CHARACTERIZATION OF CARBON NANOTUBES BY RAMAN

SPECTROSCOPY
Luis Arévalo

Abstract
The discovery and noting of carbon nanotubes (CNTs) performed by Sumio Iijima in 1991 [1]
opened a new window for the research and development upon this allotropic form of carbon, where
soon were noticed the remarkable properties this 1D material presents. These include excellent
mechanics (only below graphene´s), a thermal conductivity in the range of diamond and an electrical
conductivity in the range of the commonly used materials in electrics. Besides, this material presents
some unique properties such as superconductivity and ballistic conduction, and in some cases a
semiconducting behaviour. This set of properties is completed with an extremely low density (0.8
g/cm3) and very high surface area (300-600 m2/g) [2].
Resulting from these properties, during the last decades there has been an intense research in
the synthesis, characterization, and applications in which CNTs may be used. These applications include
energy and hydrogen storage, micro and nanoelectronics, sensors, supercapacitors, structural
composites, and even in the medical field [2-3].
Despite the progress achieved in the synthesis of CNTs during the last years, the synthesis
methods available nowadays for their production at macroscopic scale are still under research. The
mechanisms to control CNTs features (number of walls, chirality, length…) are not fully understood,
and the resulting CNTs macro assemblies include impurities (such as amorphous C or catalyst metal
particles) [4] and defects (such as vacancies, inclusions, heptagon-pentagon…) [5]. Both of them hinder,
at some extent, the exceptional properties CNTs display, so it is essential to perform a good
characterization of this material to determine its performance.
The characterization of CNTs macro assemblies usually includes electron microscopy (SEM
and TEM) to determine morphology, thermogravimetric analysis to determine composition, mechanical
and electrical testing to determine performance, and Raman spectroscopy. This last technique allows
the determination of different features of CNTs, such as the number of walls or the diameter. The
objective of the present work is to perform a study of the different features which can be determined by
the performance of this technique over CNTs.

Introduction
It did not take much time for scientists to realize that the use of Raman spectroscopy could be
a useful tool for CNTs characterization, and the first scientific article on this issue was published in
1997, only 7 years after Iijima’s discovery [6]. From that moment on, the number of publications related
to the use of Raman spectroscopy for CNTs characterization raised exponentially, and after few decades
there are numerous articles, reviews, and book chapters about this issue. The main features obtained by
performing Raman spectroscopy over CNTs and other carbonaceous species are listed down below
(with permission of [7]).

Image 1: list of the main Raman mode frequencies of CNTs, with permission of [7]. Notes: aThe frequency is
observed at Elaser = 2.41eV. bSR: first-order Raman, DR1: one phonon double resonance Raman, DR2: two
phonons double resonance Raman. cThe change of phonon frequency (in cm-1) when changing Elaser by 1 eV.
dIntraV: intravalley scattering, interV: intervalley scattering. Most values of ω and the slope ∂ω/∂E are taken

from graphite-related materials. The values for SWNTs might be shifted. eThe value of ∂ω/∂E is finite for a
double resonance process. fThis value is taken from the work of Tan et al [12].

Some of these features provide useful information over the structure of CNTs; the most
significant ones are shown below.
Radial Breathing Modes (RBMs)
These features are first order phonon modes, related exclusively to single wall CNTs
(SWCNTs), and appear in the range of 100-300 cm-1 of the Raman spectrum [8]. They correspond to the
atomic vibration of C atoms in the radial direction, as if the tube was breathing (see Image 2) [9].
These features are commonly used for the determination of
SWCNTs diameter, and a simple relationship has been found between
the RBM position (ωRBM) and the tube diameter (dt) in both individual
and bundled SWCNTs [9]:

𝜔𝑅𝐵𝑀 = 𝐴⁄𝑑 + 𝐵 [1]

𝑡

Where A = 248 cm-1 / B = 0 for isolated and A = 234 cm-1 / B

= 10 cm-1 for bundled SWCNTs. This relationship has been found to
be accurate for 1 < dt < 2 range.

Image 2: schematic representation

of the atomic vibration for the RBM
in SWCNTs. With permission of [9].
 Other information that can be assessed by RBMs is the chiral index of SWCNTs, which is a
pair of vectors (n,m) which define their structure in terms of the C atoms position (see Image 3) and
determines their electrical properties (SWCNTs can be semiconducting or metallic).

Image 3: chiral index and different types of SWCNTs regarding their chirality. Source:
http://www.intechopen.com/books/carbon-nanotubes-polymernanocomposites/polymer-carbon-
nanotube-nanocomposites

RBM signals are highly dependent on the energy of the excitation laser light, and different laser
lines show different RBM signals. Plotting dt versus Elaser gives place to what is called a Kataura plot,
a graphic showing the possible different families of SWCNTs (see Image 4) [8].

Image 4: Kataura plot. Filled black circles are semiconducting and open red circles
are metallic CNTs. Horizontal lines mark laser energies. With permission of [8].

D-Band
This feature of CNTs and other carbonaceous species is a double resonance Raman scattering
process, commonly attributed to the presence of disorder in carbon systems [10], which appears in the
1350 cm-1 region of the Raman spectra in the case of C bulk materials and at slightly lower frequencies
in the case of CNTs [9]. It worths mentioning that this frequency increases with the energy of the
excitation laser light used [7], decreases with the CNTs diameter (showing a 1/dt dependence) and is
highly dependent on CNTs chirality [9].
The most important information that can be extracted from D-band analysis is the defect
concentration of CNTs, being D-band Raman intensity relative to G-band intensity (ID / IG) a standard
index to note the degree of defects in any graphitic material [7].
 To the date there is no study over the intensity and position of D-band and the different defect
types (vacancies, heptagon-pentagon…) of individual CNTs, but in the case of bundled SWCNTs the
observation of a high intensity D-band is attributed to the presence of amorphous C [9].
G-Band
This feature is the most characteristic of all graphitic materials, a first-order Raman active mode
attributed to the vibration of C atoms in the tangential directions (see Image 5) [9].
G-band appears at 1582 cm-1 of the Raman spectrum in
the case of graphite and multi wall CNTs (MWCNTs), but in the
case of SWCNTs it is a multi-peak feature with up to six peaks
(see Image 6) that can be used to determine their diameter and
chirality independently from RBMs study [9].
A simple analysis of this feature over SWCNTs considers
the two most intense peaks, labelling them as G+ and G-. The first
corresponds to the atomic vibration along the tube´s axis, and the
second to the atomic vibration along the circumferential direction.
When comparing semiconducting and metallic SWCNTs, the
latter present remarkably broader G- bands, which allows
differentiating between them (see Image 6) [9]. Image 5: schematic representation of the
atomic vibration for the G-band tangential
A further analysis between the diameter dependence of mode in a CNT. With permission of [9].
the frequency of G+ (ω+) and G- (ω-) in semiconducting and
metallic SWCNTs reveals that while ω+ is independent from the
tube diameter (dt) in all cases, ω- decreases with it, and this
decrease differs between them. Thus, the splitting between G+ and
G- frequencies (∆𝜔𝐺 = 𝜔𝐺+ − 𝜔𝐺− ) can be used for diameter
characterization [11]. This analysis has been plotted with
experimental data (see Image 7), showing that ω- obeys the
following expression:

𝜔𝐺− = 1591 − 𝐶 ⁄𝑑𝑡2 [2]

Where 𝐶 = 𝐶𝑆 = 47.7 𝑐𝑚−1 𝑛𝑚2 for semiconducting and

𝐶 = 𝐶𝑀 = 79.5 𝑐𝑚−1 𝑛𝑚2 for metallic SWCNTs [11].

Image 6: G-band of highly ordered

pyrolytic graphite (HOPG), MWCNT
Image 7: plot of𝜔𝐺+ and 𝜔𝐺−of semiconducting (filled circles) bundles, an isolated semiconducting
and metallic (open circles) SWCNTs as a function of 1/𝑑𝑡 . With SWCNT and an isolated metallic SWCNT.
permission of [11]. With permission of [9].
Experimental
SWCNTs and MWCNTs synthesized by FC-CVD were gently provided by IMDEA Materials
Institute. These CNTs were given as macroscopic fibres of 2-4 mm width and 2-8 mm length, and a
thickness of less than 10 µm. For the sample preparation the fibres were placed over glass slides,
attached at the edges with sticky tape and embedded with isopropanol. The resulting samples were flat
and homogeneous fibres of bundles of CNTs, as Image 8 shows.

Image 8: samples of SWCNT and MWCNT fibres used to

perform Raman analysis.

Raman spectra were performed using a Renishaw PLC spectrometer with a Nd:YAG laser line
(532nm, 2.41 eV) and 5x, 20x, 50x and 100x objectives. The spectra were performed at 100-2000 cm-1
frequency range, 10 seconds of exposure time, 1% laser power and 1 accumulation. Five Raman spectra
were performed over each sample and the results were averaged for good statistics. All Raman spectra
were baselined, and cosmic rays were removed using Wire 4.4 software before any analysis.

Results and discussion

Analysis of SWCNTs
Image 9 shows the Raman spectra of SWCNT fibre sample.

Image 9: Raman spectra of SWCNT fibre. With permission of IMDEA Materials Institute.
 This image presents RBM signals at 123, 140, 158, 171, 181, 190, 226, 236, 263 and 273 cm-1
frequencies; by applying equation [1] to these values we can determine that this sample has SWCNTs
with 2.07, 1.80, 1.58, 1.45, 1.37, 1.30, 1.08, 1.03, 0.92 and 0.89 nm of diameter.
Table 1 shows the averaged values of the frequencies of D-band, G+ and G- features and the
index of D-band intensity relative to G-band (ID / IG). These values show concordance with the presence
of highly graphitic and low defective SWCNTs that comprise the sample.
Table 1: Raman results of SWCNT fibre.

𝝎𝑫 𝝎−𝑮 𝝎+𝑮
SAMPLE 𝑰𝑫 ⁄𝑰𝑮
[cm-1] [cm-1] [cm-1]
SWCNTs 1339.80 ± 3.11 1572.60 ± 2.88 1591.00 ± 0.00 0.02 ± 0.005

Analysis of MWCNTs
Image 10 shows the Raman spectra of MWCNTs fibre sample, and Table 2 shows the averaged
values of the frequencies of D-Band and G-Band and the index of D-Band intensity relative to G-Band
(ID / IG).

Image 10: Raman spectra of MWCNT fibre. With permission of IMDEA Materials Institute.

Table 2: Raman results of MWCNT fibre.

𝝎𝑫 𝝎𝑮
SAMPLE 𝑰𝑫 ⁄𝑰𝑮
[cm-1] [cm-1]
MWCNTs 1350.60 ± 0.89 1583.60 ± 0.55 0.23 ± 0.051

The absence of RBM signals and of any splitting in the G-Band confirms the presence of
MWCNTs in the sample, while the relatively low ID / IG index points to a low defect concentration.
Conclusions
Raman spectroscopy is a very powerful technique for the characterization of CNTs, essential
for the determination of their structure, number of walls, defects degree, and electrical behaviour.
Altogether with electron microscopy (SEM/TEM) and thermogravimetric analysis (TGA) it becomes a
basic technique for the characterization of any CNT material.
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