Raman scattering characterization of CVD graphite lms

Alexander N. Obraztsov
a,b,
*
, Anastasiya V. Tyurnina
a,d
, Ekaterina A. Obraztsova
a
,
Alexey A. Zolotukhin
a,b,d
, Binghai Liu
c
, Kok-Chung Chin
c
, Andrew T.S. Wee
c
a
Department of Physics, Moscow State University, Moscow 119991, Russia
b
Department of Physics and Mathematics, University of Joensuu, Joensuu 80101, Finland
c
Department of Physics, National University of Singapore, 117542 Singapore, Singapore
d
Technological Institute of Superhard and Novel Carbon Materials, 142190 Troitsk, Russia
A R T I C L E I N F O
Article history:
Received 19 December 2007
Accepted 3 March 2008
Available online 10 March 2008
A B S T R A C T
Raman spectroscopic study has been performed for thin graphite lms grown on nickel
substrates by chemical vapor deposition from a mixture of hydrogen and methane acti-
vated by a direct current discharge. Depending on the growth conditions, the CVD lms
are composed of graphene layers parallel to the substrate surface or of plate-like crystal-
lites with the predominant orientation of their graphene layers perpendicular to the sub-
strate surface. A comparison of the Raman spectra for the CVD lms and for the highly
oriented pyrolytic graphite has been performed. The mechanisms governing the Raman
scattering process in the lms are discussed. An important role of a double resonance
mechanism in the Raman spectra of these graphite-based materials has been revealed.
The Raman band positions and intensities and their dependence on excitation wavelength
conrm a high degree of the structural order in the CVD graphite lms.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Detailed analysis of graphene (a single graphite layer) is
important for understanding of fundamental properties of
nanocarbon in general. A recent development of a simple
technique for formation of isolated graphene akes has trig-
gered numerous experimental studies of its electronic proper-
ties [13]. The unique properties of a single-layer and a few-
layer graphene lms are very important for practical applica-
tions [46]. One of the most attractive peculiarities of these
materials is a specic dependence between energy and im-
pulse of electron, which is nearly linear in the proximity of
K point in the Brillouin zone. The valence and conduction
bands of the dispersion curves cross at the Fermi level. Such
electronic structure is a fundamental reason of the semimetal
(semiconductor with a zero energy gap) type of the graphite
conductivity and some other interesting effects. One of them
is the resonant Raman scattering spectra with specic band
shapes and dispersion.
Usually the Raman scattering in crystals is observed at fre-
quencies corresponding to the phonons of the Brillouin zone
center (C point). At this point, the impulses of phonons and
electrons are close to zero. A large energy gap (more than
15 eV [7]) in graphite (and graphene) at C point makes the res-
onant Raman scattering impossible at frequencies of around
1580 cm
1
, associated with the phonons from this point.
The corresponding Raman line usually called as G-line is a re-
sult of in-plane CC atoms vibrations. Near K point of the
Brillouin zone, the electron energy is linearly dependent on
its impulse and the difference between the valence and con-
duction band branches changes from a few eV to zero. For the
phonons from this region, the resonant Raman scattering is
possible when a change of the impulse of the electrons partic-
ipating in this process is somehow compensated. This situa-
tion can be realized in case of simultaneous emission (or
absorption) of a phonon with the same impulse and an elastic
interaction of the electrons with the structural defects of
graphite or when the impulses of two phonons participating
0008-6223/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2008.03.002
* Corresponding author: Address: Department of Physics, Moscow
State University, Moscow 119991, Russia. Fax: +7 495 939 2988.
E-mail address: obraz@polly.phys.msu.ru (A.N. Obraztsov).
C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8
avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ car bon
in the process compensate each other [811]. The correspond-
ing Raman scattering mechanism is usually called the dou-
ble resonance mechanism because there are two
successive electron transitions between the real states with
different energies and impulses. The Raman lines corre-
sponding to such double resonance scattering are situated
at about 1350 cm
1
(for the single-phonon scattering and
electron interaction with the defect) and 2700 cm
1
(for the
double-phonon scattering). These lines are usually marked
as D and D
*
(or 2D) lines. The Raman shift of 1350 cm
1
corre-
sponds to the phonons from K point of the Brillouin zone. As
the impulses of phonon and electron participating in the Ra-
man scattering process are practically equal, the phonon en-
ergy (or the Raman shift of the D and D
*
lines) depends on the
energy of excitation photon. This dependence is determined
by a dispersion curve for the optical phonons from K point
neighborhood because the electron and phonon impulses
are linearly dependent on the band gap width.
The strong electronphonon coupling resulting in the dou-
ble resonance effect makes possible the study of the struc-
tural and electronic properties of nanocarbon graphite-like
materials using Raman spectroscopy. The Raman spectra
may provide information about the number of graphene lay-
ers and their structural defects. In this work, the double res-
onance Raman scattering was studied to obtain information
about the nano-graphite lms which are attractive for appli-
cations in vacuum- and opto-electronics [12,13].
2. Materials and experimental conditions
The graphite lms were grown by chemical vapor deposition
(CVD) technique using a hydrogenmethane gas mixture acti-
vated by a direct current (DC) discharge. A detailed descrip-
tion of the deposition facility and the growth method has
been reported previously [14,15]. Our CVD system allows pro-
duction of different types of carbon lms ranging from poly-
crystalline diamond to carbon nanotubes. The type of
material deposited depends essentially on the methane con-
centration and on the substrate temperature. In this work,
the process parameters corresponding to the graphite phase
deposition were: the gas mixture composition H
2
:CH
4
= 92:8;
the total gas pressure of 80 Torr; the substrate temperature
about 1000 C.
The square nickel plates with a thickness about 0.5 mm
and the lateral dimensions of 10 10 mm or 25 25 mm were
used as substrates. The nickel substrates were made by cut-
ting the polycrystalline Ni sheets produced by rolling. The
substrates have been treated in pure hydrogen DC plasma
to remove the surface oxide layer before the starting of inter-
action with methane. As it has been shown earlier [14,15], the
CVD lm topology depends essentially on the deposition pro-
cess duration. When the CVD process lasted 45 min or longer,
the obtained material consisted of plate-like graphite crystal-
lites. According to the scanning and transmission electron
microscopy (SEM and TEM), the thickness of these crystallites
varied from 1 to 100 nm, while their lateral dimensions kept
around 24 lm. Every crystallite was formed by the highly-or-
dered graphene layers. For all crystallites, a preferred orienta-
tion of the basic crystal face (0001) was along the normal to
the substrate surface with a deviation of 20. In the other
directions these crystallites demonstrated a random orienta-
tion. The edge-face contact of neighboring crystallites led to
formation of a mechanically stable self-organized mesopor-
ous structure with the characteristic pore diameter of 0.5
2 lm. A typical SEM image of such nano-graphite CVD lm
is shown in Fig. 1a. A high resolution TEM (HRTEM) technique
has revealed that the thinnest part of the nano-graphite
akes is their top edge consisting of a very few atomic layers
(see Fig. 1b). The HRTEM measurements have been carried out
with JEOL JEM-2010 microscope.
A reduction of the deposition time down to 510 min led to
formation of substantially different carbon materials. In the
SEM images this kind of CVD lms demonstrated a specic
morphology with the atomically smooth surface areas sepa-
rated from each other by out-of-plane extrusions [15]. An im-
age of such lm taken with the atomic force microscopy
(AFM) (Nanoscope III Digital Instr.) is shown in Fig. 2. A typical
size of the smooth surface regions is about 0.52 lm. The
ridges forming a net on the lm surface are about 1050 nm
high. Some of the surface regions look like swells formed by
Fig. 1 The typical SEM image of the CVD nano-graphite lm (a) and HRTEM image for a top-edge fragment of the nano-
graphite crystallite (b).
964 C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8
the lm partially exfoliated from the substrate. The thickness
of the at areas on such lms was estimated as 1.5 0.5 nm
[15]. Such well-ordered graphite formation is in agreement
with the mechanism of heteroepitaxial growth of graphite
on the (111) Ni surface which occurs due to a matching of
the crystal lattice parameters of these two materials [16].
The atomic layers (graphenes) in the obtained graphite lm
are conformal with the substrate surface. The ridges on the
lm surface can be explained by the difference in the thermal
expansion coefcients of graphite and nickel [15].
The CVD graphite lms were studied by Raman spectros-
copy with different excitation wavelengths using the follow-
ing spectrometers: a Fourier-transform Raman apparatus
Bruker FRA 106 (with the excitation by a YAG:Nd laser at
1064 nm), a Jobin Yvon-T64000 spectrometer (with the excita-
tion by Ar
+
-laser at 647 and 514 nm) and a Renishaw spec-
trometer in Via Raman Microscope (using second harmonic
of YAG:Nd laser at 532 and HeCd laser at 325 nm). Special
care has been taken to avoid the material heating by the laser
irradiation in course of measurements. For this purpose the
Raman spectra were rst measured with different laser power
densities. The nal level of the laser power density was cho-
sen in the middle of the range where no temporal changes
in the line positions and shapes were observed. Raman spec-
tra of HOPG sample (HOPG SPI-3 GRADE supplied by SPI, West
Chestr, PA 19381, USA) were recorded at the same conditions
to obtain the reference data.
3. Results and discussion
Fig. 3 shows the characteristic Raman spectra of three differ-
ent types of graphite-like materials: HOPG (a), CVD lm ob-
tained on Ni substrate with deposition process lasting
during 5 min (b) and CVD lm obtained on Ni substrates with
60 min process duration (c). It should be mentioned that the
Raman spectra of the lms obtained with the process dura-
tions in range of 45180 min are independent on the deposi-
tion time. Similar spectra were obtained for the CVD lms
grown on substrates made of materials other than nickel (sil-
icon, tungsten, steel, etc.) [13,14]. Raman spectra of HOPG and
CVD lms on Ni grown during 5 min are very similar to each
other. All these spectra, normalized to the intensity of G peak
(positioned at 1580 cm
1
), have been registered with the exci-
tation wavelength 514 nm.
The Raman spectra in Fig. 3 are characteristic of this kind
of carbon materials (see e.g. [10,17]). There are three major
bands G, D, D
*
and their overtones. The D and G (or D and
D
*
[10]) peaks ratio characterizes the disorder degree of the
material studied. For the HOPG sample and for CVD lm
grown during 5 min, the D band intensity was comparable
with the noise level (see spectra a and b in Fig. 3). This con-
rms that the disorder in these samples is negligible. Usually
such spectrum shape corresponds to the single crystal graph-
ite (SCG) [17]. CVD lms grown during 5 min and shown no D
bands in their Raman spectra will be called below as SCG. It is
clearly seen from Fig. 3 that the lm deposited during 60 min
has a pronounced D band which may be attributed to struc-
tural defects including those related to the edges of the
nano-graphite akes [10]. The CVD lms demonstrating this
Fig. 2 The typical AFM image of the CVD lm obtained on nickel substrate with deposition time of 5 min.
Fig. 3 The Raman spectra of the HOPG sample (a), the CVD
lms grown on Ni substrate during 5 min (b) and 60 min (c).
The intensities in all spectra have been normalized to the G
peak value. The backgrounds of the spectra b and c have a
constant shift in vertical direction equal of 20% and 40% of
the G peak intensity, correspondingly.
C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8 965
type of the Raman spectrum will be called below as NCG
(nanocrystalline graphite).
Raman spectra obtained for the SCGand NCGsamples with
different photon energies are shown in Figs. 4 and 5, corre-
spondingly. To avoid the curve overlapping these gures con-
tain only the spectra obtained with the excitation laser
photon energies 1.2 eV (1), 2.4 eV (2) and 3.8 eV (3). The exper-
imental data registered with other photon energies (1.9 eV
wavelength 647 nm, 2.3 eV wavelength 532 nm and 2.5 eV
wavelength 488 nm) are displayed in the graphs by the points
showing the peak position of D and D
*
bands. The dependen-
cies of the peak position of the D and D
*
lines on the excitation
energy are presented in Fig. 6 also. A reduction of the Raman
shift value with the excitation energy value corresponds to
predictions made in frames of the double resonance mecha-
nism taking into account the dispersion curves for electrons
and phonons in graphite and graphite-like materials [711].
In the range of lowexcitation photon energies the dependence
is close to the linear one. A deviation from the linear behavior
is observed in the UV region. It reects a non-linearity of the
electron dispersion curve at higher energies [8].
The intensities of D and D
*
bands are very different for the
SCG and NCG samples (as it can be clearly seen from Figs. 4
and 5). For the SCG samples the intensity of D band is negligi-
ble comparing the noise level of the spectrometers used. As it
was mentioned before, D band appearance in the Raman
spectrum of graphitic materials is assigned usually to struc-
tural defects (including those related to the crystallite edges).
However, a lower intensity of D band in the Raman spectra of
HOPG and SCG samples comparing with that of NCG lms,
may also resulted from a difference in their crystallographic
orientation in respect to the excitation laser beam. Accord-
ingly to [18] this intensity is much lower for the beam direc-
tion perpendicular to the basal plane of the graphite crystal.
Our STM investigations have shown that the surface of the
SCG lms consists of the atomically at regions [15]. There-
fore we can conclude that this kind of lm is a graphite mate-
rial composed of the atomic layers parallel to the substrate
surface with the ordering comparable with that of a single-
crystalline graphite. In the back-scattering Raman geometry
the basal crystallographic plane in the case of SCG lms is di-
rected perpendicularly to the laser beam corresponding to the
case of the lowest intensity of D band for single crystal graph-
ite [18]. At the same time the dimensions of the ake-like
crystallites in NCG lms are comparable with those of the at
areas in SCG material, but their basal planes are parallel to
the laser beam. Due to this the input of their edges into the
Raman scattering at D-band frequency should be larger.
The peak intensity of the D
*
band in the Raman spectra of
SCG increases with the photon energy decrease (see Fig. 4). A
similar increase of intensities of D and D
*
bands with the
Fig. 4 The Raman spectra (left scale) of SCG CVD lm
measured with different photon energies of excitation:
spectrum 1 1.2 eV (wavelength 1064 nm), spectrum 2
2.4 eV (wavelength 514 nm) and spectrum 3 3.8 eV
(wavelength 325 nm). The peak position of D
*
band
measured with the photon energies 1.2, 1.9, 2.3, 2.4, 2.5
and 3.8 eV (right scale) are shown by ,-mark. The
intensities have been normalized to the G peak value.
Fig. 5 The Raman spectra (left scale) of NCG CVD lm
measured with different photon energies of excitation:
spectrum 1 1.2 eV (wavelength 1064 nm), spectrum 2
2.4 eV (wavelength 514 nm) and spectrum 3 3.8 eV
(wavelength 325 nm). The peak positions of the D and D
*
bands measured with the photon energies 1.2, 1.9, 2.3, 2.4,
2.5 and 3.8 eV (right scale) are shown by e-mark and h-
mark, correspondingly. The intensities have been
normalized to the G peak value.
Fig. 6 The dependencies of peak position of the D and D
*
bands on photon energy, measured for SCG (,) and NCG (e
and h, correspondingly). The marks coincide with the
experimental points shown in Figs. 4 and 5.
966 C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8
decrease of the laser photon energy was observed for NCG
samples (see Fig. 5). Fig. 7 shows the intensity dependencies
on the photon energy (inset) and on the Raman shift of D
and D
*
bands. Both dependencies may be approximated by
the exponential curves (shown by the dashed lines). This
may be explained by the interconnection between the electron
and phonon impulses which demonstrate an almost linear
behavior in K point proximity. The rise of the peak intensities
may result fromanincrease of the absolutevalue of the Raman
matrix element determining the resonance input [11] and by
the increase of the density of phonon states [9,19]. In this case
we can expect a further Dand D
*
intensity increase as the exci-
tation photon energies decay to the level corresponding to the
maximum in the density of phonon states (around 1260 cm
1
)
[9,11]. Our experimental observation coincides with the
dependence of Dband intensity on the laser photon energy re-
ported previously (see e.g. [18,20] and references in these pa-
pers). However, in one of the previous paper cited above [18]
the dependence of D
*
line positiononexcitationphotonenergy
is opposite to ours (see Fig. 7). This discrepancy may be ex-
plained by the common difculties in measurements of the
weak Raman signals in the near infrared range arising due to
the registrationsensitivity. There is no informationinthework
[18] concerning the Raman instrument parameters. But it is
known that a sensitivity of the usual photomultiplier or Si-
based CCD drops quickly with the photon energies about
1 eV. This energy corresponds to that of the outcoming pho-
tons contributing to D
*
band with the excitation at 780 nm
[18]. Thus, the reduction of the line intensity may be resulted
fromimperfectionof the registrationsystemused inthis work.
To avoid similar problem in our work different Raman spec-
trometers with sensitivities adjusted to have no spectral
dependence in the working range were used.
The shape of D
*
band is sensitive to the graphene sheets
number ranging from 1 to 5. For the bigger numbers, the Ra-
man spectrum becomes very similar to that of bulk graphite
[10]. For the SCG lms studied, we have observed the signi-
cant variations of the D
*
band shape over the sample surface.
For some points, the measured spectra were similar to known
for a xed small number of graphene layers (from 2 to 5),
while the spectra obtained in another points were similar to
those of bulk single crystal graphite. It should be noted that
for NCG samples, the D
*
band shape measured with green la-
sers was always approximately constant in all points and cor-
responded to bulk graphite. Meanwhile we have found that
the shape and intensity of D
*
band was different for the SCG
lm areas being at or forming the swells. An example of
such a difference is shown in Fig. 8.
A similar difference in the relative intensity of D
*
band was
observed between the spectra of NCG lms and SCG materials
(see Fig. 3). The D
*
band intensity increase with approximately
same ratio have been observed also in [18] where this effect
was explained by coupling of electrons in neighboring graph-
ene sheets due to their interconnection along edges and for-
mation of frill-like bent structures. However this explanation
contradicts to our observations made for essentially at graph-
ite layers where D
*
band intensity in exfoliated area are much
larger than in at regions (see Fig. 8) despite there are no addi-
tional graphene interconnections and, thus, no additional
electron coupling. This effect of the D
*
band intensity increase
may be explainedby the inuence of a conductive substrate on
the electron sub-system in the SCG lm. A better adhesion of
the at areas on the SCG lm surface leads to a stronger inu-
ence of the substrate to electrons in the graphite lm. The
electronsubstrate interactionis reduced for the lms exfoli-
ated from the substrate in the swelling area, and for the akes
standingperpendicularlytothe substrate surface. Aremoval of
the interaction with substrate leads to an increase of the num-
ber of photo-excited electrons taking part in the Raman scat-
tering and, thus, increasing of the D
*
band intensity.
Fig. 7 The dependencies of the peak intensities (normalized to that of G band) on the Raman shift and on the photon energy
(inset) for D
*
band of SCG (,), and D (e) and D
*
(h) bands of NCG. The Raman shift of D band is shown on the bottom axis. That
of D
*
band is shown on the top. The dashed lines are exponential curves interpolating the experimental dependencies. The
photon energies corresponding to the experimental points are shown with the arrows.
C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8 967
4. Conclusions
In this work, we performed a systematic study of the nano-
graphite CVD lms by Raman spectroscopy. The studied
materials were grown by CVD on nickel substrates in the con-
ditions differing only by the duration of the deposition pro-
cess. The graphite lms of nanometer thickness consisting
of graphene sheets conformal to the substrate surface were
obtained with the deposition time about 5 min. Longer pro-
cess duration led to appearance of the graphite akes consist-
ing of graphene layers oriented perpendicularly to the
substrate. The akes had a nanometer-scale thickness. For
the deposition times longer than 45 min, these akes com-
bined into the mesoporous self-organized structures. The Ra-
man spectra behavior for both types of the nano-graphite
lms was described well in frames of a double-resonance
mechanism. For the rst time we report an experimental
dependence of the peak intensity of the second order Raman
scattering on the phonons from K point of the Brillouin zone
on the excitation photon energy. This dependence is ex-
plained by the peculiarities of the absolute value of the Ra-
man matrix element determining the resonance input and
the photon density of states of graphene and graphite. We
have found also that the intensity of the second order Raman
scattering signicantly increases when the surface of the
nano-graphite species has no direct contact with the sub-
strate. This effect is explained by the removal of the conduc-
tive substrate inuence on the photo-excited electrons
participating in the Raman scattering process.
Acknowledgements
The authors are grateful to the National University of Singa-
pore for the support via EERSS Program. The work has been
supported, in part, by the INTAS (Grant 05-109-4966), by EU
FP6 (Project 12881 FERROCARBON), and by Academy of Fin-
land (Projects 123252, 124133).
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Fig. 8 An example of D
*
band shapes obtained in the
Raman spectra measured at the surface of SCG lm in at
and swelled areas. A scheme in the inset shows the
measurement points. The spectra have been normalized to
G band intensity.
968 C A R B O N 4 6 ( 2 0 0 8 ) 9 6 3 9 6 8