer diameter of the growing CNT is a force that depends on the CNT growth method and its conditions.
- the number of shots of the arc plasma gun is smaller, and the CNT having a smaller diameter is obtained. It is done.
- the catalyst particle size is controlled, if the growth temperature is higher than the above-mentioned growth temperature, for example, 700 ° C or less, it is preferable to use an arc plasma gun for film formation. There is a problem that the catalyst fine particles agglomerated to increase the particle size.
- FIG. 2 shows an embodiment of an apparatus for producing catalyst fine particles using the arc plasma gun.
- the reference numerals attached to the arc plasma gun in the figure that are the same as those in FIG. 1 indicate the same components, and a detailed description of the arc plasma gun is omitted.
- this apparatus has a cylindrical vacuum chamber 21, and a substrate stage 22 is disposed horizontally above the vacuum chamber. At the upper part of the vacuum chamber 21, a rotation mechanism 23 and a rotation drive means 24 are provided so that the substrate stage can be rotated in a horizontal plane.
- One or a plurality of processing substrates 25 are held and fixed on the surface of the substrate stage 22 facing the bottom of the vacuum chamber 21.
- One or a plurality of coaxial arc plasma guns 26 are arranged with the opening A of the anode 11 facing the vacuum chamber.
- the arc plasma gun includes a cylindrical anode 11, a rod-shaped force sword 12, and a ring-shaped trigger electrode 13.
- the anode 11, force sword 12, and trigger electrode 13 are configured to apply different voltages! RU
- the DC voltage source 19 constituting the arc power source 18 has a capability of flowing a current of several A at 800V, and the capacitor unit 20 can be charged by the DC voltage source in a fixed charging time. It has become.
- the trigger power supply 17 is composed of a pulse transformer, and is configured to boost a pulse voltage of ⁇ s with an input voltage of 200V by about 17 times to output 3.4 kV (several / ⁇ ⁇ ). It is connected so that the applied voltage can be applied to the trigger electrode 13 with a positive polarity with respect to the force sword 12.
- the vacuum chamber 21 is connected to an evacuation system 27 composed of a turbo pump, a rotary pump, or the like so that the inside of the chamber can be evacuated to about 10_5 Pa, for example.
- the vacuum chamber 21 and the anode 11 are connected to the ground potential.
- a gas introduction system having a gas cylinder 28 is connected to the vacuum chamber 21 in order to introduce an inert gas such as helium gas into the chamber and atomize ions generated from the catalyst material. It's okay.
- the capacity of the capacitor unit 20 is set to 2200 F, a voltage of 100 V is output from the DC voltage source 19, the capacitor unit 20 is charged with this voltage, and this charging voltage is applied to the anode 11 and the force sword 12. In this case, a negative voltage output from the capacitor unit 20 is applied to the catalyst material 14 via the force sword 12.
- a pulsed trigger voltage of 3.4 kV is output from the trigger power supply 17 and applied to the force sword 12 and the trigger electrode 13
- a trigger discharge occurs on the surface of the insulator 15. Electrons are emitted from the joint between the force sword 12 and the insulator 15.
- the arc current with a peak current of 1800A or more flows for about 200 seconds, and the catalytic metal vapor is discharged from the side of the force sword 12 to form plasma. Is done. At this time, the arc current flows on the central axis of the force sword 12 and a magnetic field is formed in the anode 11.
- the electrons released into the anode 11 fly under the Lorentz force opposite to the direction in which the current flows due to the magnetic field formed by the arc current, and are released into the vacuum chamber 21 from the opening A. .
- the catalytic metal vapor released from the force sword 12 contains ions and neutral particles, which are charged particles, and the charge is small compared to the mass (small charge-to-mass ratio). Neutral particles travel straight and impinge on the wall of the anode 11 Ions, which are charged particles with a large charge-to-mass ratio, fly so as to be attracted to electrons by Coulomb force, opening the anode A force vacuum chamber 21 It is released inside.
- the processing substrate 25 passes while rotating on a concentric circle having the center of the substrate stage 22 as its center. Then, the ionic force in the vapor of the catalytic metal released into the vacuum chamber 21 S When reaching the surface of each substrate, it adheres to each surface as catalyst fine particles.
- An arc discharge is induced once by one trigger discharge, and an arc current flows for 300 ⁇ sec.
- arc discharge can be generated at a period of 1 Hz.
- arc discharge is generated a predetermined number of times (for example, 5 to: LOOO times) to form catalyst fine particles on the surface of the processing substrate 23.
- the catalyst fine particle forming apparatus using a plurality of arc plasma guns may of course be performed using the 1S arc plasma gun shown.
- the remote plasma CVD method referred to in the present invention is a method in which a source gas (reaction gas) is decomposed into ion species and radical species in plasma, and ion species in the source gas obtained by the decomposition are removed. This is a method of growing CNTs using radical species as raw materials.
- the CNTs are efficiently produced at a low temperature. It can grow.
- This radical species was selected as a source gas, for example, hydrogen gas-containing gas such as hydrogen gas and ammonia (diluted gas), and methane, ethane, propane, propylene, acetylene, and ethylene power. It is a radical obtained by decomposing in a plasma a carbon atom-containing gas which is an alcohol gas selected from at least one hydrocarbon gas or methanol ethanol.
- a hydrogen atom containing gas and a carbon atom containing gas Hydrogen radicals and carbon radicals generated by decomposing mixed gas in plasma.
- a microwave that generates a large amount of radical species, such as a force that is decomposed in a plasma generated by a microwave or an RF power source.
- ionic species are also generated, and in the present invention, it is necessary to remove the ionic species. This is because the ionic species has high kinetic energy, and thus avoids adverse effects such as etching of the catalyst surface due to the impact of the ionic species.
- a shielding member as a mesh member having a predetermined mesh size is installed between the catalyst layer or the substrate on which the catalyst layer is formed and the plasma, or a bias voltage or a magnetic field having a predetermined value is applied.
- a shielding member as a mesh member having a predetermined mesh size is installed between the catalyst layer or the substrate on which the catalyst layer is formed and the plasma, or a bias voltage or a magnetic field having a predetermined value is applied.
- a positive potential of about 10 to 200 V is applied to the mesh member as a bias voltage of a predetermined value, it is possible to prevent the ion species from entering the substrate surface, and as a magnetic field of a predetermined value, If a magnetic field of about 100 gauss or more is applied to the mesh member by energizing a magnet or coil, the ion species can be prevented from entering the substrate surface, and the catalyst surface is etched by the impact of the ion species. There is nothing. Further, the shape of the mesh member is not limited as long as it can prevent or block the ion species from entering the substrate surface.
- Radical species irradiation may be performed at the start of heating the substrate to the CNT growth temperature, in the middle of the temperature increase, or may be performed at the growth temperature. .
- the timing of this radial supply may be appropriately set based on the type of catalyst metal, the thickness of the catalyst, the state of the substrate, the type of reaction gas used, the growth method, and the like.
- the heating of the substrate according to the present invention is controlled by other heating means (for example, a lamp heater or the like) rather than by the radiant heat of the plasma.
- a substrate on which a fine particle catalyst is formed by the arc plasma gun described above is used.
- the target of this arc plasma gun is one of Fe, Co and Ni, or an alloy containing at least one of these metals (for example, Fe-Co, Ni-Fe, alloys such as stainless steel and invar), etc. Or a compound (eg, Co—Ti, Fe—Ta, Co—Mo, etc.) or a mixture thereof (eg, , Fe + TiN, Ni + TiN, Co + TaN, etc.).
- the catalyst to be formed can be made finer, and at the same time, aggregation of the formed catalyst fine particles can be prevented.
- a metal selected from Ti, Ta, Sn, Mo, A1 and the like preferably a nitride selected from TiN, TaN, A1N, etc.
- a metal selected from Ti, Ta, Sn, Mo, A1 and the like preferably a nitride selected from TiN, TaN, A1N, etc.
- a metal selected from Ti, Ta, Sn, Mo, A1 and the like preferably a nitride selected from TiN, TaN, A1N, etc.
- the thickness of the catalyst for example, when forming an Fe film by an arc plasma gun method using an Fe sintered target, a film thickness of about 0.1 to 20 nm can sufficiently function as a catalyst. Fulfill.
- the film thickness is about 1 to 50 nm.
- the thickness is about 1 to 50 nm. If the film thickness is sufficient, the catalyst performs its function sufficiently.
- the surface of the catalyst layer formed by a plasma gun is activated with hydrogen radicals before CNT growth. It is convenient to perform the activation of the catalyst surface and the subsequent CNT growth in the same CVD apparatus. That is, it is convenient to perform radical species irradiation when activating the catalyst surface and radical species irradiation when performing CNT growth in a CVD apparatus that performs CNT growth.
- a hydrogen radical species generating gas (for example, hydrogen gas) is introduced into an apparatus separate from the CVD apparatus, for example, into an apparatus such as a quartz reaction tube equipped with microwave generation means, and this is performed in plasma.
- the gas containing the ionic species and radical species is passed through a mesh member having a predetermined mesh size.
- the gas containing hydrogen radical species is introduced into the CVD apparatus.
- the catalyst surface may be activated by irradiating the catalyst surface formed on the substrate placed in the apparatus.
- the design may be changed as appropriate in accordance with the object of the present invention.
- the CNT growth method of the present invention can be carried out using a known remote plasma CVD apparatus as it is or with an appropriately modified design.
- a vacuum chamber is provided, a substrate stage for mounting a substrate is provided in the vacuum chamber, and plasma is generated in the chamber on the side wall of the vacuum chamber.
- Plaz This is a plasma CVD device equipped with a gas generator and uses a CVD device that introduces CNT growth gas into a vacuum chamber and vapor-phase grows it on the surface of the substrate on which the CNTs are placed on the substrate stage. it can.
- the substrate stage is arranged so that the region force for generating the plasma is also separated so that the substrate is not exposed to the plasma generated in the vacuum chamber.
- This apparatus is provided with heating means for heating the substrate to a predetermined temperature.
- the remote plasma CVD apparatus that can be used in the present invention is also the above-mentioned known remote plasma CVD apparatus, in order to prevent the substrate from being exposed to the plasma generated in the vacuum chamber.
- a mesh member having a predetermined mesh size is provided between the region where plasma is generated and the processing substrate on the substrate stage. With this configuration, the ion species generated in the plasma are blocked and removed, and the CNT growth radical species are irradiated to grow CNTs having an alignment aligned in the direction perpendicular to the substrate.
- the surface of the catalyst provided on the substrate can be activated by irradiating the substrate surface with hydrogen radical species before CNT growth.
- a force for providing a bias power source so that a bias voltage of a predetermined value can be applied to the substrate Alternatively, means for applying a predetermined bias voltage or magnetic field may be provided.
- the gas decomposed in the plasma can reach the substrate surface while maintaining the energy state, and ion species generated in the plasma can be blocked and removed.
- the substrate surface is irradiated with a gas containing hydrogen radical species to activate the catalyst surface provided on the substrate, and the substrate is irradiated with a gas containing hydrogen radical species and carbon radical species. It is possible to grow CNTs with orientation aligned in the vertical direction.
- the remote plasma CVD apparatus shown in FIG. 3 has a vacuum chamber 32 provided with a vacuum exhaust means 31 such as a rotary pump or a turbo molecular pump.
- a gas introducing means 33 such as a shower plate having a known structure is provided on the ceiling of the vacuum chamber 32.
- the gas introduction means 33 is connected via a gas supply pipe 34 connected to the gas introduction means. Connect to the gas source, not shown.
- a substrate stage 35 on which a substrate S is placed is provided in the vacuum chamber 32 so as to face the gas introduction means 33, and the substrate stage 35 and the gas introduction means 3 are provided on the side wall of the vacuum chamber.
- a microwave generator 36 which is a plasma generator, is provided via a waveguide 37.
- the microwave generator 36 may be of any structure having a known structure, for example, a structure for generating ECR plasma using a slot antenna.
- a substrate having glass, stone, silicon, or the like, or a substrate having metal force, such as GaN, sapphire, or copper should be used.
- a substrate in which the catalytic metal Z alloy is formed in various arbitrary patterns at an arbitrary part of the surface is used.
- the metal is formed on the surface of a substrate such as glass, quartz, or Si, the catalyst is prevented from agglomerating and the adhesion between the substrate and the substrate is improved.
- the above buffer layer is provided as an underlayer so that no compound is formed in step (b).
- the vacuum exhaust means 31 is operated to exhaust the vacuum chamber 32 to a predetermined degree of vacuum.
- the microwave generator 36 is operated to generate plasma.
- the substrate S is heated to a predetermined temperature, for example, hydrogen gas is introduced into the vacuum chamber 32 and decomposed in plasma. From this decomposed gas, ionic species are removed by the mesh member or the like, and the catalyst surface provided on the surface of the substrate S is irradiated with a hydrogen radical species-containing gas to activate the catalyst metal, and thereafter in the same manner.
- a metallic mesh member 38 having a predetermined mesh size facing the substrate stage 35 between the plasma generation region P and the substrate S. Is provided.
- this mesh member By providing this mesh member, ion species are removed from the gas generated by decomposition in the plasma, and the substrate is irradiated with a decomposition gas containing only hydrogen radical species that have passed through the mesh member.
- the microphone mouth wave generator 36 is activated so that the substrate S is not exposed to the plasma generated in the vacuum chamber 32. In this case, the substrate stage 35 is disposed away from the plasma generation region P.
- a resistance heating type heating means (not shown) is incorporated in the substrate stage 35. This heating means is controlled to a predetermined temperature during activation of the catalyst and during vapor phase growth of CNT.
- the substrate is irradiated with a decomposition gas containing radical species in the same manner as described above.
- the mesh member 38 is provided, for example, in a vacuum chamber 32, which may be made of stainless steel, to be grounded or in a floating state.
- the mesh size of the mesh member 38 may be about 1 to 3 mm.
- an ion sheath region is formed by the mesh member 38, and plasma particles (ions) are prevented from entering the substrate S side, and the active metal surface of the catalyst metal provided on the substrate is prevented. Soot and CNT growth can be conveniently performed.
- the substrate stage 35 is disposed away from the plasma generation region P, it is possible to prevent the substrate S from being exposed to plasma. If the mesh size is set to be smaller than 1 mm, the gas flow is blocked. If the mesh size is set to be larger than 3 mm, the plasma cannot be blocked and ionic species also pass through the mesh member 38.
- the gas decomposed in the plasma is used. It is necessary to reach the substrate S while maintaining energy. Therefore, in addition to the mesh member 38, a bias power source 39 that applies a bias voltage to the substrate S may be provided between the mesh member 38 and the substrate S. As a result, the gas decomposed in the plasma passes through each mesh of the gas force mesh member 38 containing radical species and is smoothly sent in the direction of the substrate S.
- the bias voltage is set in the range of ⁇ 400V to 200V. Lower than 400V At a voltage, discharge is likely to occur, activation of the catalyst surface is difficult to occur, and there is a risk of damaging the substrate s and vapor-grown CNT. On the other hand, at a voltage exceeding 200V, the growth rate of CNTs slows down.
- the distance between the mesh member 38 and the substrate S placed on the substrate stage 35 is preferably set in a range of 20 to L0 Omm. If the distance is shorter than 20 mm, electric discharge is likely to occur between the mesh member 38 and the substrate S. For example, the activation of the catalyst surface is inconvenient, and the substrate S and vapor-grown CNT are damaged. There is a fear. On the other hand, when the distance exceeds 100 mm, catalyst activation and CNT growth are not performed satisfactorily, and the mesh member 38 can serve as a counter electrode when a bias voltage is applied to the substrate S. ⁇
- the substrate stage 35 and the substrate S By setting the distance between the substrate stage 35 and the substrate S as described above, if the plasma is generated after the substrate S is placed on the substrate stage 35, the substrate S is not exposed to the plasma. That is, the substrate S is not heated by the energy of the plasma force, and the substrate S can be heated only by the heating means built in the substrate stage 35. Therefore, when the catalytic metal surface is activated and when the CNTs are vapor-phase grown, the substrate temperature can be easily controlled, and the catalytic metal can be activated, and at a low temperature and damaged. This makes it possible to efficiently vapor-phase CNT on the surface of the substrate S.
- the force described for the substrate stage 35 with the heating means built-in is not limited to this. Any configuration can be used as long as the substrate S on the substrate stage 35 can be heated to a predetermined temperature. ! /
- a bias voltage is applied to the substrate S between the mesh member 38 and the substrate S so that the gas decomposed by the plasma reaches the substrate S while maintaining energy.
- the catalytic metal activation can be satisfactorily performed without damage even when the bias voltage is not applied between the mesh member 38 and the substrate S, which is not limited to this.
- CNT can be vapor-phase grown on the surface of the substrate S.
- an insulating layer such as SiO is formed on the surface of the substrate S, charge up to the surface of the substrate S is performed.
- a bias voltage may be applied to the substrate S through the bias power source 39 in the range of 0 to 200V. In this case, if the voltage exceeds 200V, the catalyst surface Can not be carried out efficiently, and the growth rate of CNTs is slow.
- a quartz tube having an inner diameter of 50 mm equipped with a microwave generator was used, and plasma was generated by introducing microwaves into the quartz tube from the outside in the lateral direction of the tube, so that a raw material gas was introduced into the tube.
- the mixed gas of methane gas and hydrogen gas was decomposed, and CNTs were grown as follows.
- a gas containing the radical species was introduced into a known remote plasma CVD apparatus, and the target substrate on which the catalyst was formed was irradiated for 5 minutes to grow CNTs.
- the generation of the gas containing the radical species can be similarly performed in the CVD apparatus when the remote plasma CVD apparatus provided with the mesh member 38 shown in FIG. 3 is used.
- Ni films were deposited as a catalyst by the arc plasma gun method (voltage 60V, 8800 / z F, substrate-target interval 8 Omm) (film thickness: film thickness of about 0.1 A per shot) Therefore, about 10A) was used.
- a substrate was prepared on which an Ni film was formed to a thickness of 1 mm as a catalyst by the EB method (process conditions: pressure 5 X 10 — 4 Pa, film formation rate 1 AZs).
- the temperature at which CNT growth occurs at a substrate of 400 ° C was the lower limit when the substrate was prepared by the EB method, but the temperature was 350 ° C when the substrate was prepared by the arc plasma gun method. CNT growth was confirmed.
- CNTs were grown by repeating the procedure described in Example 1, except that the substrate having the buffer layer TiN described in Example 1 formed with a thickness of 20 nm was used. For comparison, CNTs were grown in the same manner using a substrate with no buffer layer.
- Example 2 In accordance with the procedure described in Example 1, a nofer layer TiN was formed to a thickness of 20 nm, and 100 Ni catalysts were formed by the arc plasma gun method, and then the A1 film was formed as a catalyst protective layer by the EB method. Was formed at a thickness of lnm (process conditions: pressure 5 X 10 _4 Pa, deposition rate lAZs). Using this substrate, CNTs were grown by repeating the procedure described in Example 1.
- Example 1 As in Example 1, a quartz tube with an inner diameter of 50 mm equipped with a microwave generator was used, and an external force microwave in the lateral direction of the tube was introduced into this quartz tube.
- the CNTs were grown as follows by generating a plasma and decomposing the mixed gas of methane gas and hydrogen gas introduced as raw material gas into the tube.
- a gas containing the above radical species was introduced into a known remote plasma CVD apparatus, and the target substrate (550 ° C) on which the catalyst was formed was irradiated for 5 minutes to grow CNTs. .
- the generation of the gas containing the radical species can be similarly performed in this CVD apparatus when a remote plasma CVD apparatus provided with the mesh member 38 shown in FIG. 3 is used.
- the target substrate is a Si (lOO) substrate on which a TiN film of 20 nm is formed as a buffer layer by sputtering (process conditions: using a Ti target, N gas, pressure 0.5 Pa, power 300 W).
- the inner diameter distribution of CNT obtained by force is shown in Fig. 6 (a) (for 50 shots) and (b) (for 100 shots), and the outer diameter distribution is shown in Fig. 7 (a) (50 Departure) and (b) (in case of 100).
- the horizontal axis is the CNT diameter (nm)
- the vertical axis is the number of samples collected.
- the number of CNT graphene sheets is about 2 to 5 and the outer diameter is about 4 nm.
- the number of layers of graph encasement is increased to 5 to 10 layers. The distribution is centered around ⁇ 15nm.
- Example 4 was repeated except that the Ni layer as the catalyst was formed with 300 shots (3 nm in terms of film thickness) and 500 shots (5 nm in terms of film thickness). Has grown. As a result, in both cases, the inner diameter of the grown CNTs was about 10 nm, and the outer diameter was about 20 ⁇ m. This is because the catalyst fine particles are stacked at 300 shots (film thickness 3 nm) or more.
- brush-like CNT can be grown at a predetermined temperature, and the particle diameter of the catalyst and the inner diameter and Z or outer diameter of the grown CNT can be easily controlled.
- the invention can be applied to the field of semiconductor devices using CNTs and other technical fields. Brief Description of Drawings
- FIG. 1 is a schematic diagram schematically showing a structural example of an arc plasma gun used in the present invention.
- FIG. 2 is a schematic diagram schematically showing an example of the configuration of a catalyst layer manufacturing apparatus equipped with the arc plasma gun of FIG.
- FIG. 3 is a schematic view schematically showing an example of the configuration of a remote plasma CVD apparatus for carrying out the CNT growth method of the present invention.
- FIG. 4 SEM photograph of CNT obtained in Example 1.
- FIG. 5 is a SEM photograph of CNT obtained in Example 3.
- FIG. 6 is a graph showing the inner diameter distribution of CNT obtained in Example 4, where (a) is for 50 shots and (b) is for 100 shots.
- FIG. 7 is a graph showing the outer diameter distribution of the CNT obtained in Example 4, where (a) is for 50 shots and (b) is for 100 shots.
Abstract
Description
Claims
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KR1020087031229A KR101096482B1 (ko) | 2006-05-29 | 2007-05-29 | 카본 나노 튜브 성장용 기판, 카본 나노 튜브 성장 방법, 카본 나노 튜브 성장용 촉매의 입경 제어 방법, 및 카본 나노 튜브 직경의 제어 방법 |
US12/302,599 US20090238996A1 (en) | 2006-05-29 | 2007-05-29 | Substrate For Growth of Carbon Nanotube, Method for Growth of Carbon Nanotube, Method for Control of Particle Diameter of Catalyst for Growth of Carbon Nanotube and Method for Control of Carbon Nanotube Diameter |
JP2008517935A JP4534215B2 (ja) | 2006-05-29 | 2007-05-29 | カーボンナノチューブ成長用基板 |
CNA2007800250575A CN101484383A (zh) | 2006-05-29 | 2007-05-29 | 碳纳米管成长用基板、碳纳米管成长方法、碳纳米管成长用催化剂的粒径控制方法及碳纳米管直径的控制方法 |
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JP (2) | JP4534215B2 (ja) |
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JP2009285644A (ja) * | 2008-06-02 | 2009-12-10 | Ulvac Japan Ltd | 触媒材料の製造方法及び真空アーク蒸着装置 |
KR100975656B1 (ko) | 2008-07-24 | 2010-08-17 | 한국과학기술원 | 국부적으로 화학적 활성이 제어된 금속촉매 및 그의제조방법 |
US20100209704A1 (en) * | 2009-01-19 | 2010-08-19 | Kabushiki Kaisha Toshiba | Carbon nanotube growing process, and carbon nanotube bundle formed substrate |
JP2010269982A (ja) * | 2009-05-22 | 2010-12-02 | Nikon Corp | カーボンナノチューブ集合体の製造方法 |
JP2011512315A (ja) * | 2008-02-20 | 2011-04-21 | コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブ | 炭素基板または金属基板上でのカーボンナノチューブの成長 |
WO2013018509A1 (ja) * | 2011-07-29 | 2013-02-07 | 東京エレクトロン株式会社 | 前処理方法及びカーボンナノチューブの形成方法 |
US10378104B2 (en) | 2013-11-13 | 2019-08-13 | Tokyo Electron Limited | Process for producing carbon nanotubes and method for forming wiring |
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KR20140053979A (ko) * | 2011-07-29 | 2014-05-08 | 도쿄엘렉트론가부시키가이샤 | 전처리 방법 및 카본 나노튜브의 형성 방법 |
KR101960120B1 (ko) | 2011-07-29 | 2019-03-19 | 도쿄엘렉트론가부시키가이샤 | 전처리 방법 및 카본 나노튜브의 형성 방법 |
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CN101484383A (zh) | 2009-07-15 |
TW200815281A (en) | 2008-04-01 |
US20090238996A1 (en) | 2009-09-24 |
KR101096482B1 (ko) | 2011-12-20 |
JP4534215B2 (ja) | 2010-09-01 |
TWI429585B (zh) | 2014-03-11 |
KR20090019856A (ko) | 2009-02-25 |
JP2009298698A (ja) | 2009-12-24 |
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