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Carbon
Nanotubes: The Outlook for Commercial-Scale Manufacturing Technology |
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Ed Wijaranakula, Ph.D.
Chief Technology Officer, Infotix
Systems, Inc. - September 30, 2004
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While
researchers have known about carbon nanotubes (CNT) since 1991,
only a limited number of CNT-based products have
found their way into niche markets, such as additives to increase the strength and toughness of
a composite,
conductive polymeric films for touch screen displays and carbon nanotube tips
for the atomic force microscope (AFM), a type of high
resolution scanned-proximity probe microscope.
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The major barriers
for full commercialization of CNT materials in the
consumer mass market are their high cost and limited availability.
Considering the fact that the price of high-grade single-wall carbon nanotubes (SWNTs)
is between $350,000 to $500,000 per kilogram, the
possibility of emerging CNT-based consumer products such as high-capacity rechargeable lithium batteries
or portable fuel cells used in mobile devices, becomes
unlikely in the near future. In the consumer electronics
sector, where the CNT manufacturing
process
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is fully compatible with current
nanoelectronic processes, CNT-based
products such as high
resolution low-cost flat panel displays and power
semiconductor chips
for automobiles are already in the final stage of
development for the mass market. The
development and commercialization of CNT-based products
in other sectors
including biomedical devices, household appliances and sporting goods,
will follow as the major
CNT producers begin to ramp up their capacity and utilize
advanced manufacturing technology
to reduce costs. It should be pointed out that a
slowdown in the macro economy due to geopolitical
uncertainties and high energy costs could dampen the progress of CNT-based product
development and commercialization. Catalyzed Chemical
Vapor Deposition (CCVD) and High-Pressure
CO conversion (HiPCO) Processes -
CVD is a widely used method in the fabrication of
microelectronic devices for depositing various types of thin films
including oxide and low-k dielectrics. In a catalyzed
CVD process for SWNT and multi-walled
nanotube (MWNT) manufacturing, reactant gases
such as acetylene
(C2H2)
and methane (CH4),
diluted
with H2 or ammonia
(NH3),
are used as a carbon source. The gas mixture,
which
enters the CVD reactor at room temperature, is heated
up to temperatures ~ 700ºC using a resistance heater
before reacting with a suitable metal catalyst such as
nickel, iron or cobalt to form carbon nanotubes. The catalyst can be deposited directly on the surface of
silicon, silicon dioxide (SiO2)
or quartz substrate
surface as a thin film or in the form of catalytic
nanocrystalline. To increase the catalytic reaction and
thus the process
throughput, plasma from various sources including
radio frequency (RF) and microwave (MW) is used. The
plasma enhanced CVD (PECVD) process can be operated at
temperatures as low as 330ºC and thus is more compatible with commercial-scale
manufacturing, compared to the thermal CVD process. |
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Large-scale production
of high-purity (90% or higher) SWNTs can be done using
the "High-Pressure
CO conversion" (HiPCO) method. In this method, a
gas mix of CO with a small amount of iron pentacabonyl
Fe(CO)5
catalytic particles, is continuously flowed through
high-pressure
heated carbon monoxide
(CO) gas in a quartz flow tube reactor,
operated at ~ 1200ºC. Because CO gas
is used as the primary gas source, CNTs produced by this
method contain no hydrocarbon and are considerably cleaner than
those from other catalyzed CVD processes. Houston, TX-based Carbon Nanotechnologies,
Inc., one of the leading CNT material manufacturers,
uses this technique to produce high-graded CNTs and
fluorinated SWNTs for supercapacitor electrodes and
biomedical sensors. Although the thermal CVD, PECVD and HiPCO methods provide feasible commercial-scale CNT manufacturing
solutions with high throughput and low-cost of ownership,
the key technical
challenge is the control of metallic contamination
originating from the catalyst as well as oxygen, hydrogen
and hydrocarbon from the reactant gases.
A high level of
impurities can have a significant impact on CNT quality and
cause additional
manufacturing costs for purification. In nanoelectronics, the CVD method is considered to be
the "process of choice" because
selective CNTs can be grown on substrate using standard
microlithography processes. In addition, the CNT material can be doped
with elements including nitrogen,
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boron or potassium to
alter electronic properties which enable production of new types of active switching devices such
as field-effect transistors and
nanotube emitters. Munich, Germany-based Infineon Technologies AG (NYSE ADR:
IFX) is one of the first semiconductor
manufacturers to pioneer the low-temperature CCVD process to replace the conventional metal via
process, the vertical interconnects between two metal
layers in the chip, with ultra high current density CNT materials.
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Large
equipment manufacturers including Applied Materials (NASDAQ:AMAT)
and Novellus Systems (NASDAQ:NVLS) do not currently
offer catalyzed CVD solutions for CNT manufacturing.
In the United States, small production and research
thermal CVD and PECVD reactors are available from
specialized equipment companies such as a privately held
Carpinteria, CA-based First Nano, Inc. and Sunnyvale,
CA-based SEOCAL Inc.
Direct Spinning from Chemical Vapor Deposition - Promising
novel technology for commercial-scale manufacturing of
continuous CNT fiber has been developed by a group of
research scientists at University of Cambridge, Ya-Li Li,
et al Science 304, 276–278 (2004). In
the direct spinning CVD technique, ethanol (C2H5OH)
is used as the carbon source. A gas mix of ethanol,
ferrocene (Fe(C5H5)2)
and
thiophene (C4H4S)
vapors along with a hydrogen carrier gas are injected into
the top section of a vertical CVD reactor, operated in the
temperature range of 1050°C to 1200°C. In the reactor hot
zone, the catalyzed reaction
causes a formation of an aerogel-like
substance, an ultra low-density solid which is composed of 99.8% air.
The SWNTs are then mechanically removed from the catalyzed reaction
zone by continuous wind-up. According to the research
scientists, unlimited length of high-grade SWNTs can be spun
using this technique.
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About the Author: Dr. Ed Wijaranakula is presently the
Chief Technology Officer at Infotix Systems, Inc. Prior to Infotix Systems, he has worked with
Intel, Hewlett-Packard, Micron, Motorola and Texas Instruments and has held senior as well
as managerial positions in semiconductor manufacturing companies. He has published over 80
technical papers and holds more than 12 U.S. and foreign patents.
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