Micro-Raman Studies on DLC

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Coatings
By Gert Irmer* and Annett Dorner-Reisel

Raman scattering is an excellent tool to characterize nanocrystalline clusters and the structural
arrangement of carbon atoms in carbon-based materials. Diamond-like carbon (DLC) films are used in
many industrial applications due to their hardness, wear resistance and biological compatibility. The
properties of DLC coatings depend on the carbon coordination and incorporation of other elements,
influences onto their Raman spectra will be reviewed.

1. Introduction
Raman scattering, the inelastic scattering of photons by
fundamental excitations in molecules or solids, is a standard
non-destructive technique for the characterization of carbon-
based materials. The Raman spectra of vibrational excitations
in the various forms of carbon like diamond,[1] graphite,[2]
fullerenes,[3] nanotubes and diamondlike carbon (DLC),[4]
exhibit large differences. DLC coatings consist of amorphous
carbon with short and medium range order of sp2 and sp3 sites.
Their mechanical and optical properties depend on the sp3
content as well as on the number and size of clusters with short-
range and medium-range ordered sp2-coordinated carbon
atoms. The characteristic Raman spectra can be used to study
the structural arrangements of the carbon atoms. Raman
scattering on DLC coatings is a sensitive probe of sp2- and sp3
bonding of the carbon atoms and of the nanocrystalline
clusters. Due to the lattice disorder, the wave vector selection
rules are relaxed and phonons from the whole Brillouin zone
contribute to the Raman spectra. The observed broad bands
reflect the phonon density of states but in the case of exciting the
spectra with visible light resonance effects are essential for the
selection of the phonons which contribute to the Raman
scattering process.
By excitation with photons of visible light the Raman
spectrum is dominated by scattering of sp2 bonded graphitic
carbon, due to resonance enhancement of the Raman scattering
cross section. Two broad bands appear at about 1550 cm±1
(ªG-peakª) and at about 1360 cm±1 (ªD-peakª). Although
the visible Raman spectrum depends fundamentally on the
ordering of the sp2 bonded carbon and only indirectly on
the sp3 content, it can also be used in a restricted range of
conditions to derive information about the sp3/sp2 ratio. This
can be shown by comparison with methods, which give the
sp3/sp2 ratio more directly like electron energy loss and NMR
spectroscopy.
In the last few years several studies utilizing UV excitation
for evaluation DLC overcoats have shown that the D and G
Raman bands are significantly reduced compared to the sp3
bands. A Raman band was observed at about 1150 cm±1. It can
be attributed directly to sp3-bonded carbon (ªT-peakª).
The paper is organized as follows. The discussion of Raman
scattering in Section 2 is restricted to sp3 and sp2 bonded carbon
in diamond, graphite and amorphous carbon. For more
information and Raman scattering in other carbon materials
readers may refer to one of the numerous reviews in this
field.[5±9]
The properties of DLC overcoats are very sensitive to the
number and size of graphitic nanoclusters in their carbon
network. In Section 3 firstly the Raman spectra of nanocrystal-
line graphite and their size dependence are considered. Then
the features in the Raman spectra of hydrogenated a-C:H and
hydrogen free ta-C with nanocrystalline clusters which are
considerably smaller than 2 nm and more and more distorted
with larger sp3 bonded content are discussed. Whereas the
±
[*] Prof. G. Irmer
Technische Universität Bergakademie Freiberg
Institut für Theoretische Physik
Leipziger Str. 23, D-09596 Freiberg, Germany
E-mail: irmer@physik.tu-freiberg.de
Dr. A. Dorner-Reisel
Siemens VDO
Oststr. 7, D-09212 Limbach-Oberfrohna
E-mail: dorner@mailtuba.tu-freiberg.de

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Irmer, Dorner-Reisel/Micro-Raman Studies on DLC Coatings
Raman spectra discussed in Sections 2 and 3 were obtained by
excitation with 514.5 nm laser light, in section 4 the dependence
on the excitation wavelength is commented. Some interpreta-
tions of the D band dispersion in graphite clusters as a double
resonance effect are included in Section 4. The macroscopic
properties of DLC such as hardness, wear properties, and
biocompatibility correlate with parameters derived from fits to
their Raman spectra as discussed in Sections 3.4 and 5.
Additional elements such as nitrogen, silicon, and various
metals have been introduced in the carbonaceous structure to
modify the properties of conventional DLC. Influences on the
Raman spectra are considered in Section 5.
2. Raman Scattering in Carbon Materials
2.1. Raman Scattering Process and Raman Instrumentation
Most part of the light scattered by a carbon sample is
elastically scattered without energy shift (Rayleigh scattering).
A small part, some orders weaker in intensity is scattered
inelastically. This inelastic scattering carries information about
energetic levels of the sample. In a Raman scattering process
with incident photon energy hxL the scattered photon hxS has
lost (Stokes scattering) or gained (anti-Stokes scattering) the
energy hx of an elementary excitation, for instance vibrational
excitations in molecules or phonons in solids:
hxS ˆ hxL  hx
 (1)
The Raman scattering is sensitive to probe the local atomic
arrangement. Therefore, crystalline and amorphous phases or
the influence of strain can be detected in the Raman vibrational
spectra. Light couples to phonons through electronic excita-
tions.
When the Raman scattering process involves real inter-
mediate electronic states by excitation with energy near gaps of
the electronic band structure, the scattering cross section may
be resonantly enhanced.[10] Such resonance effects are observed
in the Raman scattering in graphite-based materials excited by
visible light (see Sec. 4).
The Raman scattering probes the electron-phonon interac-
tion as well as the confinement of the phonons and contains
information about the confined vibrational and electronic
states.
The light scattering process in an infinite crystal obeys the
pseudo-momentum conservation relation
~
hkS ˆ h~
kL  h~
q (2)
where (~kL ) denote the wave vectors of the plane waves of the
scattered (incident) light,~
q is the wave vector transferred to the
excited phonon. The energies of crystalline vibrations probed
by Raman scattering are in the range < 0.1 eV and those of the
exciting visible laser light about 2.5 eV (corresponding to the
wavelength kL» 500 nm). From Eq. 1 we get xS»xL. Therefore,
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the wave vector transferred in a typical backscattering
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experiment will be in the order of
j~
qj  4pn=kL
and much smaller than the wave vector q=2 p/a at the
boundary of the Brillouin zone, with a being the lattice constant
and n being the refractive index of the sample. That means only
excitations near the centre of the Brillouin zone (C-point) will
contribute to the Raman scattering.
If the process of light scattering by excitations is limited to
the finite space occupied by a nanoparticle, an uncertainty of
the transferred wave vector~ q occurs and excitations with wave
vectors from the whole Brillouin zone contribute to the
scattering. This effect will vary with size as well as the
eigenfrequencies of acoustical and optical phonons and the
electron-phonon interaction in small particles are influenced.
The vibrational Raman spectra of nanoparticles can therefore
be used for size determinations. Size effects will be discussed in
the Sections 3, 4 and 6.
2.1.1. High-throughput Devices
The volume sampled by the exciting laser light obeys an
inverse relationship to the absorption coefficient that increases
with decreasing sp3/sp2 ratio of the DLC film. For low sp3
contents the penetration depth is as low as tens of nanometres.
Many applications of the Raman spectroscopy benefit from
newer developments to measure the usually weak signals more
efficiently. For recording the scattered light, the charge-
coupled devices (CCD) have become very widespread during
the last ten years and are now used in the most multi-channel
Raman spectrometers. They have very high quantum efficiency
over a broad spectral range and a very low dark count level
when cooled. The separation of the Raman signals from the
much stronger elastically scattered light has been achieved in
the past by use of double- or triple-monochromators. Another
technical solution, now more and more used, are Raman
spectrometers consisting of a holographic notch filter for stray
light suppression and a single grating spectrograph. Such
spectrometers have an up to ten times larger optical through-
put, are more compact with fewer optical components and less
expensive than triple monochromators. The notch filters
suppress the incident laser light by a factor of more than 106
while the rest of the spectrum is transmitted with a high
efficiency of about 80 %. The small edge width of less than 4 nm
allows measurements of Raman shifts lower than 50 cm±1. The
application of this new generation of Raman spectrometers is
attractive for carbon overcoats with low signals, too.
Raman spectroscopy is used by many manufactures in the
disk drive industry to study and monitor protective DLC
overcoats. The new instruments reduced the average measure-
ment time on 30 nm films from between 10 and 30 min to
between 10 and 30 sec.[11] They also enable to measure in a
reasonable time much thinner overcoats (~ 2 nm) nowadays
required in the disk industry. Raman instruments designed
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specifically for the quality control of DLC deposition on
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magnetic recording disks have been introduced within the last
ten years in the market (Jobin Yvon-Horiba, Renishaw, Kaiser
Optical).
Most Raman spectrometers work with visible light; for use
with UV light they must be specially adapted. Standard silicon-
based CCD detectors are not sensitive to light below 400 nm,
special UV optics have to be used. Therefore, some practical
equipment limitations currently limit wide-scale evaluations of
DLC films with UV excitation.
2.2. sp3 Bonded Carbon, Diamond
Diamond crystallizes in the cubic diamond structure, which
consists of two interpenetrating fcc lattices, shifted from each
other by one quarter of the diagonal of the unit cell. Each sp3
bonded carbon atom is surrounded by a regular tetrahedron
formed by the nearest neighbours. Diamond belongs to the O7h
space group with two atoms per primitive cell. The diamond
crystal has only one triply degenerate optical phonon of T2g
symmetry near the centre of the Brillouin zone. This infrared
inactive phonon is observed in the Raman spectrum at
1332 cm±1 as a sharp line with halfwidth (FWHH) < 2 cm±1
(see Fig. 1). A broad weak band appears in the frequency range
2100 ... 2700 cm±1 associated with the second order Raman
scattering.
When prepared at very high pressures or during the cutting
process, a hexagonal structure of diamond with a Raman mode
at about 1319 cm±1 was observed.[1]
DLC (ta-C)
G
DLC (a-C:H)
D D'
nc-Graphite
1582
Graphite
Cluster
diamond
1332
Diamond
1000 1200 1400 1600 1800
Raman shift (cm-1)
Fig. 1. Characteristic Raman spectra of some carbon-based materials: diamond (sp3
bonded), crystalline graphite (sp2 bonded), nanocrystalline graphite (disordered sp2
bonded), a-C:H (DLC, disordered sp2/sp3 bonded) and ta-C (DLC), disordered sp2/sp3
bonded). The spectra were excited by the k = 514.5 nm Ar+ laser line.
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Nanocrystalline diamond ± known as cluster diamond - has
potential applications for ultrathin and ultrahard coatings,
nanobearings, materials for field emission displays and
lubricating materials for hard disks.[8, 12] Its Raman spectrum
shows an asymmetric broad band centred at about 1320 cm±1,
with the tail towards lower frequencies (see Fig. 1).[9] The
dependence of the peak frequency and the halfwidth on the
particle size can be explained as a confinement effect.
2.3. sp2 Bonded Carbon, Graphite
Graphite belongs to the space group D46h. The graphene
layers of carbon hexagons with small nearest-neighbour
separation of 1.421 Š have a strong in-plane bonding; the large
interlayer distance of 3.35 Š gives rise to a weak binding
between adjacent graphene layers. The zone centre optic
phonon modes (q ~ 0) can be decomposed into the following
irreducible representations:
C opt ! A2u ‡ 2 B2g ‡ E1u ‡ 2 E2g
Of these irreducible representations, only the E2g modes are
Raman active. The higher frequency E2g mode at 1582 cm±1
represents in-plane displacements against the strong in-plane
restoring forces (see Fig. 2), whereas the weak E2g mode at the
low frequency 42 cm±1 corresponds to inter-layer shear
displacements against the weak interlayer restoring forces.
The infrared active modes A2u and E1u have been observed
at 867 cm±1 and 1588 cm±1, respectively. The silent modes B2g
are optically inactive, one of them has been observed by
neutron scattering, the other has not yet been observed, and
their frequency has been estimated to be close to 870 cm±1. The
Raman spectrum of highly oriented pyrolytic graphite (HOPG)
with the E2g mode at 1582 cm±1 is shown in Fig. 1. For
disordered, polycrystalline graphite besides this band a band
at about 1350 cm±1 appears. The former band is generally called
E2g mode (G band)
A1g mode (D band)
Fig. 2. Displacements of the carbon atoms in the E2g mode (G band stretching mode) and
in the A1g mode (D band, breathing mode).
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G band and the latter D band, the letters originally standing for
graphite and diamond. However, the diamond vibrations are
always close to 1332 cm±1 and later it was learned that the origin
of the D band are graphite vibrations with wave vectors near
the Brillouin zone boundary. These A1g mode breathing
vibrations (see Fig. 2) are not active in monocrystalline
graphite, but they can be seen in disordered graphite. There-
fore, most authors call the D band disorder band, keeping the
letter.
With a valence force field calculation a close correlation
between phonons of graphite and the normal modes of small
polycyclic aromatic hydrocarbons was established. The results
show that in these systems two kinds of motions dominate the
Raman spectrum which are the equivalent in a finite domain, of
the E2g phonon of graphite at the C-point and the A phonon at
the K point of the first Brillouin zone.[13]
The dependence of the D band on the size of crystallites is
discussed in Section 3.1.
2.4. Amorphous Carbon, DLC
Typical amorphous carbon (see Fig. 1, second curve from
top) shows a broad Raman band in the range between 1000 and
1800 cm±1. It can often fitted very well by two Gaussian curves
on a linear background, centred at 1300 ... 1380 cm±1 and 1520 ...
1580 cm±1, respectively, if excited with k = 514.5 nm. Com-
monly, they are called D and G band as in the case of disordered
graphite. However, their frequencies and assignments differ
from those observed in disordered graphite. Amorphous
carbon consists of a mixture of sp2, sp3, and sp1 bonding
structures. Accordingly, many other vibrations than graphitic
ones contribute to the two bands. By excitation with visible
light the contributions due to vibrations of sp2-bonded carbon
are resonance enhanced and therefore dominating the Raman
spectrum. For UV excitation, an additional peak, the T peak, at
approximately 1100 cm-1 appears.[37,14]
This T peak is due to the C-C sp3 vibrations. The positions
and the intensity ratios of the D and G bands depend on the
sp3/sp2 ratio. For very hard, diamondlike amorphous carbon
with high content of sp3-bonded carbon the G-band dominates
and can be shifted to frequencies above 1580 cm±1 (see Fig. 1,
upper curve).
A remarkable increase of Raman signals from amorphous
carbon films due to the deposition of colloidal Ag particles was
shown.[15] This technique is called surface enhanced Raman
scattering (SERS). Because of resonance effect with surface
plasmons of Ag particles an enhancement of electric field may
occur. It is also possible, that bond polarizability may be
enhanced due to charge transfer and to bond formation
between the diamond-like carbon film surface and the Ag
particle. In addition, SERS spectra exhibit more features in
comparison to normal Raman ones. In the case of hydrogen
containing a-C:H films four peaks at 1284, 1399, 1572 and
1616 cm±1 were decomposed by Veres et. al.[15] The SERS of a-C
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films gave two bands with positions of 1434 and 1585 cm±1. The
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assignation of the observed peaks is the subject of future
studies.[15] Also other studies recommend, that the G and the D
peak really should deconvoluted. Tarrant et. al report that a
diamond-like carbon film deposited under pulsed substrate
bias appears to have more than one G peak.[16] A peak at
1550 cm±1 is referred to as the amorphous carbon ªA peakº ,
which progressively differentiates from the ªtrueº graphitic G
peak at approximately 1618 cm±1. The position and the width of
the Gaussian A peak seems to be largely determined by the
range and population of non-hexagonal sp2 bonded groupings.
In accordance with many experimental observations is the
following simplistic structural model of amorphous, diamond-
like carbon: Small graphitic nanocrystallites (< 2 nm) are
randomly embedded in a three-dimensional network of sp3-,
sp2-, and some sp1-bonded carbon atoms.
3. Raman Scattering in DLC
There are two kinds of DLC overcoats depending on the
basic ways to synthesize a DLC film: Hydrogenated DLC, or a-
C:H, with a relatively large amount of hydrogen (up to 50 at.-%)
and non-hydrogenated DLC or a-C, in which the hydrogen
content is normally less than 1 at.-%.[17] One way is to dissociate
a hydrocarbon gas (Methane, ethylene, butane etc.); the other is
by sputtering of a graphite target. Examples of suitable
processes are magnetron sputtering, cathodic arc, arc ion
plating, and plasma assisted CVD.
3.1. Graphite-like Clusters
Lattice disorder or reduction of the crystallite size relaxes the
momentum conservation for the Raman scattering process.
Phonons throughout the Brillouin zone contribute to the first
order Raman scattering process with intensities dependent on
the phonon density of states and the corresponding electron-
phonon matrix elements.
With the decrease of crystalline size in the graphitic layers
the Raman allowed band near 1580 cm±1 (G-band) is broadened
and a little shifted. Additionally, a disorder-induced band
appears near 1360 cm±1 (D-band), corresponding to phonons
near the K and M points of the Brillouin zone.
In a pioneering study, Tuinstra and Koenig have shown,[18]
that the relative intensity ratio ID/IG of the two bands depends
inversely on the planar crystalline domain size, La, determined
from X-ray diffraction linewidths. While strictly empirical, the
relationship found by Tuinstra and Koenig has been used by
numerous Authors since then to evaluate La. Later, the
relationship has been confirmed by other investigations
comparing results of Raman measurements with X-ray
diffraction measurements.[19±22] Figure 3 shows the ratio ID/
IG measured by Tuinstra and Koenig and other authors on
graphite materials in dependence on the planar crystalline
domain size La. The excitation of the Raman spectra has been
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The ID/IG ratio increases with decreasing cluster size La.

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This is accompanied by a band broadening and a shift of the G

band to higher frequencies (see Fig. 4, nc-graphite), which can
1 be understood as a size-effect: The largest phonon wavelength
possible is restricted by the domain size. Due to the uncertainty
of the wave vector transferred in the scattering process,
phonons from the vicinity of the C-point of the Brillouin zone
ID / IG

contribute, where the phonon dispersion curve has a local

maximum. Therefore, the Raman band is upshifted and
0.1 broadened. The estimated range of phonons with wave vectors
near the C-point contributing to the Raman band is shown for
various cluster sizes in the upper part of Figure 9.[23]

0.01
1 10 100
La (nm)
Fig. 3. Raman intensity ratio ID/IG in dependence on the in-plane crystallite size La for
disordered graphite materials. The data were taken from j Tuinstra and Koenig;[18] +
Lespade et al.;[19] ~ Nakamizo et al.;[20] ; e Nathan et al.;[22] d Gruber et al.[21] The dashed
line corresponds to Eq. 3.
performed with the 514.5 nm Ar+ laser line. The dashed line
presents the fit of the data corresponding to the relationship
ID =IG ˆ k†=La (3)
with C(514.5 nm) ~ 4.4 nm. The coefficient C(k) depends on the
excitation wavelength due to resonance effects (see Sec. 4).
Because the D-band is correlated to in-plane breathing
vibrations (see Fig. 2) and the vibrations along the c-axis are not
Raman active, the Raman spectrum is not sensitive to the
crystalline size Lc perpendicular to the layers which can be
obtained by X-ray diffraction, too.
Eq. 3 holds over the range 2 nm < La < 30 nm as shown in
Figure 3. The minimum La for which the relation has been
verified with X-ray diffraction measurements is 2 nm.
3.2. a-C:H
The properties of a-C:H (Hydrogenated amorphous carbon
films) strongly depend on the energy with which the hydro-
carbon precursors impact the growing film surface. The
hardest films (ªdiamondlikeª) are formed only in a small
energy range with maximized sp3 content.[24, 25] Hydrogen
changes the carbon network by converting C=C groups into sp3
bonded CH-CH groups.
The main features observed in the Raman spectra of a-C:H
are
(i) The G peak frequency decreases with increasing sp3/sp2
ratio from 1600 to ~ 1520 cm±1.
(ii) The D peak intensity decreases with increasing sp3/sp2
ratio.
(iii) The relation ID/IG ~ 1/La (Eq. 3) obtained for nc-
graphite, is no longer valid.
In a-C:H the size of graphite like entities is considerable
smaller than 2 nm. Small clusters are more distorted, until they
open up. Because the D peak is correlated to the breathing
modes of rings, its intensity is proportional to the number and
clustering of graphite like aromatic rings.
Ferrari and Robertson assume that the intensity ratio ID/IG
corresponds to the number and size of sp2-bonded sites
according to the relationship[26]

ID =IG ˆ C0 k† L2a (4)

3 nc-graphite a-C:H a-C

For the constant values C¢ (514.5 nm) ~ 0.0055 and
C¢ (514.5 nm) ~ 0.0028 were reported.[26, 27] Thus, starting from
sp3 = 0 sp3/sp2 sp3/sp2 small clusters and going to larger ones in a-C:H, the D band
ID/IG

2
indicates ordering, whereas in nanocrystalline carbon the ID/IG
intensity ratio increases with decreasing cluster size indicating
1 disorder.[26]
The ID/IG intensity ratio and the G band position obtained
with Raman measurements are correlated with the sp3/sp2
0 ratio as can be seen in Figure 5. All sp3/sp2 ratios of the data
1520 1560 1600 1600 1560 1520 1520 1560 1600 included were determined with independent methods. The
sp3/sp2 ratio of the DLC films has been measured directly by
G band position (cm-1) electron-energy-loss spectroscopy (EELS) and NMR,[26, 28] (dots
Fig. 4. Plot of the Raman intensity ratio ID/IG vs. Raman frequency of the G band for nc- in Fig. 5) or has been obtained from measurements of the
graphite (sp2 bonded) and for DLC (a-C:H, a-C) with increasing sp3/sp2 ratio. optical Tauc gap,[25, 28] (crosses in Fig. 5) using the observed

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2.5
2 a-C:H
ID / IG
1.5
1
0.5
0
1560
ν(G) (cm-1)
1540
1520
1500
0.2 0.4 0.6 0.8 1 0.4
sp3/sp2
Fig. 5. Raman intensity ratio ID/IG and Raman frequency of the G band in dependence on
the sp3/sp2 ratio for DLC (a-C:H). The sp3/sp2 ratio was determined by EELS
measurements (d Ferrari et al),[26] absorption measurements (~ Tamor et al.),[25] and
NMR measurements ( j Dorner-Reisel et al).[83]
relationship between sp3/sp2 ratio and optical gap.[29] The
dashed lines are only guidelines for the eye. With increasing
sp3/sp2 ratio the graphite like sp2-cluster become smaller in
number and size and the ID/IG ratio is decreased. The chains
responsible for the E2g C(sp2)-C(sp2) stretching mode are now
shorter, giving rise to lower vibrational frequencies and
downshift of the G peak.
While six-member ring structures are the most stable, rings
of other sizes are possible, for example five- and seven-member
rings, and necessary in order to impart curvature in small
clusters. For example, such rings are observed in fullerenes and
nanotubes. Both breathing (A type) and stretching vibrations (E
type) exist with frequencies in the range observed in a-C films.
Siegal et al. performed deconvolution of the Raman spectra
using the vibrational frequencies of idealized five-, six-, and
seven-member p-bonded topologies.[30]
3.3. a-C, ta-C (Hydrogen free)
The hardest, most ªdiamondlikeº carbons, ªtetrahedral
bonded amorphousº ta-C, obtain up to 85 % sp3 bonded carbon.
Hydrogen free a-C with high sp3/sp2 ratio shows the
following features in the Raman spectra (see Fig. 6):
(i) The G peak frequency is upshifted from 1530 to
~ 1570 cm±1 with increasing relative sp3 concentration.
(ii) The ID/IG ratio is very low and disappearing for large sp3
content. For very high sp3 values the G band is nearly
symmetrical.
(iii) At ~ 600 cm±1 a Raman band is observed which is absent
in hydrogenated a-C.
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0.8 ta-C
ID / IG
0.4
0
1570
ν(G) (cm-1)
1560
1550
1540
1530
1520
0.6 0.8 1
sp3/sp2
Fig. 6. Raman intensity ratio ID/IG and Raman frequency of the G band in dependence on
the sp3/ sp2 ratio for tetraamorphous carbon DLC (ta-C). The sp3/sp2 ratio was determined
by EELS measurements (d Prawer et al.,[80] j Ferrari et al.,[26] ~ Anders et al.).[81, 82]
As the sp3 content increases, the sp2 bonded clusters become
smaller, the carbon rings are more distorted, open up and break
into segments with chains of C=C groups. Therefore, the D
band, which is due to the breathing mode of aromatic sp2 rings,
vanishes. The G band is now mainly due to the bond stretching
vibrations of small chainlike clusters with conjugated p
bonding.
A comparison with Raman measurements on nanocrystal-
line diamond and on ion beam amorphized diamond shows
that there are no vibrational modes for sp3 bonded carbons at
energies exceeding 1400 cm±1.[31] This result is confirmed by
calculations of the vibrational density of states (VDOS) of
diamond showing two maxima at about 600 cm±1 and near
1200 cm±1 in the VDOS.[32, 33]
The high frequency of the G peak in ta-C has also been
attributed to its high compressive macroscopic stress.[34, 35]
However, it was verified by annealing up to complete stress
release that only small structural changes were induced in ta-
C.[36]
The upshift of the G peak could be explained by an increased
number of oleofinic sp2 groups in chains. Their vibrational
frequencies are above the frequency of the G peak of graphite.
This effect can be seen more clearly by UV excitation of the
Raman spectra,[37] where the Raman band was observed at
about 1660 cm±1 (by excitation with 244 nm). In the case of
excitation with visible light this band is too weak to been seen
due to strong resonant enhanced contributions.
The Raman band observed at ~ 600 cm±1 in hydrogen free a-
C corresponds to a strong band observed in nanodiamond and
corresponds to the calculated maximum in the VDOS of
diamond indicating sp3 bonded carbon.[31. 32] On the other
hand, the frequency of that band also roughly corresponds to
the acoustic and out-of-plane optical vibrational modes of
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 699

graphite,[38, 39] as stated by Tamor and Vassell.[25] Further it is
REVIEWS
not clear why the band is not seen in a-C:H.[25]
3.4. Correlation Between Raman Spectra and Overcoat
Properties
The macroscopic properties of DLC (for instance hardness,
wear properties, optical gap, density) correlate with parame-
ters derived from fits to their Raman spectra. For a-C:H
overcoats it was found that the G peak position is correlated
with the hardness: The films are harder and more dense with
decreasing G peak frequency corresponding to enhanced
relative sp3 content. Tamor et al. found that the hardness and
the density of the diamondlike carbon films increases with
increased halfwidth of the G line.[25]
It was also shown that the frequency of the G band correlates
with tribochemical wear rates,[40] a DLC overcoat with good
wear properties and durability needs a high relative amount of
sp3-bonded carbon.
The decrease in tribochemical reactivity is due to the
reduced affinity for chemisorption of oxygen, which forms
surface oxides: Whereas sp2-bonded carbon readily reacts with
oxygen, sp3 bonded carbon does not.[41]
Further, the optical gap in hydrogenated films found in
absorption measurements, can be correlated with the G line
position and the ID/IG ratio.[35]
The optical band gap of DLC is considerably lower than that
of diamond (~ 5.5 eV). It is controlled by the p states of sp2 sites
and narrows nearly linear with increasing sp2 content.[42]
Maximum optical gaps observed are ~ 4 eV in a-C:H and
3.5 eV in ta-C, the minimum gap is about 0.5 eV for high sp2
content.[42, 43]
Therefore, DLC films with high sp3/sp2 ratio are transparent
for visible light (514.5 nm corresponds to 2.41 eV) whereas
films with high sp2 content are not. Accordingly, the light
penetration depth and the Raman scattering volume depend on
the sp3/sp2 ratio. The dependence can be used to estimate this
ratio, for instance if the exciting light penetrates the film partly
and a Raman signal from the substrate is observable as in the
case of silicon substrate.
A method for measuring the thickness of carbon overcoats
on sliders was proposed by Varanasi et al.[44] They used the
Raman band intensity as measure of the thickness as a function
of wear. A linear dependence of the G peak height of the
thickness was found for films in the thickness range 1±
10 nm.[11] The thickness to be measured should be much
smaller than the laser light penetration depth, which is
dependent on the DLC film properties and the laser wave-
length used. The method is only useful for monitoring the film
thickness in a well-controlled deposition process, because the
Raman peak intensity is dependent on the thickness and the
DLC film properties as well.
The blood compatibility of DLC films is also influenced by
the sp3/sp2 ratio. It was shown that the ID/IG intensity ratio in
the Raman spectra is correlated with the adherent in vitro blood
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Irmer, Dorner-Reisel/Micro-Raman Studies on DLC Coatings
platelet quantity, which was controlled with optical microsco-
py and SEM. The films were synthesized by plasma immersion
ion implantation-deposition and the proper sp3/sp2 ratio was
controlled using suitable C2H2/ Ar gas ratio during deposi-
tion.[45]
In vitro studies with bone marrow cell cultures point out that
Ti4+ ions directly affect the function of the bone cells called
osteoblasts in terms of secretion of osteocalcin and formation of
mineralized matrix.[46, 47] By adding titanium to the diamond-
like carbon matrix, different cellular reactions of bone marrow
cells were improved.[48] It is suggested by Schroeder et. al that
titanium-induced effects on cell cultures were due to a contact
mechanism of bone marrow cells to the titanium containing
diamond-like carbon film or to modified protein adsorption.[48]
4. Resonance Raman Scattering in DLC
In the last sections, the discussion of features in the Raman
spectra influenced by specific properties of the DLC overcoats
was based on results obtained by excitation with the 514.5 nm
Ar+ laser line that is mostly used for characterisation of DLC
overcoats. The Raman scattering cross section of the sp2-
bonded graphitic clusters in DLC films is enhanced by
resonance for excitation with visible light. For excitation with
the 514.5 nm line the Raman scattering cross section of
graphitic bonded carbon is more than fifty times greater than
that of sp3 bonded carbon, which is not influenced by
resonance. Therefore, the frequencies, intensities and band-
widths of the Raman bands depend on the excitation
wavelength used. That means that the direct comparison of
Raman spectra from different DLC coatings requires the same
excitation conditions. The influence of the resonance effect in
DLC coatings depends on the sp3/sp2 ratio: For small sp3
content the changes in the Raman spectra of DLC are similar to
those observed in nc-graphite whereas larger effects are
observed in DLC with more sp3 bondings.
Figure 7 shows Raman spectra of nanocrystalline graphite
(planar domain size ~ 3 nm) and a DLC overcoat with low sp3
content £ 10 % excited at various laser wavelengths.
The G band frequency in nc-graphite is not dependent on the
wavelength. This band arises from a first order Raman process
with participation of phonons near the C-point of the Brillouin-
zone. The shift to the higher frequency 1594 cm -1 and the
halfwidth broadening in comparison with crystalline graphite
(1582 cm -1) can be explained as a size-effect (wave vector
uncertainty). Phonons near the C-point (where the LO phonon
dispersion curve is bent up, see Fig. 9) contribute with higher
frequencies than at the C-point.
The D band is much more influenced by resonance effects:
The frequency is downshifted with about 0.2 cm±1/nm and the
ID/IG ratio increases with the wavelength of the exciting laser.
This can be understood in the context of the double resonance
Raman effect that will be discussed later.
The behaviour of the Raman spectra of the DLC overcoat if
changing the excitation wavelength is qualitatively similar due
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Irmer, Dorner-Reisel/Micro-Raman Studies on DLC Coatings

increased excitation wavelength similar as in nc-graphite, but

REVIEWS
nc-graphite DLC
1321 1594
the frequency shift is much more pronounced (about
~1580
0.47 cm±1/nm) than in the case of nc-graphite. Another feature,
1330 not observed in nc-graphite, is the downshift of the G band with
Raman intensity

excitation wavelength. With increased sp3 content, the graphit-

676 nm
like aromatic clusters are small with pronounced size depen-
1352
1355 dent vibrations of different frequencies, whereas in DLC
1365
overcoats with larger clusters their vibrational properties are
514 nm more similar and can be described with dispersion curves
1380 calculated for graphene layers (Fig. 9).
Systematic resonance Raman measurements on different
458 nm kinds of carbon materials were already performed by Vidano et
al.[49] They observed that the frequency of the D-band rapidly
800 1200 1600 2000 800 1200 1600 2000 decreases with increasing excitation wavelength. In this work it
was also reported that the upshift of the overtone of the D-band,
Raman shift (cm-1)
the so-called G¢-band (observed at about 2700 cm±1 for
Fig. 7. Raman spectra of nanocrystalline graphite and DLC (low sp3 content) excited with
laser light of different wavelength. The D band is shifted to lower frequencies with
excitation wavelength 488 nm) was found to be approximately
increased wavelength whereas the G band is nearly not influenced. two times the upshift of the D-band. Nearly the same excitation
energy dependences found other authors in different carbon
materials containing aromatic structures such as hydrogenated
amorphous carbon,[50±53] carbon black,[54] glassy carbon and
to the dominance of sp-bonded clusters with graphitelike
crystalline graphite,[55, 56] carbon nanotubes.[57, 58]
domains.
The D-band frequency increases with increasing laser
The resonance behaviour of DLC overcoats with more sp3
energy in the range 44-51 cm±1/eV for various sp2 carbon
content is more complicated.
materials.[56, 59, 60]
Figure 8 shows Raman spectra of a DLC overcoat with sp3/
2 In the model of Tuinstra and Koenig the appearance of the
sp ratio of about 0.3. The spectra were excited with the lines of
D-band was explained with relaxation of the wave vector
an Ar+laser (458 nm), Nd:YAG laser (532 nm), and a Kr+ laser
conservation in finite crystallites,[18] thereby allowing some
(676 nm), respectively. A linear background was subtracted
modes to show Raman activity. This model was later
before fitting the spectra with two Gaussian functions. The D
theoretically supported by the study of the A1g breathing
band intensity is increased and its frequency downshifted with
modes in small aromatic clusters and by correlating the
observed disorder-induced bands to structures in the vibra-

676 nm DLC 458 nm

514 nm
676 nm
10 nm

1496
2 nm
5 nm

1291

1600 LO
iTO
1200
ωPh(cm-1)
Raman intensity

LA
oTO
532 nm 800
1529
iTA
400
1344
oTA
0
Energy (eV)

10
σ∗ π∗
0 σ π
458 nm
1556 -10

-20
1388
Γ Wave vector K
Fig. 9.Phonon dispersion and the electronic bands r,pr*andp* along
 
2p 2p
C 0; 0† K ;
800 1200 1600 3a 3a
Raman shift (cm-1) of a single graphite layer.[66, 67] A resonant transition near the K point between the upper
valence band p and the conduction band p* excited with laser light of wave vector k ~ is
Fig. 8. Raman spectra of DLC (sp3/sp2 ~ 30 %) excited at different wavelengths. The D shown. It corresponds to phonons with wave vector ~ q near K (D band) selected by the
band as well as the G band is shifted to lower frequencies with increased wavelength. double resonance condition j~ qj ˆ 2 ~k ~ K:

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tional density of states resulting from finite-crystal-size
REVIEWS
effects.[19, 61, 62] However, these models fail to explain the
dispersion of the D-band with laser excitation energy. The
attribution of dispersive effects to the selective sampling of
carbon clusters with various sizes La excited at different
wavelengths is in contradiction with the fact that dispersion
of the second-order G¢-band in single-crystal graphite (La ®¥)
is experimentally observed which shows no disorder-induced
D band.[51]
In the last few years, there has been significant advance in
the understanding of the origin and dispersion of the D band.
The observed effects were explained in terms of the coupling
between electrons and phonons in a wave vector selective
resonance Raman scattering process.[26, 55, 59, 60, 63±65]
Thomsen and Reich proposed a model in terms of a double
resonance Raman process for the origin of the D band.[63] Saito
et al. showed that the experimental Raman observations of the
D band dispersion can be placed according to the double
resonance theory.[65] They succeeded in assigning many other
dispersive phonon modes previously observed in resonance
Raman experiments in sp2 carbons.
The double resonance Raman effect occurs when both the
intermediate and the initial (or final) state are actual electronic
states. Electronic transitions between the p and the p* electronic
bands with energies corresponding to visible photons only
occur in the vicinity of the K point in the Brillouin zone (see
Fig. 9). Near the K point both the energy Ec of the conduction
band p and the energy Ev of the valence band p* depend linear
on the wave vector ~ k and a resonance between the laser energy
EL and the electronic transition with energy DE=Ec ± Ev occurs
at different wave vectors ~ k in the Brillouin zone dependent on
the laser energy
p
EL ˆ DE Dk† ˆ Ec Dk† Ev Dk† ˆ 3ac0 Dk
where D~ k =~
kK- ~
k is the difference between the wave vector kK at
the K point and the wave vector ~ kK, a = 0.246 nm is the in-plane
graphite lattice constant and c0 » 3 eV is the tight-binding
overlap energy parameter.[65] The resonance enhanced elec-
tronic transitions select the phonons with wave vector ~ q from
the Brillouin zone, which can contribute in the scattering
process.
In Figure 9 the phonon dispersion curves of a graphite layer
are shown.[66,67] The density of (k,q) pairs which satisfy the
double resonance conditions peaks for the LO band at different
wave vectors near the K point in dependence on the exciting
laser energy. This is shown in the upper part of Figure 9 for the
energy range of visible laser lines often used in Raman
experiments (488 nm: 2.54 eV, 514.5 nm: 2.41 eV, 633 nm:
1.96 eV).
For UV excitation wavelengths (244 nm) the resonance
effect is much smaller than for excitation with visible or near-
infrared excitation. The sp2 Raman bands are significantly
reduced compared to the sp3 Raman bands. Gilkes et al. have
shown that there is a direct correlation between a band
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Irmer, Dorner-Reisel/Micro-Raman Studies on DLC Coatings
observed at about 1150 cm±1 (so called ªT bandº) and the sp3
fraction.[37] A correlation was found between this band and the
predicted vibrational density of states (VDOS) in amorphous
sp3 carbon.
5. Incorporation of Other Elements in DLC
5.1. Hydrogen
The role of hydrogenation of DLC was already discussed in
the last sections. Here, we discuss another aspect of hydrogen
incorporation, which influences the measured Raman spectra
of a-C:H overcoats.
With increased hydrogen content, and therefore, the
number of sp3 sites, the optical gap increases. As a conse-
quence, the background luminescence increases. The Raman
spectrum is positioned on this background. Because relatively
small changes in the hydrogen content are observable in slope
changes of the background luminescence, the slope is some-
times used to characterize the H content. This method works
most effectively if green or blue laser excitation is used which
generate the DLC Raman spectra on the steepest slope of the
luminescence. Within the disk drive industry there have been
developed a number of algorithms to relate the slope of the
fluorescence background to the H concentration.[11] They work
within a limited range of parameters. Problems arise if the
substrates contribute to the background: The slope changes
with film thickness because the substrate contribution changes.
An appealing feature of UV-Raman measurements is the
possibility to directly monitor covalently bound hydrogen and
nitrogen within the DLC overcoat. In the C-H stretching region
hydrogen bound to both sp3 carbon (~ 2900 cm±1) and sp2
carbon (~ 3100 cm ±1) has been observed in the Raman
spectra.[68]
Additional elements such as nitrogen, silicon, boron,
fluorine, phosphorus and various metals have been introduced
in the carbonaceous structure to modify the properties of
conventional DLC coatings, in particular hardness, friction,
wear, biocompatibility, optical and electrical characteristics.
5.2. Nitrogen
In the last few years, it was found, that incorporating N into
DLC films yields tribological and chemical properties, which
were, in some cases, superior to that of hydrogenated
amorphous carbon or ta-C.[27,69] Compared to DLC, carbon
nitride coatings exhibited a slight improvement in hardness,
coefficient of friction, roughness, and corrosion. CNx coatings
on cultures of mouse fibroblasts and human endothelial cells
provided a comparable or better surface for the cellular
attachment, growth, and morphology.[70] Papakonstantinou
et al. studied the incorporation of nitrogen in ta-C with about
76 % sp3 content.[27] They found that incorporation of a small
amount of nitrogen, 2 at.-%, reduces the clustering of the sp2
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Irmer, Dorner-Reisel/Micro-Raman Studies on DLC Coatings
phase and improves the nanomechanical properties of the
films. Hardness and elastic modulus were measured as a
function of the depth. For higher nitrogen concentrations the
Raman spectra indicated an increase in the size of the sp2
graphitic clusters. Up to 2 at.-% N the samples exhibited a
single, relatively symmetric G band near 1560 cm±1. For higher
concentrations two bands appear which were resolved at
1575 cm±1 (G band) and 1375 cm±1 (D band) for 17 at.-% N,
indicating that incorporation of nitrogen causes progressive
graphitisation in the ta-C films.
Bhattacharyya et al. reported similar results for nitrogenated
a-C:H films.[71] At very small amount of nitrogen incorporation
aromatic rings are broken, however at higher nitrogen
concentrations sp2 bonded clusters increase in size. It is found
that with the increase of the nitrogen concentration the ratio
between the C-N bonds and the C=N bonds increases
corresponding with the shift of the G peak to higher wave
numbers and the increase of the ID/IG ratio.
For N concentrations >25 % Chowdhury et al. observed in
the Raman spectra a peak between the D and G peaks at
1455 cm±1,[72] which they called the N peak and attributed it to
N=N bonding vibrations.[73]
5.3. Silicon
By addition of silicon to a-C:H films (from 0 % up to about
9 %) an increase in the sp3 fraction from 0.27 up to 0.85 was
observed, as deduced from X-ray photoelectron spectroscopy
(XPS).[74] The Raman spectra showed a decrease in the ID/IG
ratio and shifts of the G band and the D band to lower
frequency. However, upon silicon incorporation, the mechani-
cal and tribological properties are degraded. It is suggested that
increased hydrogen content in the deposits when silicon is
incorporated is a reason, as is shown by an increased Raman
spectral background slope.
5.4. Titan, Wolfram
Ti or W-containing DLC films are nanocomposites consist-
ing of nanocrystalline (some few nm) TiC or WC embedded in
an amorphous hydrocarbon matrix.[75] Hardness and elastic
modulus exhibit monotonic increases as the Ti and W
concentrations increase. Because the crystal structure of cubic
TiC and WC is of the NaCl type, TiC and WC are both first-
order Raman inactive, the observed Raman spectra show the
typical bands of a-C:H. The ID/IG ratio decreases gradually
with increasing carbide fraction.[75]
5.5. Phosphorus
Mechanically hard, electrical conducting diamond-like
carbon films containing 0 to 26 at.% phosphorus have been
deposited by pulsed laser ablation of graphite/phosphorus
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targets.[76] The Raman spectra of these phosphorus modified
REVIEWS
diamond-like carbon films lack the sharp peak at 350 cm±1,
generally attributed to P9 cages. The absence of any Raman
signal in the 650±770 cm±1 range, that is the region in which
Raman active C-P bond stretching modes would be expected,
suggests relatively little C-P bonding in the films and that the
carbon and phosphorus each prefer to aggregate as localised
clusters.
Furthermore, as seen for many other dopants such as
nitrogen, the incorporation of phosphorus causes a marked
increase in the intensity ratio of the D band to the G band. This is
interpreted in terms of an increased propensity for nanocrys-
talline graphite formation and possible formation of fullerene-
like structures in the amorphous matrix.[76]
5.6. Calcium, Oxygen
Improved biocompatibility of DLC coatings with Ca-O-
incorporation was tested with cell cultures of mouse fibro-
blasts.[77] Graphitic nanoclusters were detected in the Ca-O
modified DLC by high resolution TEM. This result corresponds
to Raman spectra, where the shift of the D-peak to higher
frequency and enhanced ID/IG intensity ratio were observed in
comparison with DLC coatings without Ca-O, indicating
enhancement of sp2-bonded nanoclusters.[77±79]
6. Summary
Raman scattering is a relatively easy, fast and non-
destructive method for the characterization of DLC. The
Raman spectra contain information about the sp3/sp2 ratio of
the carbon bonding. Many mechanical and tribological proper-
ties of DLC films depend on this ratio. In DLC overcoats for
biomedical applications dependence of adhesion and biocom-
patibility on the sp3/sp2 ratio was found. The frequencies of the
observed G-band and the D-band are sensitive to small changes
of the sp3/sp2 content. Therefore, frequency shifts are reliable
parameters to characterize DLC overcoats as routinely used in
the hard disk industry. The intensity ratio ID/IG of the two
bands is also correlated to the sp3/sp2 ratio and can be used for
characterization. By excitation with visible light the Raman
spectra are dominated by the resonance enhanced graphite
Raman spectra and the frequencies and intensities depend on
the excitation wavelength used. Therefore, comparison of the
Raman spectra of different DLC-materials requires use of the
same excitation wavelength. By UV excitation sp3 bonded
carbon is probed more directly.
Received: January 11, 2005
Final version: January 22, 2005
±
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