Combination of Confocal Raman
Spectroscopy and Electron Microscopy
on the Same Individual Bundles of
Single-Walled Carbon Nanotubes
Chaoyang Jiang, Jixue Li, Jialong Zhao, Ute Kolb, and Alf Mews*
Institut fu ¨ r Physikalische Chemie, UniVersita ¨ t Mainz, Mainz D-55099, Germany
Received August 7, 2002; Revised Manuscript Received August 30, 2002
ABSTRACT
We report a method to investigate the same individual single-walled carbon nanotube (SWNT) bundles with both transmission electron microscopy
(TEM) and Raman spectroscopy. Free-standing individual bundles are obtained by depositing a solution of suspend SWNTs on a carbon film
with a regular pattern of holes, which can be localized by TEM and also by confocal Raman microscopy. While most of the TEM images
predict that the bundles consist of tubes with a similar diameter, we will show that occasionally a certain tube diameter can be associated
with a particular radial breathing mode frequency of the Raman spectrum.
Single-walled carbon nanotubes (SWNTs) are one-dimen-
sional molecular structures with diameters in the range of a
few nanometers. The outstanding mechanical and electrical
properties of these materials have generated significant
activity in both fundamental and applied research.
1,2
For
example, scanning probe tips
3
have been made using SWNTs
because of their high mechanical strength. Also, the pos-
sibility of nanoscale electronic devices was shown by the
realization of single-electron transistors made from SWNTs.
4,5
In principle, a SWNT can be either metallic or semicon-
ducting, depending on its diameter and chirality. Moreover,
SWNTs made by arc-discharge
6
and laser ablation
7
methods
usually self-tangle into bundles containing both metallic and
semiconducting tubes. Therefore, the structural and electronic
analysis of SWNT bundles is of great interest, particularly
in the view of bundle applications.
The structural properties of individual bundles can be
investigated by several microscopic techniques.
6-11
In cases
of high resolution transmission electron microscopy (HR-
TEM) it was even possible to directly observe cross sections
of SWNT bundles when the bundle axis was perpendicular
to the image plane. From these experiments it was argued
that the triangular lattice of SWNT bundles is formed by
nanotubes that are similar in diameter.
6,7
A powerful
technique to probe the electronic properties of bundles and
also individual SWNTs is the method of Raman microscopy
and spectroscopy.
12-14
One of the features in a typical Raman
spectrum of SWNTs is the radial breathing mode (RBM) in
the region of 100-350 cm
-1
. Because the RBM frequency
is sensitive to the tube diameter and chirality,
12,15
a structural
analysis of the SWNTs can also be performed by the method
of Raman spectroscopy.
The relationship between the tube diameter d and the RBM
frequency ω
RBM
has been investigated by several groups and
can, in principle, be described by the following formula:
Bandow and co-authors used a force constant model and
calculated a constant value of x ) 224 independent of the
chirality of the tubes.
16
Jorio et al.
17
used a combination of
theory and Raman experiments where they could assign even
the (n,m) chiral vector to individual SWNTs by using a
parameter of x ) 248. In addition, there have been many
different ab initio calculations on the lattice dynamics of
individual SWNTs and bundles. For example, Henrard et
al. obtained that the expected RBM frequency is not
independent of the tube chirality
11
and also predicted an
upshift in frequency by 5-15% for tubes within bundles
18
(see also Figure 4). A possible bundle effect has also been
reported by other groups.
19,20
An experimental correlation between the frequency and
diameter distributions of SWNT samples can, in principle,
be performed by investigating the same set of samples with
Raman spectroscopy and TEM or X-ray diffraction.
21,22
In
this work we try to avoid averaging over the whole SWNT
ensemble by investigating the same SWNTs with TEM and
Raman spectroscopy. We present a method to directly
correlate the structural and spectroscopic properties of * Corresponding author. E-mail: alf.mews@mail.uni-mainz.de.
d[nm] ) x/ω
RBM
[cm
-1
] (1)
NANO
LETTERS
2002
Vol. 2, No. 11
1209-1213
10.1021/nl025738o CCC: $22.00 © 2002 American Chemical Society
Published on Web 09/28/2002