Raman Spectroscopy of CVD Carbon Thin

Films Excited by Near-Infrared Light

Margit Ko os, Mikl os Veres, Sara T oth, and Mikl os F ule
Research Institute for Solid State Physics and Optics of the Hungarian Academy
of Sciences, Konkoly Thege M.u. 29-33, H-1121 Budapest, Hungary
koos@szfki.hu
Abstract. The interpretation of the Raman spectra of amorphous carbon thin
lms is still controversial. The concept of their decomposition into D and G peaks
does not work in some cases, when presence of additional bands can be deduced
from the shape of the spectra. One to investigate these extra component bands is to
change the excitation wavelength. This results in the enhancement of the Raman
scattering cross-section of the dierent structural units. Our investigations were
aimed to detect the component bands become intense by using infrared excitation
(785 nm) in the Raman spectra of amorphous carbon thin lms prepared from
benzene and methane in a wide range of deposition parameters. By comparing the
visible and infrared excited Raman spectra it will be proven that the well-known
G band of the a-C:H layers consists of two components, one of which exhibiting
no dispersion. It will be also shown that he infrared excitation makes distinguish-
able Raman bands assigned to delocalized () electronic structure due to resonant
enhancement of the scattering.
1 Introduction
1.1 The Raman Eect
When monochromatic light of frequency
L
scatters in a medium, scattered
light intensities shifted from
L
by certain
i
values can be observed in the
spectrum of the scattered light. The value of these shifts depends on the
properties of the scattering media and it does not vary when changing
L
.
This phenomenon is the Raman scattering. During a Raman experiment
the scattered light is measured, and it is represented in relative wavenumbers,
taking the laser wavenumber being equal to zero.
Raman scattering is an inelastic scattering of light on elementary exci-
tations of the medium. The elementary excitations are usually rotational or
vibrational transitions of a molecule or lattice vibrations (phonons) in a solid.
The inelastic scattering is a two-phonon process, where the absorption of an
incoming photon of energy E
L
=
L
with energy transfer and the creation
of an
S
scattered photon take place simultaneously in the medium. The
energy dierence is equal to the energy of the elementary excitation.
If the energy transfer is positive (
L

S
) the process is called Stokes
scattering, the opposite case (
L

S
) is known as anti-Stokes scattering.
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 423445 (2006)
Springer-Verlag Berlin Heidelberg 2006
424 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
The E = E
0
cos (
L
t ) electromagnetic eld of frequency
L
acting on a
medium induces a dipole moment
in
determined by the polarizability of the
medium:

in
= E = E
0
cos (
L
t ). (1)
A molecule or an elementary cell consisting of N atoms has 3N degrees of
freedom, 3 of which are transitional, 3 (2 for a linear system) are rotational
and 3N 6 (3N 5 for a linear system) are vibrational ones. 3N Cartesian
coordinates are needed to describe the motion of such a system. It is suitable
to use internal coordinates, describing the variations of bond lengths and
bond angles during vibrations. Combining these coordinates, the orthogonal
vibrational normal modes of the molecule (cell) can be described. The
ij
components of the polarizability tensor can be expressed through the normal
coordinates of the system:

ij
= (
ij
)
0
+

ij
Q
k

0
Q
k
+
1
2

k,k

ij
Q
k
Q

Q
k
Q

k
+ . (2)
Restricting (2) to rst-order terms, combining (1) with (2) and applying
trigonometric identities, we get:

in,ij
= (
ij
)
0
E
0
cos (
L
t)
+
1
2

ij
Q
k

0
Q
k
E
0
{cos [(
L
+)t +
k
] + cos [(
L
)t
k
]} . (3)
From (3) it can be seen that during a scattering process a medium will
emit photons at frequencies
L
,
L
+ and
L
corresponding to Rayleigh,
anti-Stokes and Stokes scattering, respectively. While Raleigh scattering does
always exist, Raman scattering occurs only if the polarizability of the medium
changes during the scattering process. The rst-order terms of the polariz-
ability tensor represent the components of the Raman tensor R.
Energy and momentum are conserved in the Raman process:

S
=
L

k
S
= k
L
+k
ph
, (4)
where k
L
, k
S
and k
ph
are the momenta of the incoming and scattered photons
and of the phonon, respectively. According to (4), the energy loss of the
photon equals the energy of the lattice vibration. Considering that, for the
visible light the 10
4
cm
1
magnitude of k
L
and k
S
is much less than the
size of the rst Brillouin zone of the crystals (about 10
10
cm
1
), it can be
concluded that only zone centre phonons participate in the scattering.
Raman Spectroscopy of CVD Carbon Thin Films 425
In the classical picture described above, the mechanism of the scattering
does not matter. The quantum mechanical treatment of the process considers
the electronphoton and electronphonon interactions through their Hamilto-
nians H
eR,
and H
eph,
( and being the polarizations of the incoming
and scattered photons, respectively). The core of the quantum mechanical
treatment of the Raman scattering is the transition matrix element K
2f,10
:
K
2f,10
=

a,b

S
,f ,i|H
eR,
|0,f ,b0,f,b|H
eph
|0,0,a0,0,a|H
eR,
|
L
,0,i
(
E
L
E
e
ai
i
)(
E
S
E
e
bi
i
)
, (5)
where |
L
, 0, i is the initial state characterized by the incoming photon of
E
L
=
L
energy, by the phonon in 0 state (no excited phonon) and by the
electron in ground state i. The nal state
S
, f , i| is characterized by the
photon of E
S
=
S
energy, by the phonon in the f state and by the electron
in the ground state; a and b are the intermediate states participating in the
scattering process. E
e
ai
and E
e
bi
are the energy dierences of states a and i as
well as b and i, respectively; is the lifetime of the excited states. According
to (5) the Raman scattering is a three-step process consisting of:
(a) absorption of the incoming photon with transition of the electron into an
excited state (creation of an electronhole pair)
(b) inelastic scattering of the electron on a phonon
(c) recombination of the electron and the hole with emission of the scattered
photon
The three steps take place simultaneously. The electron can be excited from
the ground state either into a virtual state or into an existing state. In the
latter case, the scattering is resonant.
The K
2f,10
matrix element is related to the Raman tensor (R) through
the polarization vectors of the incoming (e
L
) and scattered (e
S
) light:
K
2f,10
= e
L
R e
S
.
The scattered intensity is proportional to the square of the transition matrix
element:
I |K
2f,10
|
2
.
It is dicult to calculate the intensity of the process since the transition
matrix elements are dicult to determined.
The number of lines observed in the Raman spectra is less than the num-
ber of phonons existing in the crystal. This is not only due to the degeneracy
of the phonons, but it is because of the number of phonons which can partic-
ipate in the scattering is limited by the selection rules. The rst restriction
is that the scattering takes place only on zone-centre phonons. Additionally,
during the scattering the polarizability of the medium should change, which
426 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
requires the phonons to have certain symmetries. The simplest way to deter-
mine whether a given phonon will cause a nonzero polarizability change is to
take into account group theory considerations.
When the energy of the incoming or outgoing photon is close to an existing
energy transition of the medium, a signicant increase in the Raman intensity
can be observed due to resonant enhancement of the scattering. Depending
on whether the resonance is for the incoming or scattered light, one can
distinguish between incoming and outgoing resonances.
In noncrystalline materials there is no elementary cell and the periodicity
is lost. This leads to breakdown of the selection rules. As a result, in these ma-
terials any phonon can participate in the scattering. However, the vibrations
will not be extended in the whole crystal, instead they will be localized. The
Raman spectrum is obtained by summing all of these localized vibrations [1]:
I () = (
L
)
4

b
C
b

[1 +n(, T)] g
b
() , (6)
where C
b
is the coupling coecient of vibrational transitions, g
b
is the den-
sity of vibrational states, n(, T) is the BoseEinstein distribution function.
From (6) it can be seen that the Raman intensity is determined by the density
of vibrational states.
1.2 Raman Spectra of Carbon Materials
The basic electronic conguration of a stand-alone carbon atom diers from
that during bonding. In the latter case, the electronic orbitals of carbon
combine, forming hybridized orbitals: sp
3
, sp
2
and sp hybridization states are
known for carbon atoms, which form three-dimensional, layered and chain-
like structures like diamond, graphite and carbyne. In disordered carbons,
atoms of dierent hybridization are mixed. Besides, hydrogen can also be
present in the structure. Because of the large variety of atomic arrangements
in carbon materials, their properties, both crystalline and amorphous, vary
in a wide range.
Among the several dierent models proposed for the a-C:H [2, 3], nowa-
days the cluster model [4, 5] has found wide acceptance since that best de-
scribes the electronic structure of amorphous carbons. Most of the experi-
mental data obtained for a-C:H lms were successfully explained with this
model. The cluster model is based on considerations of the H uckel approx-
imation, treating the and states separately [4]. It was found that the
bonding of carbon atoms favours a clustering of sp
2
sites predominanatly
into planar structures formed by sixfold rings. As a result, in the amorphous
carbon matrix there are sp
2
clusters of dierent sizes surrounded by a matrix
of sp
3
carbon atoms. It should be noted that the cluster model was reformu-
lated [6]. According to it, in clusters, the sp
2
hybridized carbon atoms can be
Raman Spectroscopy of CVD Carbon Thin Films 427
arranged, besides into rings, into chains too [7, 8]. The energy of the states
of the cluster strongly depends on the size and on the level of conjugation of
the cluster. The higher the cluster size, the lower the gap between the valence
and conduction

states. The energy of the states is much higher than

that of ones.
Raman spectroscopy has been proved to be a very suitable method for
structural characterization of carbon materials [9, 10, 11, 12, 13, 14, 15]. The
method is highly sensitive to changes in the bonding conguration of carbon
atoms, especially to that of sp
2
hybridized ones, since the states of the
sp
2
clusters result in narrow band gaps, which cause the Raman scattering
process to be resonantly enhanced.
The Raman spectrum of diamond consists of one zone-centre mode at
1332 cm
1
having T
2g
symmetry. In the spectrum of single crystal graphite,
a peak can be observed at 1580 cm
1
corresponding to zone-centred E
2g
mode, usually labelled as G (graphitic) band, assigned to CC stretching
vibrations of the atoms in hexagonal rings of the graphene sheet. Besides,
an interplanar E
2g
stretching vibration mode is also present at 42 cm
1
[16].
In nonperfect or microcrystalline graphite, another band of A
1g
symme-
try, called the D (disordered) peak [17], corresponding to breathing vibra-
tions of the hexagonal rings at the grain boundaries, appears at 1350 cm
1
.
The D band is a result of a double resonant scattering process activated by
the defects of the crystal [18]. There are other bands of small intensity ob-
served in the Raman spectra of graphite [19], as well as intensive second- and
higher-order peaks above 2000 cm
1
[20], but these are not relevant for the
interpretation of the spectra of amorphous carbons. Due to the specic band
structure of graphite, where the conduction and valence bands cross at the
K point but a forbidden gap exists in other points of the Brillouin zone, the
Raman scattering in graphite is always resonant. On the contrary, the band
gap of diamond is around 5 eV, hence for visible excitation the intensity of
its 1332 cm
1
mode is about one ftieth that of the G peak of graphite [21].
The Raman spectra of amorphous carbons consist of a broad band in the
10001700 cm
1
range. This composite band is usually decomposed into two
peaks centred around 1350 and 1580 cm
1
, which are near the position of
D and G bands of microcrystalline or nonperfect graphite. This similarity
was the origin of the labelling and rst explanation of the Raman spectra
of amorphous carbons [9]. The D band of amorphous carbon materials is
assigned to breathing vibrations of rings or ring-like structures; the stretching
modes of these species give rise to the scattering in the G band region [14].
However, besides the stretching vibrations of carbon atoms arranged in rings,
those forming chains also contribute to the G band [13]. The parameters of
the two bands (position, width and their intensity ratio) are used for the
characterization of carbon-containing materials [10, 11].
The shape of the Raman spectrum is considered to depend on the sp
2
/sp
3
ratio, clustering of the sp
2
hybridized carbon atoms and arrangement of these
428 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
atoms in the clusters [15]. The position of the G band indicates the type of
arrangement of carbon atoms in the clusters: if its value is around 1580 cm
1
,
the clusters have graphitic character, while lower positions indicate a dier-
ent arrangement. The peak width is the measure of structural ordering: the
narrower the peak, the more ordered the structure. Another parameter used
for a-C:H thin layers characterization is the intensity ratio of D and G bands.
The I
D
/I
G
ratio was found to be related to the size of the sp
2
clusters in the
amorphous carbon structure. It is assumed that for microcrystalline graphite
the I
D
/I
G
ratio is inversely proportional to the crystallite size L
A
[22]:
I
D
I
G
=
c
L
A
. (7)
Experimental measurements performed on ta-C thin lms showed that for
amorphous carbons having sp
2
clusters below 2 nm size the ratio is pro-
portional to the square of the cluster size L
C
[14, 23]:
I
D
I
G
= c

L
C
2
. (8)
The constants c and c

in (7) and (8) were found to be dependent on the

excitation energy. The I
D
/I
G
ratio is the measure of ordering of the a-C:H
structure. The higher the intensity ratio, the higher the cluster size, thus the
higher the ordering of the structure.
Raman spectroscopic measurements with dierent excitation wavelengths
can furnish additional information on the a-C:H structure [10, 24, 25, 26, 27].
The bonding sites having sp
2
carbon atoms are generally arranged into clus-
ters of dierent sizes, which exhibit band gap depending on cluster size. For
dierent laser energies, E
L
, the conditions of resonant Raman scattering will
be fullled for dierent clusters, whose band gaps are equal to that. How-
ever, the vibrational frequency depends on the cluster size: the higher the
size, the lower the frequency of the vibrations [28]. Additionally, when using
lasers in the UV region, the sp
3
sites can be resonantly excited, thus their
bonding conguration can also be examined. A characteristic feature of the
D and G bands in the Raman spectra of amorphous carbon is their disper-
sion, the shift of the peak position when changing the excitation energy. The
dispersion was also observed for the D band of graphite [29]. It was found
that for dierent amorphous carbons (hydrogenated and nonhydrogenated)
the rate of the shift varies in a wide range [15]. For a-C:H thin lms (poly-
meric and diamond-like) the position of both D and G bands shifts to higher
wavenumbers with the increase of E
L
[15, 24, 30].
It was found that in graphite the Raman scattering cross-section is
strongly enhanced for the phonons having wavevector k
ph
equal to the
wavevector k of the electronic transition excited by the incident photon [29].
For diverse E
L
, this condition is fullled for phonons at dierent distances
from the K point of the zone boundary, hence the energy of the phonon par-
ticipating in the scattering also varies with E
L
[18]. In a-C:H the dispersion
Raman Spectroscopy of CVD Carbon Thin Films 429
of the bands is dierently explained. Since there is no Brillouin zone, the se-
lection rules have no meaning. As noted earlier, when changing the excitation
energy, dierent clusters will participate in resonant scattering. The band gap
of the cluster is inversely proportional to its size. Thus, the higher the E
L
,
the lower the mean size of the clusters involved in the resonant scattering.
The lower the cluster size, the higher the frequency of its vibrations.
Up to now, systematic Raman investigations on amorphous carbon thin
lms of dierent types were performed mainly with excitations in the visible
and UV region [11, 12, 14, 15]. The aim of the increase of the probe energy was
that the sp
3
hybridized carbon sites, having higher band gap, could be excited
too. However, the resonant enhancement of Raman scattering from graphitic
structure or/and materials containing several sp
2
bonded sites arranged in
nanoclusters at low-energy excitation can provide additional information on
the structure of the a-C:H lms. In the following, results of Raman spectro-
scopic studies, performed with visible and infrared excitations, on a series
of a-C:H samples prepared by radio-frequency chemical vapour deposition at
dierent self-bias voltages, from benzene and methane, will be presented in
detail.
2 Infrared Excited Raman Spectroscopy
of Amorphous Carbon Thin Films
2.1 a-C:H Thin Films Prepared from Benzene
The a-C:H thin lm samples were deposited onto Si substrates by radio-
frequency (2.54 MHz) chemical vapour deposition (CVD) method [31] from
benzene at dierent chamber pressures (820 Pa) and self-bias voltages (10
700 V). The electrode with the substrate had negative self-bias potential,
however, for simplicity, in the following only the magnitude of the self-bias
voltage is given without the sign. Raman spectroscopic measurements
were carried out on the samples using a Renishaw 1000 Raman spectrometer
attached to a microscope. A 488 nm (2.54 eV) line of an Ar ion laser and a
785 nm (1.58 eV) diode laser served as excitation sources. The 100 objective
focused the excitation beam to a spot having diameter of 1 m. Baseline
correction on the measured spectra was performed by tting their baseline to
a Gaussian function and subtracting the tted data from the experimentally
measured ones. Raman spectra of a-C:H thin layers measured at 488 nm
of probe wavelength are shown in Fig. 1. The data are normalized on their
maxima. The change of the shape of the spectra with self-bias well reects the
evolution of the amorphous carbon structure. In the spectrum of the sample
prepared at 10 V the G peak is located around 1600 cm
1
. With the increase
of self-bias up to 300 V, it shifts to lower wavenumbers and, above this voltage,
the peak positions move into opposite direction. The intensity of the D band
also increases with self-bias. The spectra of the samples prepared at low
430 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 1. Raman spectra excited by 488 nm of a-C:H thin lms prepared from benzene
at pressure of 18 Pa and dierent self-bias voltages
deposition voltages have bad signal/noise ratios due to the high intensity of
the luminescence background. The weak peak around 1000 cm
1
, observable
in some spectra, arises from the Si substrate.
In the 10001700 cm
1
wavenumber region the spectra were tted to two
Gaussians. The dependence of the position and peak width of the G and D
bands on the self-bias voltage is shown in Fig. 2, where data obtained for a
series of samples prepared at 8 Pa are also provided. It can be seen that there
is a minimum in the position of the G peak around 300 V, where diamond-like
layers are formed, while the D band has the lowest location around 100200V.
Above 500 V, the G peak position increases and approaches the 1580 cm
1
peak of graphite. The peak width decreases, implying that some kind of
ordering takes place in the a-C:H structure. In this region, the graphitization
of the structure begins, and above 600 V of self-bias, the structure can be
considered as graphitic a-C:H.
Similar behaviour is observable for the G peak parameters at low voltages,
where polymeric a-C:H layers are formed. For the samples prepared below
30 V, it reaches the position of 1600 cm
1
, well above the G peak position
Raman Spectroscopy of CVD Carbon Thin Films 431
Fig. 2. Dependence of (a) the peak position and (b) the peak width on self-bias
voltage of the D and G bands of a-C:H thin lms prepared from benzene at pressures
of 8 and 18 Pa
of graphite, suggesting that the G peak in the spectra of these samples does
not arise from graphitic domains. The band narrowing suggests the ordering
of the structure.
In Fig. 3, it can be seen that the I
D
/I
G
ratio has a minimal value in the
diamond-like a-C:H lms, around 300 V self-bias. As we discussed before, the
D band can be attributed to scattering of breathing modes rings or ring-like
structure formed by sp
2
-hybridized carbon atoms, while stretching modes of
both rings and chains formed by sp
2
sites contribute to scattering in the G
432 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 3. Dependence of intensity ratio of the D and G bands of the Raman spectra
of a-C:H lm prepared from benzene at pressures of 8 and 18 Pa on self-bias voltage
band region. Hence, the I
D
/I
G
ratio indicates the ratio of the amount of (sp
2
)
ring-like structural units to the total amount of (sp
2
) rings and chains. The
increase of the I
D
/I
G
ratio is due to the presence of benzene rings or of their
substituted forms in the structure, below 300 V self-bias. At the same time,
the formation of graphitic structure, at large deposition voltages, explains
the increase of the I
D
/I
G
ratio in that region. This explanation is in good
accordance with the change of the G peak position with self-bias. Above and
below that region, the a-C:H structure becomes more ordered. On strength
of the analysis of the G band behaviour, one can conclude that this ordering
in polymeric and graphitic layers has dierent origin. This is supported by
Raman spectroscopic investigations performed with infrared excitation.
In several works [13, 32, 33, 34], it is noted that the use of two peaks for
the decomposition of the Raman spectra of a-C:H thin lms is inaccurate,
so the tted curve diers from the experimental one. This suggests that not
only structural units, vibrating at frequencies of G and D peaks, contribute
to the spectra. However, since it is dicult to determine the parameters of
the extra peaks, the attempts made for their assignment have controversial
results [13, 15, 33]. One way to obtain additional information on these bands
is to change the excitation wavelength, since the dispersion of the peaks can
be dierent.
Earlier investigations showed that the Raman scattering spectra of the
amorphous carbon materials excited in the infrared light region can give
additional information on the bonding structure [35]. Raman spectra of the
samples measured by 785 nm excitation are shown in Fig. 4. The region
Raman Spectroscopy of CVD Carbon Thin Films 433
Fig. 4. Raman spectra excited by 785 nm of a-C:H thin lms prepared from benzene
at pressure of 18 Pa and dierent self-bias voltage U
SB
around 1000 cm
1
was cut out since, due to the resonance enhancement, the
Raman scattering intensity arising from the Si substrate is several orders of
magnitude higher than that of the a-C:H lms. By comparing Figs. 1 and 4,
it can be concluded that there are signicant dierences in the spectra of
the same samples, especially at low self-bias voltages. While broad bands are
characteristic of the 488 nm excited spectra, sharp peaks, at 1200, 1300, 1450
and 1600 cm
1
wavenumbers, can be found in the infrared excited ones of
these lms. Besides the 10001600 cm
1
region, a broad band can also be
seen around 1800 cm
1
. The increase of the self-bias results in broadening
of the bands and shifting of their positions. At 120 V self-bias new bands
appear in the spectra around 1200 cm
1
.
The spectra were decomposed by sets of Gaussian and Lorentzian curves.
It is convenient to analyse the narrow bands in the spectra of polymeric lms
separately from broad bands.
Figure 5 compares the Raman spectrum of the a-C:H lm prepared at
10 V self-bias with that of the benzene. Additionally, the spectrum of the
part of the lm detached from the substrate is also provided. It can be seen
434 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 5. Comparison of the Raman spectra excited by 785 nm of (a) benzene,
(b) detached from the substrate and (c) as-prepared a-C:H thin lm deposited
from benzene at pressure of 18 Pa and 10 V of self-bias
that bands at 1190 and 1607 cm
1
in the spectra of the a-C:H lm arise
from the presence of benzene rings in the structure. Another benzene peak
at 1007 cm
1
, masked by the band of Si substrate, is observable only in the
spectra of the detached lm. The dierences in the band positions can be
explained considering that there are not separate benzene rings, but substi-
tuted ones present in the structure. The substitution changes the symmetry
of the molecule, thus forbidden Raman bands appear in the spectra too.
Peaks at 1037, 1160, 1288 and 1448 cm
1
are related to substituted benzene,
whose presence was supported by infrared transmission measurements [36]
(not presented here).
It is accepted that the sp
3
carbon atoms contribute to the Raman spectra
when it is excited in the UV region. Contrarily to this, information on the
bonding conguration of sp
3
hybridized carbon atoms can also be deduced
from the infrared excited spectra of the a-C:H lms prepared at low self-
bias voltages. The small peak around 1382 cm
1
is presumably related to
symmetric CH deformation vibrations of sp
3
CH
3
groups. This mode usually
has low Raman intensity, but not in the case of sp
3
CH
3
group attached
to carbon atoms having double or triple bonds or to a benzene ring. The
asymmetric pair of the vibration is around 1450 cm
1
, overlapped by the
1448 cm
1
mode of benzene. The characteristic CH mode of sp
3
CH
2
group
contributes to the spectra at 1300 cm
1
. The evolution of these bands with
self-bias voltage (Fig. 4) evidences the intact benzene rings are present in the
spectra of the a-C:H lms up to 80 V.
The decomposition shows that, as a background of these narrow peaks,
there are two broad bands, observable in the spectra of the 10 V sample,
centred at 1378 and 1599 cm
1
. Their position is similar to that of the D and
Raman Spectroscopy of CVD Carbon Thin Films 435
G bands in the spectrum excited by 488 nm (Fig. 2). The G band position
(1599 cm
1
) is higher than that in graphite (1580 cm
1
). It is close to the
1607 cm
1
peak of the substituted benzene. This suggests that the sp
2
carbon
atoms in the amorphous carbon matrix have an arrangement close to that
they have in a benzene molecule. Presumably, the amorphous phase of the
sample contains a high amount of distorted benzene rings.
As the self-bias increases, the shape of the spectra changes signicantly. In
the spectra of the 80 and 120 V samples, in the 10001700 cm
1
wavenumber
range, four broad bands are observable, centred around 1140, 1260, 1430 and
1566 cm
1
. The close position of the 1566 cm
1
peak to the G peak in the
488 nm excited Raman spectrum of the sample (at 1560 cm
1
) suggests that
this band is the G one, too. However, we must take into account that the
D and G bands of a-C:H have dispersion. By estimating from the dispersion
rates up to 785 nm of excitation, the D band of a-C:H lms has to be located
around 1250 cm
1
and the G one is around 1430 cm
1
. By comparing these
values with the data obtained for the 120 V sample, it can be assumed that
the 1260 and 1430 cm
1
peaks of that correspond to the D and G peaks.
So one gets the conclusion that there are two bands in the infrared excited
spectrum that correspond to the G band: one, at lower wavenumbers, around
1430 cm
1
, showing dispersion, and the second, around 1566 cm
1
, having
no dispersion.
In Fig. 6 the dependence of the positions and widths of the broad bands,
found in the 785 nm excited Raman spectra, on the self-bias voltage are
shown. In the spectrum of the 10 V sample, the band showing no dispersion
(G
(nd)
in the following) is located at 1599 cm
1
. The increasing self-
bias causes the shift of the band position to lower wavenumbers. It reaches
1570 cm
1
at 120 V and does not vary signicantly above that voltage value.
The band width is almost the same in the whole self-bias range. The position
of the G peak that shows dispersion (G
(d)
in the following) uctuates
around 1430 cm
1
and broadens with the increasing self-bias.
The position of the D band located at 1378 cm
1
in the spectrum of
the 10 V lm decreases rapidly with the increase of the self-bias, down to
1230 cm
1
at 200 V, to the position expected with considering the disper-
sion. Above that voltage the band position does not change remarkably up
to 500 V and increases above that value. As it was noted earlier, the disper-
sion of the bands in amorphous carbons is due to the size distribution of the
clusters having dierent band gaps. If one goes into the details of the phenom-
enon, which was observed also in hydrocarbon polymers built of conjugated
chains (chains consisting of sp
2
carbon atoms connected with alternating
single and double bonds), it turns out that it is not the size that determines
the band gap of a cluster, but the delocalization of the electrons in it. The
cluster size is only the upper limit for the delocalization length. The level
of delocalization is determined by the lengths of conjugated regions, which
depend on the bonding conguration of the sp
2
carbon atoms. Several fac-
436 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 6. Dependence of (a) the position and (b) width on self-bias voltage of the
broad bands found in the Raman spectra excited by 785 nm of a-C:H thin lms
prepared from benzene
tors can aect on the delocalization length of a conjugated chain, including
kinks, breaks in the periodicity of the alternating bonds and attachment of
side-chains. It is known that the benzene molecule has an electronic congu-
ration such that its electrons are delocalized only within the ring, but not
out of it.
From the absence of the G
(d)
band and the downshift of position of the D
peak up to 80 V self-bias, it can be concluded that the increasing deposition
Raman Spectroscopy of CVD Carbon Thin Films 437
voltage causes the increase of the extent of electron delocalization in sp
2
clusters. The behaviour of the G
(nd)
band indicates that the atomic arrange-
ment in the clusters of a-C:H matrix transforms. In the layers prepared at
low self-biases, mainly distorted benzene rings form the cluster, while, with
the increase of the voltage, the ratio of carbon atoms arranged into chains
rises, as well as the delocalization length characteristic for the clusters. The
amount of the intact benzene rings also decreases with the increasing self-bias
from 10 V, and above 120 V they are completely destroyed.
Above 120 V self-bias, the G
(d)
peak broadens and its intensity increases
relative to the G
(nd)
band. In the spectra of the 300 V sample, the two
bands overlap, so as they can easily be treated as one. When the structure
becomes graphitic (700 V), the G
(nd)
band rises since there are graphitic
rings present in the structure.
The decomposition showed the presence of another broad peak located
at 1130 cm
1
in the spectra of samples deposited at self-biases in the 80
200 V range. The band shifts to higher wavenumbers with increasing self-bias.
A similar band in the spectra of a-C:H was reported earlier and was related
to vibrations of sp
2
chains (trans-polyacethylene-like structural units) [37],
sp
3
carbon phase [38] and nano-crystalline diamond [13, 33]. The peak ap-
pears together with the 1430 cm
1
one, which was assigned to CC stretch-
ing vibrations of structural units having large delocalization lengths of their
electrons. A typical representative of hydrocarbon chains, built of sp
2
carbon atoms, is trans-polyacethylene. It has characteristic Raman peaks
around 1450 cm
1
and 1100 cm
1
, both showing dispersion. Presumably,
the 1130cm
1
band can be assigned to vibrations of sp
2
chains. Model cal-
culations showed that, for short polyacethylene chains, the position of the
latter band strongly depends on the chain length too, and shifts to lower
wavenumbers with increasing chain length, while there is no such eect ob-
servable for the other band [39]. The increase of the peak position with self-
bias shows that, as the lms become more diamond-like, the length of the
conjugated chains decreases in the clusters. Above 200 V, the band cannot
be decomposed due to its overlapping with the D band.
In conclusion, it was shown that infrared-excited Raman spectroscopy is
an excellent tool for characterization of dierent types of a-C:H thin lms. It
can provide additional information on the bonding conguration of carbon
atoms in the structure. The spectra recorded by near-infrared excitation were
decomposed into four peaks. It was found that the G peak has two compo-
nents, one of which shows dispersion, while the position of the other does not
change with excitation wavelength. In the lower wavenumber region, besides
the D band around 1130 cm
1
, another peak appears in the spectra, related
to vibrations of carbon atoms arranged into chains.
By using the infrared-excited Raman spectroscopy, the evolution of the
structure of a-C:H layers prepared from benzene was investigated. It was
shown that, at low self-bias voltages (up to 120 V), intact (substituted) ben-
438 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
zene rings embedded into the amorphous structure. In addition, the amor-
phous matrix of the lm prepared at 10 V contains structural units not dif-
fering remarkably from benzene. Their content, as well as that of substituted
benzene decreases with increasing self-bias. The sp
2
carbon atoms arrange
into chains. The small delocalization length also increases with deposition
voltage. From 120 V to 400 V, the chains dominate the sp
2
clusters. The
increasing with self-bias graphitic character will dominate the spectra of the
samples above 400 V.
Visible and infrared excited Raman spectroscopic measurements were also
performed on a-C:H samples prepared from methane in a wide self-bias range.
In the following, the results of these investigations will be presented.
2.2 a-C:H Thin Layers Prepared From Methane
The methane lms were prepared similarly to benzene ones at chamber pres-
sures of 13 Pa. The Raman spectra of the a-C:H lms excited at 488 nm
are shown in Fig. 7. The shape of the spectra is similar to those presented
in Fig. 1. The only dierence is that there was not so high a luminescence
background observable in the samples prepared at low voltages.
The spectra were analysed similarly to the benzene ones. Figure 8 shows
the variation of positions and widths of D and G bands with the self-bias
voltage. Contrarily to the layers prepared from benzene (Fig. 2), the positions
of both bands increase monotonically with the self-bias. The peak width of
the D band increases also monotonically, while that of the G peak, after
a small increase, decreases above 60 V. The comparison with the results
obtained for the a-C:H lms deposited from dierent source gases shows
that in the low self-bias range the sample series prepared from benzene and
methane behave dierently. In case of the benzene layers, the presence of
ring-like units (distorted benzene rings) in the amorphous structure causes
the G peak to appear around 1600 cm
1
. On the contrary, in the 30 V sample
prepared from methane, the G peak is located at 1537 cm
1
, suggesting that
chain-like structural units are mainly present in the sp
2
clusters. The shift
of the G band to higher wavenumbers with increasing self-bias indicates the
increase of the amount of ring-like structures in the sp
2
clusters of the lm.
This is supported by the change of the I
D
/I
G
ratio of the lms (Fig. 9),
which also diers from that of the benzene ones. It rises monotonically with
the increasing self-bias, showing the increase of the ratio of the rings in the
structure.
The huge dierence in the bonding structure of a-C:H lms prepared
from methane and benzene at low self-biases are also evidenced from their
Raman spectra excited at 785 nm. While the spectra of the benzene lms are
characterized by narrow peaks (Fig. 4), those of methane layers are composed
of broad bands (Fig. 10). The spectrum of the layer prepared from methane
at 30 V self-bias is similar to the spectra of the lms prepared from benzene
at 300500 V potential and evolves with the increase of the self-bias similarly
Raman Spectroscopy of CVD Carbon Thin Films 439
Fig. 7. Raman spectra excited by 488 nm of a-C:H thin lms prepared from
methane at dierent self-bias voltage U
SB
to the benzene ones above 300 V, where the sites have large delocalization
length.
The spectra were decomposed by a set of four Gaussians. The variation of
the positions and peak widths of the component bands with self-bias voltage
are shown in Fig. 11. The positions of component bands are similar to those
found in the benzene samples above 200 V self-bias. This implies that these
peaks have the same origin. Hence, the infrared-excited Raman spectra of
methane layers also have the D, G
(d)
and G
(nd)
bands (around 1230, 1430
and 1570 cm
1
, respectively), as well as the peak assigned to vibrations of sp
2
carbon atoms arranged into chains (around 1150 cm
1
). The position of the
latter band, located in the spectra of the 30 V sample at 1105 cm
1
, shifts to
lower wavenumbers with the increase of the self-bias, showing the increase of
the sp
2
chain lengths of in the clusters [39], and becomes undetectable in the
spectrum of the 600 V sample. In the lms prepared from benzene, the band
is positioned at higher wavenumbers, indicating the smaller chain lengths in
the clusters of those layers.
440 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 8. Dependence of (a) the peak position and (b) the peak width on self-bias
voltage of the D and G bands of a-C:H thin lms prepared from methane
The position and width of the G
(d)
band do not change signicantly with
the increase of the self-bias, but its intensity decreases as the graphitic char-
acter of the structure strengthens. This is accompanied by the shift of the
G
(nd)
peak from 1560 cm
1
to higher wavenumbers.
The comparison of the bonding conguration of the a-C:H thin layers
prepared from methane and benzene shows that the structure of the lms
prepared under similar conditions diers signicantly at low self-biases. In
the benzene molecule, the carbon atoms have preferential arrangement. At
Raman Spectroscopy of CVD Carbon Thin Films 441
Fig. 9. Dependence of intensity ratio of the D and G bands of the Raman spectra
of a-C:H lm prepared from methane on self-bias voltage
Fig. 10. 785 nm excited Raman spectra of a-C:H thin lms prepared from methane
at dierent self-bias voltage U
SB
442 Margit Koos, Miklos Veres, Sara Toth, and Miklos F ule
Fig. 11. Dependence of (a) the position and (b) width on self-bias voltage of the
broad bands found in the Raman spectra excited by 785 nm of a-C:H thin lms
prepared from methane
low ion energies, the amorphous carbon matrix mainly consists of distorted
benzene rings, so that besides intact rings, distorted benzene rings are also
present in the a-C:H matrix. This arrangement causes the electrons to be
highly localized in the rings of clusters. As the ion energy increases, these
rings are destroyed in the plasma, as well as during the bombardment of
the surface of the growing lm, and the atoms rearrange, forming sp
2
clus-
ters characterized by large delocalization lengths. Clusters containing large
Raman Spectroscopy of CVD Carbon Thin Films 443
amount of sp
2
chains develop in the self-bias region, where diamond-like a-
C:H forms. With further increase of the deposition voltage, the graphitic
clusters will dominate in the layer.
On the contrary, for the methane molecule consisting of only one carbon
atom, there is no preferential arrangement. Therefore, during lm formation,
the topology of the carbon atoms develops without initial constraints, except-
ing for the bonding angles, set by the hybridization state of the carbon atom.
The sp
2
clusters, formed at low self-biases, are built of carbon atoms arranged
in both rings and chains and have large delocalization lengths, compared to
the benzene ones prepared under similar conditions. The increase of the de-
position voltage up to the region, where diamond-like carbon deposits, causes
the lengthening of the sp
2
chains. Above this self-bias, the graphitization of
the structure starts, similarly to the benzene layers.
In conclusion, it was shown that Raman scattering excited in the near-
infrared region can provide additional information about the bonding cong-
uration of of a-C:H thin lms in a wide range of deposition conditions. Hence,
it can be dependably used for quality control of these materials. The method
was proved to be highly sensitive to the arrangement of the carbon atoms in
the sp
2
clusters. The discrepant dispersion of the component peaks made the
composite spectra to be decomposed more obvious, and it could give an ex-
perimental basis for the assignment of the bands found in the Raman spectra
of a-C:H.
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Index
states, 423, 426
states, 427
a-C, 428
a-C:H, 426, 428443
sp
2
-bonded clusters, 426429, 435,
437439, 442, 443
Raman Spectroscopy of CVD Carbon Thin Films 445
cluster conjugation level, 427
cluster size, 426429, 435
sp
2
-chains, 427, 431, 432, 435439, 443
chain length, 439, 443
sp
2
-rings, 426, 427, 431, 434, 435, 437,
438, 442, 443
distorted rings, 435, 437, 438, 442
six-fold rings, 426
sp
3
/sp
2
bonding ratio, 427
ta-C, 428
amorphous carbon thin lms, 423
chemical vapour deposition (CVD)
radio frequency CVD, 429
cluster model, 426
clustering, 426429, 435, 437, 438
coherence length, 428
crystallite size, 428
D band, 427432, 434438, 440
D/G band intensity ratio, 428, 431,
432, 438, 441
diamond, 426, 427
diamond-like carbon (DLC), 428, 430,
431, 437, 443
dispersion, 423, 428, 432, 435437, 439,
440, 443
electron-phonon coupling, 425
electron-photon coupling, 425
G band, 423, 427432, 435, 437, 438,
440
dispersive G band, 435437, 439, 440
non-dispersive G band, 435, 437, 439,
440
graphene, 427
graphite, 426428, 430, 431, 435
graphitization, 430, 438, 443
H uckel approximation, 426
multi-wavelength Raman spectroscopy
(MWRS), 428
normal modes, 424
phonons, 423, 425
zone centre phonons, 424
polarizability, 424, 425
polarizability tensor, 424
Raleigh scattering, 424
Raman scattering, 423
anti-Stokes scattering, 423
infrared excitation, 423, 429,
432435, 437439
Raman intensity, 426
Raman spectrum, 426
Raman tensor, 424, 425
resonant Raman scattering, 425, 428
selection rules, 425
breakdown of the selection rules,
426
Stokes scattering, 423
visible excitation, 423, 424, 427, 429,
438