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Fullerene Nanotubes (Buckytubes)

New Materials (& New Devices)


from CARBON

R. E. Smalley
University of Tokyo
Departments of Chemistry and Physics
February 22, 2001
Rice University

MOLECULAR PERFECTION:
The FULLERENE IDEAL

•The Strongest fiber that will ever be made.


•Electrical Conductivity of Copper or Silicon.
•Thermal Conductivity of Diamond.
•The Chemistry of Carbon.
•The size and perfection of DNA.

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Predicted
Tensile Strength
of single-wall
Nanotubes
>100 GPa

>30% strain
to failure

Yakobson, et al., Comp.


Mat. Sci. 8, 341 (1997).

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Twisted Tubes
Don’t Break

Yakobson, et al.,
J. Comp.-Aided Mat.
Design 3, 173 (1996).

A new class of molecules


for organic chemistry

Same old chemistry.

But these organic molecules conduct electricity!

Some Background on carbon nanotubes


Multiwalled carbon nanotubes have been made for over 100 years.
Rodger Bacon, J. Appl. Physics 31, 285 (1960)
and shown to be nested, concentric tubes consisting of scrolls of graphene sheets
•They were also made from hydrocarbon vapor + vapor phase catalyst
by Morinobu Endo in late ’70s, and by Gary Tibbetts et. al. in the ’80s
•They were made more cleanly from hydrocarbons + supported catalyst
by Howard Tennent in ’80s
• They were rediscovered and “fullerenized” by Sumio Iijima in 1991
where they appeared to be nested fullerene tubes
• They are now believed to be a mixture of scrolls and nested single walled tubes
[eg. Malcolm Green et. al., Chem. Phys. Lett. 249, 413 (1996) ]
• At least so far, they are all highly defected materials – not true molecules.

Single-walled carbon nanotubes are true fullerenes, they are “buckytubes”


• C70 was the first step in the right direction – the littlest buckytube
• longer fullerene tubes were made in laser ablation experiments in late 1980’s
• they were present in vapor-grown carbon fibers made by the Endo method
• they are now produced in carbon arcs, laser ablation, and by CVD
• large scale (ktons) production will come from high pressure CO (HiPco) process

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The LASER-OVEN METHOD OF BUCKYTUBE PRODUCTION

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Purified “Bucky paper” (a tangle of ropes)

http://cnst.rice.edu/tubes.html

• Purified swnt from laser/oven method


• Original price (Sept. 1998): $2000/g
• Current price (Sept 2000): $1000/g
• Total Sales (Sept. ‘98 to Dec ‘00):
~$400,000 (~ 300 grams)
60% US, 30% Europe,
15% Japan, 5 % other
• ONR has made 75 g available to DoD
researchers (66 g shipped to date)
• commercial spin-off now completed
to Carbon Nanotechnologies Inc.

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The HiPco Process
Single walled carbon nanotubes (swnt)
from Hi pressure CO ( Pco)

1 step

Gas phase

R. E. Smalley
CNL
Rice University

the HiPco PROCESS


Fen
CO + CO 900-1200 C
CO2 + C(swnt)
10-400 atm

• Catalyst cluster is nucleated in gas phase from Fe(CO)5


with Ni(CO)4 as nucleation aid
• CO is preheated to 1000 C and rapidly mixed
with Fe/Ni carbonyl precatalyst in CO at 150 C
• Highly turbulent mixing brings catalyst to active temperature in < 1 msec
• Product is nearly pure swnt with ~ 1 atom % catalyst
• Optimization can make this much better (and make the tubes much longer)
• Diameter of nanotube depends on Pco and catalyst addition rate
• Diameter can be as small as 0.7 nm (the size of C60 )
• Current HiPco apparatus produces >25g/day
•It’s all Chemical Engineering from here on out
• Ultimate process will resemble the Haber-Bosch Process [N2 + 3 H2 2 NH3 ]
• Time to commercial production at ktons/day level is now dependant primarily on
developing applications
• Carbon Nanotechnologies Inc., CNI , has been formed to develop this market
and to scale up the HiPco process to ktons/day and beyond.

TM
A Special talent of HiPco Buckytubes :

SUPER-ROPING
Purified HiPco Raw HiPco
(air bake 150C, then 850C in Ar, then conc. HCl wash) 80 C in Oleum for 24 hrs.

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…field-emitters for flat-panel displays…

SWNT emitters

…RFI shielding…

…lithium-ion battery anodes…

(SWNT)

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Buckytube
Electro-
mechanical
NanoActuators
~1% length change per volt

Baughman et al., Science 284, 1340 (1999)

…probes and sensors…

Sensors DNA Sequencing


Direct haplotyping of kilobase-size DNA using carbon nanotube probes, A. T. Woolley, C. Guillemette, C.-L. Cheung,
D. E. Housman, and C. M. Lieber, Nature Biotechnology 18, 760 (2000)

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Buckytube-FET

C. Dekker, Delft, Netherlands

SOURCE DRAIN

T-tube transistor
(tube FET)
GATE

T-tube cross

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…Molecular Electronics…

Conductivity and molecular perfection


allows nanotubes to be used as switches
and memory elements.

Carbon Nanotube-Based Nonvolatile Random Access Memory for Molecular Computing, T. Rueckes, K. Kim, E.
Joselevich, G. Y. Tseng, C.-L. Cheung, and C. M. Lieber, Science 289, 94 (2000).

Side-Wall Chemistry of SWNT

F2 250oC
F F F F F F F F F F F F

F F F F F F F F F F F F

H2N-NH2
Br-Mg-R OR Li-R
R R R R R R R R R R R R

heat
O2
R R R R R R R R R R R R

R: -CH3, -C(CH3)3 etc.

Wrapped single walled carbon nanotubes


can be made to be soluble in water (and therefore in the cytoplasm of cells)

This merges the best of the “dry side” of nanotechnology


(extreme strength, electrical, and thermal conductivity)
with the best of the “wet side” -- ie. Cellular Life

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Macroscopic, Highly-Aligned Nanotube Material

At Right, an entirely new material made of aligned


single-wall carbon nanotubes. It is a thin (approx. 1.5µ)
membrane having about 1014 individual nanotubes per
cm2 oriented in the same direction. This is by far the
largest sample of an organized nanotube material ever
made. It is expected to have novel thermal and
electrical properties, and is the starting point for growth
of bulk materials having the incomparable physical,
electrical and chemical properties of nanotubes. This
SEM image of a 3-mm wide area shows clearly that the
material is highly-anisotropic, tearing in ribbons along
the direction of tube orientation. We prepared the material by using a strong (27
Tesla) magnetic field to align nanotube segments
(250 nm median length) suspended in a
water/surfactant mixture. Alignment of the
suspended tubes is shown at left, where
transmission of polarized light by the nanotube
suspension is shown as a function of angle
between the light polarization and the magnetic field
direction for several values of the field. At higher
fields, the signal clearly saturates, indicating
excellent alignment. The aligned material was
prepared by slowly filtering an aligned suspension.
During filtration, the individual tube segments self-
assemble into a macroscopic, planar array of
parallel tubes, creating the material shown above.

This now has been made to work at 7 Tesla.

Continuous Fullerene Fibers and Cables


Spinning nanotubes into fibers and cables

Spinneret Partial alignment


Heat
SWNT
solution

Eject nanotubes into


solvent where they
precipitate out
Heat and tension

>10 microns Aligned fiber


(108 tubes)

Single Crystal Fullerene Nanotube Arrays

Quite likely the basis of the Strongest, Lightest, Toughest


Materials that will ever be made out of anything.

It may be possible to grow these


materials from high pressure CO at
rates of >1 meter per hour

May be able to convert growth to


BN nanotube crystalline arrays
by switching to high pressure N2
plus borazine vapor (B3N3H3).

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VISUALIZE

SUCCESS

2001 A SPACE ODDESY

Smalley’s research group shown here celebrating


the first successful growth of the buckytube single crystal!

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