US20100193350A1 - Method for making carbon nanotube-base device - Google Patents
Method for making carbon nanotube-base device Download PDFInfo
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- US20100193350A1 US20100193350A1 US11/416,724 US41672406A US2010193350A1 US 20100193350 A1 US20100193350 A1 US 20100193350A1 US 41672406 A US41672406 A US 41672406A US 2010193350 A1 US2010193350 A1 US 2010193350A1
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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
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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
- 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
- C01B2202/08—Aligned nanotubes
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/843—Gas phase catalytic growth, i.e. chemical vapor deposition
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/844—Growth by vaporization or dissociation of carbon source using a high-energy heat source, e.g. electric arc, laser, plasma, e-beam
Definitions
- the present invention generally relates to a method for making a carbon nanotube-based device.
- Carbon nanotubes are very small tube-shaped structures essentially having the composition of a graphite sheet, formed as a tube. Carbon nanotubes produced by arc discharge between graphite rods were first discovered and reported in an article by Sumio Iijima entitled “Helical Microtubules of Graphitic Carbon” (Nature, Vol. 354, Nov. 7, 1991, pp. 56-58). Carbon nanotubes have very good electrical conductance due to their structure. They are also chemically stable, and have very small diameters (less than 100 nanometers) and large aspect ratios (length/diameter). Due to these and other properties, it has been suggested that carbon nanotubes can play an important role in fields such as microscopic electronics, materials science, biology and chemistry.
- nanotubes promise to have a wide range of applications, better control is needed over the building and organization of nanotube-based architectures. Normally, the orientation of growing nanotubes is controlled such that the nanotubes are rectilinear and parallel to each other. Chemical vapor deposition has been used to produce nanotubes vertically aligned on catalyst-printed substrates.
- carbon nanotubes obtained by the above-mentioned methods are aligned along a linear direction, and/or extend perpendicularly from the substrates. Furthermore, the method of using an external field such as an electric field or a magnetic field, to control a direction of growth of the carbon nanotubes is difficult to apply in generating localized complicated structures with plural orientations of the carbon nanotubes. Accordingly, the range of diversity of different kinds of carbon nanotube-based devices is limited.
- a method for making a carbon nanotube-based device includes the following steps of: providing a substrate having a shadow mask layer formed thereon, the shadow mask layer being configured for defining an unmasked surface area on the substrate; disposing a sputter source on the shadow mask layer, the sputter source being configured for supplying a catalyst material and depositing the catalyst material onto the substrate; forming a catalyst layer including at least one catalyst block on the unmasked surface area of the substrate, a thickness of the at least one catalyst block being gradually decreased from a first end thereof to an opposite second end thereof, and the at least one catalyst block having a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest; introducing a carbon source gas; and forming at least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process, wherein the at least one carbon nanotube array being arc-shaped, and bending in a direction of deviating from the region.
- the growth rate of carbon nanotubes is associated with a thickness of the catalyst layer used to grow them on.
- the carbon nanotubes grow fastest when the catalyst layer has a certain optimum thickness.
- the thickness of the catalyst layer is greater than the optimum thickness, the thicker the catalyst layer, the slower the growth rate of carbon nanotubes; when the thickness of the catalyst layer is less than the optimum thickness, the thinner the catalyst layer, the slower the growth rate of carbon nanotubes.
- the thickness of the catalyst layer is deliberately controlled, so that the thickness gradually varies from a first end to an opposite second end, and somewhere the catalyst layer has a thickness proximal or equal to the optimum thickness for growing carbon nanotube; additionally, carbon nanotubes have inherently strong Van der Waals force interactions therebetween. Thereby, a carbon nanotube-based device with plural orientations of carbon nanotubes is obtainable.
- FIG. 1 is a schematic, cross-sectional view of one stage in a procedure for sputter-depositing a catalyst layer on a substrate in accordance with the first embodiment
- FIG. 2 is a schematic, cross-sectional view of a subsequent stage in a procedure for sputter-depositing a catalyst layer on the substrate of FIG. 1 ;
- FIG. 3 is an isometric view of the substrate of FIG. 2 with the catalyst layer formed thereon, after the shadow mask layer being removed, and a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest, of the catalyst layer being marked;
- FIG. 4 is similar to FIG. 3 , but showing the catalyst layer patterned into a plurality of catalyst blocks positioned at opposite sides of the region;
- FIG. 5 is an enlarged, side view of the substrate and catalyst blocks of FIG. 4 after being annealed;
- FIG. 6 is an enlarged, side view of a carbon nanotube-based device in accordance with the first embodiment, obtained by treating the catalyst blocks of FIG. 5 ;
- FIG. 7 is an isometric view of the carbon nanotube-based device of FIG. 6 ;
- FIG. 8 is a schematic, cross-sectional view of one stage in a procedure for sputter-depositing a catalyst layer on a substrate in accordance with the second embodiment
- FIG. 9 is a schematic, cross-sectional view of a subsequent stage in a procedure for sputter-depositing a catalyst layer on a substrate of FIG. 8 ;
- FIG. 10 is a schematic, cross-sectional view of the substrate of FIG. 9 with the catalyst layer formed thereon, after the shadow mask layer being removed, and a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest, of the catalyst layer being marked;
- FIG. 11 is an isometric view of the substrate of FIG. 10 with the catalyst layer formed thereon;
- FIG. 12 is similar to FIG. 11 , but showing the catalyst layer patterned into a plurality of catalyst blocks positioned at opposite sides of the region;
- FIG. 13 is an enlarged, side view of the substrate and catalyst blocks of FIG. 12 after being annealed;
- FIG. 14 is an enlarged, side view of a carbon nanotube-based device in accordance with the second embodiment, obtained by treating the catalyst blocks of the substrate of FIG. 13 ;
- FIG. 15 is an isometric view of the carbon nanotube-based device of FIG. 14 .
- FIGS. 1-4 together illustrate successive stages in a process for forming a catalyst layer on a substrate, in accordance with the first embodiment.
- a substrate 10 is first provided.
- Suitable substrate materials include a variety of materials, including metals, semiconductors and insulators such as silicon (Si), glass and metal sheets. It is possible that the substrate 10 will, in practice, be a portion of a device, e.g., a silicon-based integrated circuit device, on which nanotube formation is desired.
- a shadow mask layer 40 is formed on the substrate 10 and located at one end portion thereof to define an unmasked surface area 12 of the substrate 10 to be exposed.
- the shadow mask layer 40 is usually made from photo-resist, metal, metallic oxide, or metallic nitride.
- the shadow mask layer 40 has a suitable height (as denoted by h in FIG. 1 ) to shade a sputter source 20 disposed above the shadow mask layer 40 , in order to sputter-deposit a catalyst layer having a gradient thickness on the substrate 10 .
- the shadow mask layer 40 has a plurality of sidewalls 42 substantially perpendicular to the substrate 10 .
- the height of the shadow mask layer 40 is usually less than mean free path of a catalyst atom generated from the sputter source 20 under a predetermined sputter-deposition process.
- the mean free path S of a catalyst atom satisfies the condition (1):
- the sputter source 20 is configured for supplying a catalyst material and depositing the catalyst material onto the substrate 10 , so as to form a catalyst layer having a gradient thickness via a sputter-deposition process.
- the catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof.
- a distance from the sputter source 20 to the substrate 10 is greater than the mean free path of a catalyst atom generated from the sputter source 20 under a predetermined sputter-deposition process.
- the sputter source 20 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material.
- the sputter source 20 having a linear sputter target
- an optimum solution is that a reciprocating movement of the substrate 10 relative to the sputter source 20 along a direction perpendicular to the linear sputter target is implemented.
- the sputter source 20 has a surface sputter target.
- a catalyst layer 30 having a gradient thickness is formed on the unmasked surface area 12 of the substrate 10 via a sputter-deposition process.
- the catalyst layer 30 is located at one side of the shadow mask layer 40 .
- the catalyst layer 30 has a region with a thickness proximal or equal to, an optimum thickness at which carbon nanotubes growing fastest.
- a thickness of the catalyst layer 30 is gradually varied from one end thereof to another opposite end thereof
- a thickness T( ⁇ ) of a position of the catalyst layer 30 distant from the shadow mask layer 40 with a distance of ⁇ approximately satisfies the following condition (2):
- T ( ⁇ ) T 0 /2 ⁇ (1+ ⁇ / ⁇ square root over ( ⁇ 2 +h 2 ) ⁇ ) (2)
- T 0 is a thickness of the position under a situation that no shadow mask layer 40 exists on the substrate 10 during the sputter-deposition process
- h is a height of the shadow mask layer 40 .
- an obvious gradient thickness exists in the region where ⁇ varies from 0 to 2h.
- the size of the region is correlated with the height of the shadow mask layer 40 .
- the height h of the shadow mask layer 40 is in the range from 0.1 micrometers to 10 millimeters; correspondingly, the length (starting from the shadow mask layer 40 ) of the region having obvious gradient thickness is in the range from 0.2 micrometers to 20 millimeters
- the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device.
- the shadow mask layer 40 is removed from the substrate 10 .
- a region 32 of the catalyst layer 30 is marked for purpose of determining the growth direction of carbon nanotubes. That is, under certain conditions for growing carbon nanotubes by a chemical vapor deposition process, the carbon nanotubes grow fastest at where a region of the catalyst layer 30 has an optimum thickness. If the conditions for growing the carbon nanotubes by the chemical vapor deposition process are predetermined, the optimum thickness can be determined accordingly.
- the catalyst material is iron
- a carbon source gas is ethylene
- a temperature at which the carbon nanotubes are grown is about 700° C. (degrees Celsius).
- an optimum thickness of the catalyst layer 30 for growing carbon nanotubes is about 5 nm, i.e., the region 32 in this condition has a thickness proximal or equal to 5 nanometers.
- the catalyst layer 30 can be patterned to meet various configurations of resultant carbon nanotube-based devices.
- the patterned catalyst layer 30 includes at least one catalyst block having a gradient thickness.
- a thickness of the at least one catalyst block gradually varies from a first end thereof to an opposite second end thereof
- the least one catalyst block somewhere has a thickness proximal or equal to the optimum thickness for growing carbon nanotubes.
- the patterned catalyst layer 30 when the patterned catalyst layer 30 is made from iron, a thickness of the thickest end of each of the catalyst blocks is in the range from 5 nm to 20 nm, and a thickness of the thinnest end of each the catalyst blocks is in the range from 1 nm to 10 nm.
- the patterned catalyst layer 30 includes a plurality of catalyst blocks 33 , 34 staggeringly positioned at opposite sides of the region of optimum thickness 32 .
- a thinnest end of each of the catalyst blocks 34 has a thickness approximately equal to the optimum thickness, and a thickest end of each of the catalyst blocks 33 has a thickness approximately equal to the optimum thickness.
- the pattern is defined using a photolithography process.
- a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned.
- the formation of such a catalyst layer is actually the product of a series of substeps.
- a shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the substrate 10 , to define an unmasked surface area same to the pretermined pattern.
- FIGS. 5-6 together illustrate successive stages in a process for forming a carbon nanotube-based device with plural orientations of carbon nanotubes based on the above-described catalyst layer 30 , in accordance with the first embodiment.
- the substrate 10 with the catalyst blocks 33 , 34 is annealed in an oxygen-containing environment at about 300° C., thereby oxidizing the catalyst blocks 33 , 34 to form nano-sized catalyst oxide particles 33 ′, 34 ′. Consequently, the thinner a portion of the catalyst blocks 33 , 34 is, the smaller the diameters of the catalyst oxide particles 33 ′, 34 ′ formed from that portion are. Likewise, the thicker a portion of the catalyst blocks 33 , 34 is, the larger the diameters of the catalyst oxide particles 33 ′, 34 ′ formed from that portion are.
- the treated substrate 10 is placed in a furnace (not shown), a carbon source gas is continuously introduced into the furnace, and then a chemical vapor deposition process similar to that of defining the region 32 of the catalyst layer 30 is implemented.
- the carbon source gas with a protective gas together are continuously introduced into the furnace at a predetermined temperature (e.g. 500-900° C.).
- the carbon source gas can be acetylene, ethylene, methane or any suitable carbon-containing gas.
- the protective gas can be a noble gas or nitrogen.
- the protective gas and carbon source gas are introduced at suitable flow rates respectively (e.g. 160 sccm and 80 sccm respectively).
- a plurality of carbon nanotube arrays 50 , 51 extending from the substrate 10 can be formed.
- the carbon source gas is decomposed into carbon atoms and hydrogen gas in a catalytic reaction process catalyzed by the nano-sized catalyst oxide particles 33 ′, 34 ′.
- the catalyst oxide particles 33 ′, 34 ′ are deoxidized to catalyst particles 33 ′′, 34 ′′ by the hydrogen gas.
- More detailed information on growth of a carbon nanotube array is taught in U.S. Pat. No. 6,232,706 entitled “Self-Oriented Bundles of Carbon Nanotubes and Method of Making Same,” which is incorporated herein by reference. Due to inherently strong Van der Waals force interactions between the carbon nanotubes, the carbon nanotubes are bundled together, and the carbon nanotube arrays 50 , 51 extend in arc shapes bending in directions deviating from the region of the optimum thickness 32 .
- a resultant carbon nanotube-based device 100 with plural orientations of the carbon nanotube arrays 50 , 51 can be formed.
- the carbon nanotube-based device 100 includes the substrate 10 , and a plurality of carbon nanotube arrays 50 , 51 extending from the catalyst layer 30 , supported by the substrate 10 .
- the carbon nanotube arrays 50 , 51 are arc-shaped, and bend in respective directions deviating from the region 32 .
- the catalyst layer 30 only formed at one side of the shadow mask layer 40 , so all the carbon nanotube arrays 50 , 51 of the carbon nanotube-based device 100 totally extend along two different directions (as shown in FIG. 6 ).
- FIGS. 8-12 together illustrate successive stages in a process for forming a catalyst layer on a substrate, in accordance with the second embodiment.
- a substrate 70 is first provided.
- Suitable substrate materials include a variety of materials, including metals, semiconductors and insulators such as silicon (Si), glass and metal sheets. It is possible that the substrate 70 will, in practice, be a portion of a device, e.g., a silicon-based integrated circuit device, on which nanotube formation is desired.
- a shadow mask layer 80 is formed on the substrate 70 and located at a middle portion thereof, to define an unmasked surface area 72 of the substrate 70 to be exposed.
- the shadow mask layer 80 is usually made from photo-resist, metal, metallic oxide, or metallic nitride.
- the shadow mask layer 80 has a suitable height (as denoted by h in FIG. 7 ) to shade a sputter source 60 disposed on the shadow mask layer 80 , in order to sputter-deposit a catalyst layer having a gradient thickness on the substrate 70 .
- the shadow mask layer 80 has a plurality of sidewalls 82 substantially perpendicular to the substrate 70 .
- the height of the shadow mask layer 80 is usually less than mean free path of a catalyst atom generated from the sputter source 60 under a predetermined sputter-deposition process.
- the mean free path (S) of a catalyst atom satisfies the condition (1) as the first embodiment described.
- the sputter source 60 is configured for supplying a catalyst material and depositing the catalyst material onto the substrate 70 , so as to form a catalyst layer having a gradient thickness via a sputter-deposition process.
- the catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof.
- a distance from the sputter source 60 to the substrate 70 is greater than the mean free path of a catalyst atom generated from the sputter source 60 under a predetermined sputter-deposition process.
- the sputter source 60 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material.
- the sputter source 60 having a linear sputter target
- an optimum solution is that a reciprocating movement of the substrate 70 relative to the sputter source 60 along a direction perpendicular to the linear sputter target is implemented.
- the sputter source 60 has a surface sputter target.
- a catalyst layer 90 having a gradient thickness is formed on the unmasked surface area 72 of the substrate 70 , via a sputter-deposition process.
- the catalyst layer 90 is located around the shadow mask layer 80 , and has a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest.
- a thickness of the catalyst layer 90 is gradually varied from one end thereof to another opposite end thereof.
- a thickness T( ⁇ ) of a position of the catalyst layer 90 distant from the shadow mask layer 80 with a distance of ⁇ approximately satisfies the condition (2) as the above-described. It is realized from the condition (2) that an obvious gradient thickness exists in the region where ⁇ varies from 0 to 2h; and the size of the region is correlated with the height of the shadow mask layer 80 . In practice, the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device.
- the shadow mask layer 80 is removed from the substrate 70 .
- a region 92 of the catalyst layer 90 is marked for purpose of determining the growth direction of carbon nanotubes.
- a method for defining the region 92 of the catalyst layer 90 is similar to that as the first embodiment described.
- the catalyst layer 90 can be patterned to meet the various configurations of resultant carbon nanotube-based devices.
- the patterned catalyst layer 90 includes at least one catalyst block having a gradient thickness.
- a thickness of the at least one catalyst block gradually varies from a first end thereof to an opposite second end thereof.
- the least one catalyst block somewhere has a thickness proximal or equal to the optimum thickness for growing carbon nanotubes.
- the patterned catalyst layer 90 includes a plurality of catalyst blocks 93 , 94 , 95 , 96 each positioned at a side of the region 92 .
- a thinnest end of each of the catalyst blocks 93 , 96 has a thickness proximal or equal to the optimum thickness, and a thickest end of each of the catalyst blocks 94 , 95 has a thickness proximal or equal to the optimum thickness.
- the pattern is defined using a photolithography process.
- a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned.
- the formation of such a catalyst layer is actually the product of a series of substeps.
- a shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the substrate 90 , to define a unmasked surface area same to the predetermined pattern.
- FIGS. 13-14 together illustrate successive stages in a process for forming a carbon nanotube-based device with plural orientations of carbon nanotubes based on the above-described catalyst layer 90 , in accordance with the second embodiment.
- the substrate 70 with the catalyst blocks 93 , 94 , 95 , 96 is annealed in an oxygen-containing environment at about 300° C., thereby oxidizing the catalyst blocks 93 , 94 , 95 , 96 to form nano-sized catalyst oxide particles 93 ′, 94 ′, 95 ′, 96 ′. Consequently, the thinner a portion of the catalyst blocks 93 , 94 , 95 , 96 is, the smaller the diameters of the catalyst oxide particles 33 ′, 34 ′ formed from that portion are. Likewise, the thicker a portion of the catalyst blocks 93 , 94 , 95 , 96 is, the larger the diameters of the catalyst oxide particles 93 ′, 94 ′, 95 ′, 96 ′ formed from that portion are.
- the treated substrate 70 is placed in a furnace (not shown), a carbon source gas is introduced into the furnace, and then a chemical vapor deposition process similar to that of defining the region 92 of the catalyst layer 90 is implemented.
- a plurality of carbon nanotube arrays 101 , 102 , 103 , 104 extending from the substrate 70 can be formed.
- the carbon source gas is decomposed into carbon atoms and hydrogen gas in a catalytic reaction process catalyzed by the nano-sized catalyst oxide particles 93 ′, 94 ′, 95 ′, 96 ′.
- the catalyst oxide particles 93 ′, 94 ′, 95 ′, 96 ′ are deoxidized to catalyst particles 93 ′′, 94 ′′, 95 ′′, 96 ′′ by the hydrogen gas.
- the carbon nanotubes Due to inherently strong Van der Waals force interactions between the carbon nanotubes, the carbon nanotubes are bundled together, and the carbon nanotube arrays 101 , 102 , 103 , 104 extend in arc shapes bending in respective directions of deviating from the region 92 .
- a resultant carbon nanotube-based device 1000 with plural orientations of the carbon nanotube arrays 101 , 102 , 103 , 104 can be formed.
- the carbon nanotube-based device 1000 includes the substrate 70 , and a plurality of carbon nanotube arrays 101 , 102 , 103 , 104 extending from the catalyst layer 90 (as shown in FIG. 14 ), supported by the substrate 70 .
- the carbon nanotube arrays 101 , 102 , 103 , 104 are arc-shaped, and bend in respective directions deviating from the region 92 .
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Abstract
Description
- This application is related to one copending U.S. patent application entitled “METHOD FOR MAKING CARBON NANOTUBE-BASED DEVICE”, concurrently filed here with (Docket No. US7938), and having the same assignee as the instant application. The disclosure of the above-indentified application is incorporated herein by reference.
- The present invention generally relates to a method for making a carbon nanotube-based device.
- Carbon nanotubes are very small tube-shaped structures essentially having the composition of a graphite sheet, formed as a tube. Carbon nanotubes produced by arc discharge between graphite rods were first discovered and reported in an article by Sumio Iijima entitled “Helical Microtubules of Graphitic Carbon” (Nature, Vol. 354, Nov. 7, 1991, pp. 56-58). Carbon nanotubes have very good electrical conductance due to their structure. They are also chemically stable, and have very small diameters (less than 100 nanometers) and large aspect ratios (length/diameter). Due to these and other properties, it has been suggested that carbon nanotubes can play an important role in fields such as microscopic electronics, materials science, biology and chemistry.
- Although carbon nanotubes promise to have a wide range of applications, better control is needed over the building and organization of nanotube-based architectures. Normally, the orientation of growing nanotubes is controlled such that the nanotubes are rectilinear and parallel to each other. Chemical vapor deposition has been used to produce nanotubes vertically aligned on catalyst-printed substrates.
- There have been reports of growth of aligned carbon nanotubes using chemical vapor deposition, for instance, Z. F. Ren et al. entitled “Synthesis of large arrays of well-aligned carbon nanotubes on glass” (Science, Vol. 282, Nov. 6, 1998, pp. 1105-1107), S. S. Fan et al. entitled “Self-oriented regular arrays of carbon nanotubes and their field emission properties” (Science, Vol. 283, Jan. 22, 1999, pp. 512-514), B. Q. Wei et al. entitled “Organized assembly of carbon nanotubes” (Nature, Vol. 416, Apr. 4, 2002, pp. 495-496), Yoon-Taek Jang et al. entitled “Lateral growth of aligned mutilwalled carbon nanotubes under electric field” (Solid State Communications, Vol. 126, 2003, pp. 305-308), and Ki-Hong Lee et al. entitled “Control of growth orientation for carbon nanotubes” (Appl. Phys. Lett., Vol. 82, Jan. 20, 2003, pp. 448-450).
- However, carbon nanotubes obtained by the above-mentioned methods are aligned along a linear direction, and/or extend perpendicularly from the substrates. Furthermore, the method of using an external field such as an electric field or a magnetic field, to control a direction of growth of the carbon nanotubes is difficult to apply in generating localized complicated structures with plural orientations of the carbon nanotubes. Accordingly, the range of diversity of different kinds of carbon nanotube-based devices is limited.
- What is needed is to provide a method for making a carbon nanotube-based device with plural orientations of carbon nanotubes.
- In a preferred embodiment, a method for making a carbon nanotube-based device is provided. The method includes the following steps of: providing a substrate having a shadow mask layer formed thereon, the shadow mask layer being configured for defining an unmasked surface area on the substrate; disposing a sputter source on the shadow mask layer, the sputter source being configured for supplying a catalyst material and depositing the catalyst material onto the substrate; forming a catalyst layer including at least one catalyst block on the unmasked surface area of the substrate, a thickness of the at least one catalyst block being gradually decreased from a first end thereof to an opposite second end thereof, and the at least one catalyst block having a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest; introducing a carbon source gas; and forming at least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process, wherein the at least one carbon nanotube array being arc-shaped, and bending in a direction of deviating from the region.
- Theoretically, the growth rate of carbon nanotubes is associated with a thickness of the catalyst layer used to grow them on. Under certain conditions for growing carbon nanotubes by a chemical vapor deposition process, the carbon nanotubes grow fastest when the catalyst layer has a certain optimum thickness. In particular, when the thickness of the catalyst layer is greater than the optimum thickness, the thicker the catalyst layer, the slower the growth rate of carbon nanotubes; when the thickness of the catalyst layer is less than the optimum thickness, the thinner the catalyst layer, the slower the growth rate of carbon nanotubes. If the thickness of the catalyst layer is deliberately controlled, so that the thickness gradually varies from a first end to an opposite second end, and somewhere the catalyst layer has a thickness proximal or equal to the optimum thickness for growing carbon nanotube; additionally, carbon nanotubes have inherently strong Van der Waals force interactions therebetween. Thereby, a carbon nanotube-based device with plural orientations of carbon nanotubes is obtainable.
- Other advantages and novel features will become more apparent from the following detailed description of embodiments when taken in conjunction with the accompanying drawings.
- The components in the drawings are not necessarily to scale, the emphasis instead being placed upon clearly illustrating the principles of the present method for making a carbon nanotube-based device. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
-
FIG. 1 is a schematic, cross-sectional view of one stage in a procedure for sputter-depositing a catalyst layer on a substrate in accordance with the first embodiment; -
FIG. 2 is a schematic, cross-sectional view of a subsequent stage in a procedure for sputter-depositing a catalyst layer on the substrate ofFIG. 1 ; -
FIG. 3 is an isometric view of the substrate ofFIG. 2 with the catalyst layer formed thereon, after the shadow mask layer being removed, and a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest, of the catalyst layer being marked; -
FIG. 4 is similar toFIG. 3 , but showing the catalyst layer patterned into a plurality of catalyst blocks positioned at opposite sides of the region; -
FIG. 5 is an enlarged, side view of the substrate and catalyst blocks ofFIG. 4 after being annealed; -
FIG. 6 is an enlarged, side view of a carbon nanotube-based device in accordance with the first embodiment, obtained by treating the catalyst blocks ofFIG. 5 ; -
FIG. 7 is an isometric view of the carbon nanotube-based device ofFIG. 6 ; -
FIG. 8 is a schematic, cross-sectional view of one stage in a procedure for sputter-depositing a catalyst layer on a substrate in accordance with the second embodiment; -
FIG. 9 is a schematic, cross-sectional view of a subsequent stage in a procedure for sputter-depositing a catalyst layer on a substrate ofFIG. 8 ; -
FIG. 10 is a schematic, cross-sectional view of the substrate ofFIG. 9 with the catalyst layer formed thereon, after the shadow mask layer being removed, and a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest, of the catalyst layer being marked; -
FIG. 11 is an isometric view of the substrate ofFIG. 10 with the catalyst layer formed thereon; -
FIG. 12 is similar toFIG. 11 , but showing the catalyst layer patterned into a plurality of catalyst blocks positioned at opposite sides of the region; -
FIG. 13 is an enlarged, side view of the substrate and catalyst blocks ofFIG. 12 after being annealed; -
FIG. 14 is an enlarged, side view of a carbon nanotube-based device in accordance with the second embodiment, obtained by treating the catalyst blocks of the substrate ofFIG. 13 ; and -
FIG. 15 is an isometric view of the carbon nanotube-based device ofFIG. 14 . - The exemplifications set out herein illustrate at least one preferred embodiment, in one form, and such exemplifications are not to be construed as limiting the scope of the present method for making a carbon nanotube-base device in any manner.
-
FIGS. 1-4 together illustrate successive stages in a process for forming a catalyst layer on a substrate, in accordance with the first embodiment. - Referring to
FIG. 1 , asubstrate 10 is first provided. Suitable substrate materials include a variety of materials, including metals, semiconductors and insulators such as silicon (Si), glass and metal sheets. It is possible that thesubstrate 10 will, in practice, be a portion of a device, e.g., a silicon-based integrated circuit device, on which nanotube formation is desired. - A
shadow mask layer 40 is formed on thesubstrate 10 and located at one end portion thereof to define anunmasked surface area 12 of thesubstrate 10 to be exposed. Theshadow mask layer 40 is usually made from photo-resist, metal, metallic oxide, or metallic nitride. Theshadow mask layer 40 has a suitable height (as denoted by h inFIG. 1 ) to shade asputter source 20 disposed above theshadow mask layer 40, in order to sputter-deposit a catalyst layer having a gradient thickness on thesubstrate 10. Advantageously, theshadow mask layer 40 has a plurality ofsidewalls 42 substantially perpendicular to thesubstrate 10. The height of theshadow mask layer 40 is usually less than mean free path of a catalyst atom generated from thesputter source 20 under a predetermined sputter-deposition process. The mean free path S of a catalyst atom satisfies the condition (1): -
- where, d is a diameter of the catalyst atom, p is an operating pressure of the sputter-deposition process, k is the Boltzmann constant (1.38066×10−23 J/K (Joule per kelvin)), T is an operating absolute temperature of the sputter-deposition process. For example, when the T≈273.15 kelvin, p=1 pascal; the mean free path S of a catalyst iron atom is approximately equal to 13.5×10−3 meters.
- The
sputter source 20 is configured for supplying a catalyst material and depositing the catalyst material onto thesubstrate 10, so as to form a catalyst layer having a gradient thickness via a sputter-deposition process. The catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof. Generally, a distance from thesputter source 20 to thesubstrate 10 is greater than the mean free path of a catalyst atom generated from thesputter source 20 under a predetermined sputter-deposition process. Thesputter source 20 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material. In the case of thesputter source 20 having a linear sputter target, an optimum solution is that a reciprocating movement of thesubstrate 10 relative to thesputter source 20 along a direction perpendicular to the linear sputter target is implemented. In the illustrated embodiment, thesputter source 20 has a surface sputter target. - Referring to
FIG. 2 , due to the shading effect of theshadow mask layer 40 to the catalyst material generated from thecatalyst source 20, acatalyst layer 30 having a gradient thickness is formed on the unmaskedsurface area 12 of thesubstrate 10 via a sputter-deposition process. Thecatalyst layer 30 is located at one side of theshadow mask layer 40. Thecatalyst layer 30 has a region with a thickness proximal or equal to, an optimum thickness at which carbon nanotubes growing fastest. A thickness of thecatalyst layer 30 is gradually varied from one end thereof to another opposite end thereof - Generally, a thickness T(λ) of a position of the
catalyst layer 30 distant from theshadow mask layer 40 with a distance of λ approximately satisfies the following condition (2): -
T(λ)=T 0/2×(1+λ/√{square root over (λ2 +h 2)}) (2) - where, T0 is a thickness of the position under a situation that no
shadow mask layer 40 exists on thesubstrate 10 during the sputter-deposition process; h is a height of theshadow mask layer 40. - It is realized from the condition (2) that an obvious gradient thickness exists in the region where λ varies from 0 to 2h. The size of the region is correlated with the height of the
shadow mask layer 40. For example, when the height h of theshadow mask layer 40 is in the range from 0.1 micrometers to 10 millimeters; correspondingly, the length (starting from the shadow mask layer 40) of the region having obvious gradient thickness is in the range from 0.2 micrometers to 20 millimeters In practice, the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device. - Referring to
FIG. 3 , theshadow mask layer 40 is removed from thesubstrate 10. Aregion 32 of thecatalyst layer 30 is marked for purpose of determining the growth direction of carbon nanotubes. That is, under certain conditions for growing carbon nanotubes by a chemical vapor deposition process, the carbon nanotubes grow fastest at where a region of thecatalyst layer 30 has an optimum thickness. If the conditions for growing the carbon nanotubes by the chemical vapor deposition process are predetermined, the optimum thickness can be determined accordingly. In the illustrated embodiment, as an example, the catalyst material is iron, a carbon source gas is ethylene, a temperature at which the carbon nanotubes are grown is about 700° C. (degrees Celsius). Accordingly, an optimum thickness of thecatalyst layer 30 for growing carbon nanotubes is about 5 nm, i.e., theregion 32 in this condition has a thickness proximal or equal to 5 nanometers. - Referring to
FIG. 4 , thecatalyst layer 30 can be patterned to meet various configurations of resultant carbon nanotube-based devices. Thepatterned catalyst layer 30 includes at least one catalyst block having a gradient thickness. In particular, a thickness of the at least one catalyst block gradually varies from a first end thereof to an opposite second end thereof The least one catalyst block somewhere has a thickness proximal or equal to the optimum thickness for growing carbon nanotubes. - Advantageously, when the
patterned catalyst layer 30 is made from iron, a thickness of the thickest end of each of the catalyst blocks is in the range from 5 nm to 20 nm, and a thickness of the thinnest end of each the catalyst blocks is in the range from 1 nm to 10 nm. In the illustrated embodiment, thepatterned catalyst layer 30 includes a plurality of catalyst blocks 33, 34 staggeringly positioned at opposite sides of the region ofoptimum thickness 32. A thinnest end of each of the catalyst blocks 34 has a thickness approximately equal to the optimum thickness, and a thickest end of each of the catalyst blocks 33 has a thickness approximately equal to the optimum thickness. The pattern is defined using a photolithography process. - It is understood that, a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned. The formation of such a catalyst layer is actually the product of a series of substeps. A shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the
substrate 10, to define an unmasked surface area same to the pretermined pattern. After a catalyst layer sputter-deposition process similar to the process as above-mentioned being implemented, and the shadow mask layer being removed using a lift-off process, a catalyst layer having the predetermined pattern can be directly obtained. -
FIGS. 5-6 together illustrate successive stages in a process for forming a carbon nanotube-based device with plural orientations of carbon nanotubes based on the above-describedcatalyst layer 30, in accordance with the first embodiment. - Referring to
FIG. 5 , thesubstrate 10 with the catalyst blocks 33, 34 is annealed in an oxygen-containing environment at about 300° C., thereby oxidizing the catalyst blocks 33, 34 to form nano-sizedcatalyst oxide particles 33′, 34′. Consequently, the thinner a portion of the catalyst blocks 33, 34 is, the smaller the diameters of thecatalyst oxide particles 33′, 34′ formed from that portion are. Likewise, the thicker a portion of the catalyst blocks 33, 34 is, the larger the diameters of thecatalyst oxide particles 33′, 34′ formed from that portion are. - Subsequently, the treated
substrate 10 is placed in a furnace (not shown), a carbon source gas is continuously introduced into the furnace, and then a chemical vapor deposition process similar to that of defining theregion 32 of thecatalyst layer 30 is implemented. In particular, the carbon source gas with a protective gas together are continuously introduced into the furnace at a predetermined temperature (e.g. 500-900° C.). The carbon source gas can be acetylene, ethylene, methane or any suitable carbon-containing gas. The protective gas can be a noble gas or nitrogen. The protective gas and carbon source gas are introduced at suitable flow rates respectively (e.g. 160 sccm and 80 sccm respectively). - Referring to
FIG. 6 , a plurality ofcarbon nanotube arrays substrate 10 can be formed. During the process of growing thecarbon nanotube arrays catalyst oxide particles 33′, 34′. Thus thecatalyst oxide particles 33′, 34′ are deoxidized tocatalyst particles 33″, 34″ by the hydrogen gas. More detailed information on growth of a carbon nanotube array is taught in U.S. Pat. No. 6,232,706 entitled “Self-Oriented Bundles of Carbon Nanotubes and Method of Making Same,” which is incorporated herein by reference. Due to inherently strong Van der Waals force interactions between the carbon nanotubes, the carbon nanotubes are bundled together, and thecarbon nanotube arrays optimum thickness 32. - Referring to
FIG. 7 , a resultant carbon nanotube-baseddevice 100 with plural orientations of thecarbon nanotube arrays device 100 includes thesubstrate 10, and a plurality ofcarbon nanotube arrays catalyst layer 30, supported by thesubstrate 10. Thecarbon nanotube arrays region 32. In the illustrated embodiment, because thecatalyst layer 30 only formed at one side of theshadow mask layer 40, so all thecarbon nanotube arrays device 100 totally extend along two different directions (as shown inFIG. 6 ). -
FIGS. 8-12 together illustrate successive stages in a process for forming a catalyst layer on a substrate, in accordance with the second embodiment. - Referring to
FIG. 8 , asubstrate 70 is first provided. Suitable substrate materials include a variety of materials, including metals, semiconductors and insulators such as silicon (Si), glass and metal sheets. It is possible that thesubstrate 70 will, in practice, be a portion of a device, e.g., a silicon-based integrated circuit device, on which nanotube formation is desired. - A
shadow mask layer 80 is formed on thesubstrate 70 and located at a middle portion thereof, to define anunmasked surface area 72 of thesubstrate 70 to be exposed. Theshadow mask layer 80 is usually made from photo-resist, metal, metallic oxide, or metallic nitride. Theshadow mask layer 80 has a suitable height (as denoted by h inFIG. 7 ) to shade asputter source 60 disposed on theshadow mask layer 80, in order to sputter-deposit a catalyst layer having a gradient thickness on thesubstrate 70. Advantageously, theshadow mask layer 80 has a plurality ofsidewalls 82 substantially perpendicular to thesubstrate 70. The height of theshadow mask layer 80 is usually less than mean free path of a catalyst atom generated from thesputter source 60 under a predetermined sputter-deposition process. The mean free path (S) of a catalyst atom satisfies the condition (1) as the first embodiment described. - The
sputter source 60 is configured for supplying a catalyst material and depositing the catalyst material onto thesubstrate 70, so as to form a catalyst layer having a gradient thickness via a sputter-deposition process. The catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof. Generally, a distance from thesputter source 60 to thesubstrate 70 is greater than the mean free path of a catalyst atom generated from thesputter source 60 under a predetermined sputter-deposition process. Thesputter source 60 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material. In the case of thesputter source 60 having a linear sputter target, an optimum solution is that a reciprocating movement of thesubstrate 70 relative to thesputter source 60 along a direction perpendicular to the linear sputter target is implemented. In the illustrated embodiment, thesputter source 60 has a surface sputter target. - Referring to
FIG. 9 , acatalyst layer 90 having a gradient thickness is formed on the unmaskedsurface area 72 of thesubstrate 70, via a sputter-deposition process. Thecatalyst layer 90 is located around theshadow mask layer 80, and has a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest. A thickness of thecatalyst layer 90 is gradually varied from one end thereof to another opposite end thereof. - Generally, a thickness T(λ) of a position of the
catalyst layer 90 distant from theshadow mask layer 80 with a distance of λ approximately satisfies the condition (2) as the above-described. It is realized from the condition (2) that an obvious gradient thickness exists in the region where λ varies from 0 to 2h; and the size of the region is correlated with the height of theshadow mask layer 80. In practice, the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device. - Referring to
FIGS. 10 and 11 , theshadow mask layer 80 is removed from thesubstrate 70. Aregion 92 of thecatalyst layer 90 is marked for purpose of determining the growth direction of carbon nanotubes. A method for defining theregion 92 of thecatalyst layer 90 is similar to that as the first embodiment described. - Referring to
FIG. 12 , thecatalyst layer 90 can be patterned to meet the various configurations of resultant carbon nanotube-based devices. Thepatterned catalyst layer 90 includes at least one catalyst block having a gradient thickness. In particular, a thickness of the at least one catalyst block gradually varies from a first end thereof to an opposite second end thereof. The least one catalyst block somewhere has a thickness proximal or equal to the optimum thickness for growing carbon nanotubes. - In the illustrated embodiment, the
patterned catalyst layer 90 includes a plurality of catalyst blocks 93, 94, 95, 96 each positioned at a side of theregion 92. A thinnest end of each of the catalyst blocks 93, 96 has a thickness proximal or equal to the optimum thickness, and a thickest end of each of the catalyst blocks 94, 95 has a thickness proximal or equal to the optimum thickness. The pattern is defined using a photolithography process. - It is understood that, a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned. The formation of such a catalyst layer is actually the product of a series of substeps. A shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the
substrate 90, to define a unmasked surface area same to the predetermined pattern. After a catalyst layer sputter-deposition process similar to the process as above-mentioned being implemented, and the shadow mask layer being removed using a lift-off process, a catalyst layer having the predetermined pattern can be directly obtained. -
FIGS. 13-14 together illustrate successive stages in a process for forming a carbon nanotube-based device with plural orientations of carbon nanotubes based on the above-describedcatalyst layer 90, in accordance with the second embodiment. - Referring to
FIG. 13 , thesubstrate 70 with the catalyst blocks 93, 94, 95, 96 is annealed in an oxygen-containing environment at about 300° C., thereby oxidizing the catalyst blocks 93, 94, 95, 96 to form nano-sizedcatalyst oxide particles 93′, 94′, 95′, 96′. Consequently, the thinner a portion of the catalyst blocks 93, 94, 95, 96 is, the smaller the diameters of thecatalyst oxide particles 33′, 34′ formed from that portion are. Likewise, the thicker a portion of the catalyst blocks 93, 94, 95, 96 is, the larger the diameters of thecatalyst oxide particles 93′, 94′, 95′, 96′ formed from that portion are. - Subsequently, the treated
substrate 70 is placed in a furnace (not shown), a carbon source gas is introduced into the furnace, and then a chemical vapor deposition process similar to that of defining theregion 92 of thecatalyst layer 90 is implemented. - Referring to
FIG. 14 , a plurality ofcarbon nanotube arrays substrate 70 can be formed. During the process of growing thecarbon nanotube arrays catalyst oxide particles 93′, 94′, 95′, 96′. Thus thecatalyst oxide particles 93′, 94′, 95′, 96′ are deoxidized tocatalyst particles 93″, 94″, 95″, 96″ by the hydrogen gas. Due to inherently strong Van der Waals force interactions between the carbon nanotubes, the carbon nanotubes are bundled together, and thecarbon nanotube arrays region 92. - Referring to
FIG. 15 , a resultant carbon nanotube-based device 1000 with plural orientations of thecarbon nanotube arrays substrate 70, and a plurality ofcarbon nanotube arrays FIG. 14 ), supported by thesubstrate 70. Thecarbon nanotube arrays region 92. In the illustrated embodiment, because thecatalyst layer 90 formed around theshadow mask layer 80, so all thecarbon nanotube arrays FIG. 15 ). - It is believed that the present embodiments and their advantages will be understood from the foregoing description, and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the examples hereinbefore described merely being preferred or exemplary embodiments of the invention.
Claims (21)
T(λ)=T 0/2×(1+λ/√{square root over (λ2 +h 2)})
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