US20060210467A1 - Producing a stable catalyst for nanotube growth - Google Patents

Producing a stable catalyst for nanotube growth Download PDF

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Publication number
US20060210467A1
US20060210467A1 US11/082,437 US8243705A US2006210467A1 US 20060210467 A1 US20060210467 A1 US 20060210467A1 US 8243705 A US8243705 A US 8243705A US 2006210467 A1 US2006210467 A1 US 2006210467A1
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carbon
catalyst
forming
step comprises
applying
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US11/082,437
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Inventor
Steven Smith
Bernard Coll
Jaime Quintero
Yi Wei
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Motorola Solutions Inc
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Motorola Inc
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Priority to US11/082,437 priority Critical patent/US20060210467A1/en
Assigned to MOTOROLA, INC. reassignment MOTOROLA, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COLL, BERNARD F., QUINTERO, JAIME A., SMITH, STEVEN M., WEI, YI
Priority to PCT/US2006/005838 priority patent/WO2006101637A2/en
Priority to CNA200680004863XA priority patent/CN101133190A/zh
Priority to JP2007548626A priority patent/JP2008525183A/ja
Priority to EP06735485A priority patent/EP1859084A2/en
Publication of US20060210467A1 publication Critical patent/US20060210467A1/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1271—Alkanes or cycloalkanes
    • D01F9/1272—Methane

Definitions

  • the present invention generally relates to a catalytic process for growing carbon nanotubes and more particularly to a process for producing a stable and highly reactive catalyst for carbon nanotube growth.
  • Carbon is one of the most important known elements and can be combined with oxygen, hydrogen, nitrogen and the like. Carbon has four known unique crystalline structures including diamond, graphite, fullerene and carbon nanotubes.
  • carbon nanotubes refer to a helical tubular structure grown with a single wall or multi-wall, and commonly referred to as single-walled nanotubes (SWNTs), or multi-walled nanotubes (MWNTs), respectively. These types of structures are obtained by rolling a sheet formed of a plurality of hexagons. The sheet is formed by combining each carbon atom thereof with three neighboring carbon atoms to form a helical tube.
  • Carbon nanotubes typically have a diameter in the order of a fraction of a nanometer to a few hundred nanometers.
  • a carbon nanotube is known to be useful for providing electron emission in a vacuum device, such as a field emission display.
  • the use of a carbon nanotube as an electron emitter has reduced the cost of vacuum devices, including the cost of a field emission display.
  • the reduction in cost of the field emission display has been obtained with the carbon nanotube replacing other electron emitters (e.g., a Spindt tip), which generally have higher fabrication costs as compared to a carbon nanotube based electron emitter.
  • the manufacturing costs for vacuum devices e.g., a field emission display
  • a carbon nanotube can be further reduced if the carbon nanotube is grown on the field emission substrate from a catalytic surface using chemical vapor deposition or other film deposition techniques.
  • Nanotube growth can be conducted as a last deposition process preventing the degradation of the electron emitter properties by other device processing techniques or steps (e.g., wet processes).
  • Carbon nanotubes can also function as either a conductor, like metal, or a semiconductor, according to the rolled shape and the diameter of the helical tubes.
  • metallic-like nanotubes it has been found that a one-dimensional carbon-based structure can conduct a current at room temperature with essentially no resistance. Further, electrons can be considered as moving freely through the structure, so that metallic-like nanotubes can be used as ideal interconnects.
  • semiconductor nanotubes are connected to two metal electrodes, the structure can function as a field effect transistor wherein the nanotubes can be switched from a conducting to an insulating state by applying a voltage to a gate electrode. Therefore, carbon nanotubes are potential building blocks for nanoelectronic devices because of their unique structural, physical, and chemical properties.
  • the CVD process has allowed selective growth of individual SWNTs, and simplified the process for making SWNT based devices.
  • the choice of catalyst materials that can be used to promote SWNT growth in a CVD process has typically been limited to Fe/Mo nanoparticles.
  • the catalytic nanoparticles were usually derived by wet chemical routes, which are time consuming and difficult to use for patterning small features.
  • Another approach for fabricating nanotubes is to deposit metal films using ion beam sputtering to form catalytic nanoparticles.
  • CVD growth of SWNTs at temperatures of 900° C. and above was described using Fe or an Fe/Mo bi-layer thin film supported with a thin aluminum under layer.
  • the required high growth temperature prevents integration of CNTs growth with other device fabrication processes.
  • Ni has been used as one of the catalytic materials for formation of SWNTs during laser ablation and arc discharge process as described by A. Thess, R. Lee, P. Nikolaev, H. Dai, P. Petit, J. Robert, C. Xu, Y. H. Lee, S. G. Kim, A. G. Rinzler, D. T. Colbert, G. E. Scuseria, D. Tomanet, J. E. Fischer, and R. E. Smalley in Science, 273, 483 (1996) and by D. S. Bethune, C. H. Kiang, M. S. de Vries, G. Gorman, R. Savory, J. Vazquez, and R. Beyers in Nature, 363, 605 (1993).
  • an oxidation layer forms on the catalyst nanoparticles in the ambient environment.
  • hydrogen is used in the reduction phase of growth cycle, to remove the oxidation prior to growing the nanotubes.
  • this must be done immediately prior to growing the nanotubes and depending on the CNT growth technique and process conditions employed, such as thermal versus plasma enhanced, active gas composition, gas temperature, not all of the oxidation is removed.
  • This results in a decrease of catalyst activity and in a reduction of the active site density leading consequently to the prevention of carbon nanotubes from growing on the catalyst as desired.
  • the embodiment of this disclosure involves the passivation of the catalyst with a diamond like carbon (DLC) layer prior growth process, it permits an increase of catalyst activity and selectivity resulting in better carbon nanotubes, as compared to known art catalyst.
  • DLC diamond like carbon
  • a process is provided for preparing a catalyst.
  • a catalyst is formed over a substrate.
  • a gas comprising hydrogen and carbon is applied to the catalyst, wherein a carbon seeding layer is formed on the catalyst.
  • Carbon nanotubes may then be grown from the catalyst having the carbon seeding layer thereon.
  • FIG. 1 is a cross sectional view of a previously known catalyst structure
  • FIG. 2 is a cross sectional view of the previously known catalyst structure being subjected to a gas in accordance with the preferred process of the present invention
  • FIG. 3 is a cross sectional view of the preferred embodiment of the present invention.
  • FIG. 4 is a flow chart showing the steps in one embodiment of the present invention.
  • FIG. 5 is as graph showing field emission performance of carbon nanotubes grown in accordance with the preferred embodiment of the present invention versus field emission performance of carbon nanotubes grown with prior art technology.
  • a previously known process comprises depositing a metal 16 on a dielectric layer 14 such as silicon dioxide or silicon nitride grown or formed in ambient air on the substrate 12 .
  • the substrate 12 comprises silicon; however, alternate materials, for example, silicon, glass, ceramic, metal, a semiconductor material, or a organic material are anticipated by this disclosure.
  • Substrate 12 can include control electronics or other circuitry, which are not shown in this embodiment for simplicity.
  • the metal 16 is molybdenum, but may comprise any metal.
  • a layer of metal 18 is deposited on the metal 16 to support the catalyst 20 thereon.
  • the metal 18 is aluminum, but may be any support material having inert interaction with the catalyst 20 .
  • the catalyst 20 preferably comprises nickel, but could comprise any one of a number of other materials including cobalt, iron, and a transition metal or oxides and alloys thereof.
  • the catalyst 20 may be formed in any number of ways known in the industry. One preferred method would be to form a relatively smooth film and subsequently etching the film to provide a rougher surface, or catalyst 40 .
  • carbon nanotubes includes any elongated carbon structure.
  • the structure 10 having the catalyst 20 thereon may be exposed to ambient for some time prior to growing the carbon nanotubes 28 . This exposure can allow ambient contaminants to be physi-absorbed or chemi-absorbed onto the catalyst 20 , where one effect can be the formation of an oxide layer 22 to be formed on the catalyst 20 .
  • hydrogen or a hydrogen-containing gas is introduced into the chamber to aid in chemically scrubbing the catalyst surface and promotes the reduction of surface contaminants including the oxidized catalyst layer.
  • the chemical scrubbing efficiency of the catalyst scales with higher temperature, as such low temperature methods for growing carbon nanotubes 28 become less efficient in chemically scrubbing the catalyst, which can lead to poor catalytic reactivity resulting in fewer carbon nanotubes 28 .
  • the structure 10 is placed in a chamber (not shown) and subjected to a gas 24 .
  • the gas 24 preferrably comprises methane (CH4), but may comprise any combination of hydrogen and carbon.
  • the gas 24 is then excited to form a plasma which produces carbon and hydrogen radicals and ions.
  • the gas 24 can form a film ranging from a hydrogen-rich amorphous carbon (polymer-like) to a more dense amorphous carbon having lower hydrogen content and is classically referred to as a diamond-like carbon (DLC) film.
  • Process temperatures for DLC films can range from 15° C. to 600° C.
  • the gas 24 must comprise sufficient hydrogen to chemically reduce any oxides formed on the catalyst 22 while also depositing a dense amorphous carbon (DLC) 26 or a DLC matrix that consisting of DLC clusters supported in an amorphous carbon layer 26 having sufficient thickness to completely passivate the catalyst and is generally 5 nm or greater.
  • DLC dense amorphous carbon
  • the DLC passivation layer 26 subsequently becomes a catalyst seeding layer during the carbon nanotube growth process and significantly enhances catalytic reactivity.
  • Carbon nanotubes 28 are then grown from the catalyst 20 having the carbon layer 26 formed thereon in a manner known to those skilled in the art. Although only a few carbon 20 and carbon nanotubes 28 are shown, those skilled in the art understand that any number of carbon 20 and carbon nanotubes 28 could be formed.
  • the carbon nanotubes 28 may be grown, for example, as electron emitters for use in display devices or as conductive elements in sensors or electronic circuits. It should be understood that any nanotube having a height to radius ratio of greater than 100, for example, would function equally well with some embodiments of the present invention. Additionally, the catalyst 20 may be formed by any process known in the industry, e.g., co-evaporation, co-sputtering, co-precipitation, wet chemical impregnation, incipient wetness impregnation, adsorption, ion exchange in aqueous medium or solid state, before having the present invention applied thereto.
  • a conductive layer 16 , 18 is formed 42 over a substrate 12 and catalyst 20 are then formed 44 on the conductive layer 16 , 18 .
  • a gas 24 comprising carbon and hydrogen is applied 46 to the catalyst 20 to form a carbon seeding layer 26 on the catalyst 20 .
  • Carbon nanotubes 28 may then be grown 48 from the catalyst 20 having the carbon seeding layer 26 thereon.
  • the graph illustrates the improved emission current density of the present invention versus the known art.
  • the samples were created and tested alike except for data curves 52 and 54 the samples have seen pre-deposition of a DLC seeding layer over the catalyst 20 prior to HF-CVD processing.
  • the samples associated with curves 56 and 58 were submitted to only hydrogen gas reduction step during HF-CVD to remove any oxide.
  • the results reported in FIG. 5 show that the field emission current density extracted with catalyst 20 samples 52 and 54 processed using the present invention, are an order of magnitude better than the prior art catalyst samples 56 and 58 .
  • the “improvement” resulting from the present invention catalyst is mainly due to longer carbon nanotubes, thinner carbon nanotubes, higher density of carbon nanotubes, and less defective carbon nanotubes.
  • the high current density measured for catalyst samples 52 and 54 reflect a higher density and more uniform carbon nanotube growth. Furthermore, the sharpness of the I-V characteristics exhibited by curves 52 and 54 and their low threshold of emission current, are an indication of carbon nanotube growth with better form factor (longer and thinner) due to better activity of carbon seed layer 26 passivated catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
US11/082,437 2005-03-17 2005-03-17 Producing a stable catalyst for nanotube growth Abandoned US20060210467A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US11/082,437 US20060210467A1 (en) 2005-03-17 2005-03-17 Producing a stable catalyst for nanotube growth
PCT/US2006/005838 WO2006101637A2 (en) 2005-03-17 2006-02-17 Producing a stable catalyst for nanotube growth
CNA200680004863XA CN101133190A (zh) 2005-03-17 2006-02-17 制备用于纳米管生长的稳定催化剂
JP2007548626A JP2008525183A (ja) 2005-03-17 2006-02-17 ナノチューブ成長用の安定な触媒の製造
EP06735485A EP1859084A2 (en) 2005-03-17 2006-02-17 Producing a stable catalyst for nanotube growth

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US11/082,437 US20060210467A1 (en) 2005-03-17 2005-03-17 Producing a stable catalyst for nanotube growth

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JP (1) JP2008525183A (ja)
CN (1) CN101133190A (ja)
WO (1) WO2006101637A2 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100029063A1 (en) * 2007-01-16 2010-02-04 Northrop Grumman Space & Mission Systems Corporation Carbon nanotube fabrication from crystallography oriented catalyst
US20100209704A1 (en) * 2009-01-19 2010-08-19 Kabushiki Kaisha Toshiba Carbon nanotube growing process, and carbon nanotube bundle formed substrate
US20120282461A1 (en) * 2010-01-19 2012-11-08 Kabushiki Kaisha Riken Member having hydrogen-containing, hard, amorphous carbon coating and its production method

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5089898B2 (ja) * 2006-03-20 2012-12-05 株式会社アルバック カーボンナノチューブの成長方法
JP5293126B2 (ja) * 2008-12-01 2013-09-18 富士通株式会社 半導体装置の製造方法
CN107601458B (zh) * 2017-09-12 2020-07-28 刘云芳 一种单壁碳纳米管的制备方法

Citations (8)

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Publication number Priority date Publication date Assignee Title
US6087765A (en) * 1997-12-03 2000-07-11 Motorola, Inc. Electron emissive film
US6303226B2 (en) * 1999-05-03 2001-10-16 Guardian Industries Corporation Highly tetrahedral amorphous carbon coating on glass
US6346189B1 (en) * 1998-08-14 2002-02-12 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube structures made using catalyst islands
US6475573B1 (en) * 1999-05-03 2002-11-05 Guardian Industries Corp. Method of depositing DLC inclusive coating on substrate
US6548313B1 (en) * 2002-05-31 2003-04-15 Intel Corporation Amorphous carbon insulation and carbon nanotube wires
US20040184981A1 (en) * 2003-03-19 2004-09-23 Liang Liu Carbon nanotube array and method for forming same
US20040250753A1 (en) * 2002-11-22 2004-12-16 Kang Sung Gu Method for forming carbon nanotubes with post-treatment step
US20070003471A1 (en) * 2003-03-31 2007-01-04 Fujitsu Limited Method of manufacturing carbon nanotubes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6087765A (en) * 1997-12-03 2000-07-11 Motorola, Inc. Electron emissive film
US6346189B1 (en) * 1998-08-14 2002-02-12 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube structures made using catalyst islands
US6303226B2 (en) * 1999-05-03 2001-10-16 Guardian Industries Corporation Highly tetrahedral amorphous carbon coating on glass
US6475573B1 (en) * 1999-05-03 2002-11-05 Guardian Industries Corp. Method of depositing DLC inclusive coating on substrate
US6548313B1 (en) * 2002-05-31 2003-04-15 Intel Corporation Amorphous carbon insulation and carbon nanotube wires
US20040250753A1 (en) * 2002-11-22 2004-12-16 Kang Sung Gu Method for forming carbon nanotubes with post-treatment step
US20040184981A1 (en) * 2003-03-19 2004-09-23 Liang Liu Carbon nanotube array and method for forming same
US20070003471A1 (en) * 2003-03-31 2007-01-04 Fujitsu Limited Method of manufacturing carbon nanotubes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100029063A1 (en) * 2007-01-16 2010-02-04 Northrop Grumman Space & Mission Systems Corporation Carbon nanotube fabrication from crystallography oriented catalyst
US7678672B2 (en) 2007-01-16 2010-03-16 Northrop Grumman Space & Mission Systems Corp. Carbon nanotube fabrication from crystallography oriented catalyst
US20100127240A1 (en) * 2007-01-16 2010-05-27 Northrop Grumman Space & Mission Systems Corp. Carbon nanotube fabrication from crystallography oriented catalyst
US7893423B2 (en) 2007-01-16 2011-02-22 Northrop Grumman Systems Corporation Electrical circuit device having carbon nanotube fabrication from crystallography oriented catalyst
US20100209704A1 (en) * 2009-01-19 2010-08-19 Kabushiki Kaisha Toshiba Carbon nanotube growing process, and carbon nanotube bundle formed substrate
US8609199B2 (en) * 2009-01-19 2013-12-17 Kabushiki Kaisha Toshiba Carbon nanotube growing process, and carbon nanotube bundle formed substrate
US20120282461A1 (en) * 2010-01-19 2012-11-08 Kabushiki Kaisha Riken Member having hydrogen-containing, hard, amorphous carbon coating and its production method
US9546425B2 (en) * 2010-01-19 2017-01-17 Kabushiki Kaisha Riken Member having hydrogen-containing, hard, amorphous carbon coating and its production method

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EP1859084A2 (en) 2007-11-28
WO2006101637A3 (en) 2007-11-15
JP2008525183A (ja) 2008-07-17
CN101133190A (zh) 2008-02-27
WO2006101637A2 (en) 2006-09-28

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