
An artist's representation of an amine functional
group attached to an AFM tip approaching a carbon nanotube surface
in toluene solution. Translucent blue shape on the nanotube
represents the polarization charge forming on the nanotube as the
result of the interaction with the approaching molecule. Chemical
force microscopy measures the tiny forces generated by this single
functional group interaction.
Illustration by Scott Dougherty, LLNL
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A recent report by a team of Lawrence Livermore National Laboratory
researchers and colleagues found that the interaction strength does
not follow conventional trends of increasing polarity or repelling
water. Instead, it depends on the intricate electronic interactions
between the nanotube and the functional group.
�This work pushes chemical force microscopy into a new territory,�
said Aleksandr Noy, lead author of the paper that appeared
in the Oct. 14, 2007, online issue of the
journal, Nature Nanotechnology.
Understanding the interactions between carbon nanotubes (CNTs) and
individual chemical functional groups is necessary for the engineering
of future generations of sensors and nano devices that will rely on
single-molecule coupling between components. Carbon nanotubes are
extremely small, which makes it particularly difficult to measure the
adhesion force of an individual molecule at the carbon nanotube
surface. In the past, researchers had to rely on modeling, indirect
measurements and large microscale tests.
But the Livermore team went a step further and smaller to get a more
exact measurement. The scientists were able to achieve a true single
function group interaction by reducing the probe-nanotube contact area
to about 1.3 nanometers (one million nanometers equals one millimeter).
Adhesion force graphs showed that the interaction forces vary
significantly from one functionality to the next. To understand these
measurements, researchers collaborated with a team of computational
chemists who performed ab initio simulations of the interactions of
functional groups with the sidewall of a zig-zag carbon nanotube.
Calculations showed that there was a strong dependence of the
interaction strength on the electronic structure of the interacting
molecule/CNT system. To the researchers delight, the calculated
interaction forces provided an exact match to the experimental results.
�This is the first time we were able to make a direct comparison
between an experimental measurement of an interaction and an ab initio
calculation for a real-world materials system,� Noy said. �In the past,
there has always been a gap between what we could measure in an
experiment and what the computational methods could do. It is exciting
to be able to bridge that gap.�
This research opens up a new capability for nanoscale materials
science. The ability to measure interactions on a single functional
group level could eliminate much of the guess work that goes into the
design of new nanocomposite materials, nanosensors, or molecular
assemblies, which in turn could help in building better and stronger
materials, and more sensitive devices and sensors in the future.
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