Characterization of diamond films by Raman spectroscopy

Diane S. Knight and William B. White

Materials Research Laboratory, The Pennsylvania State University, University Park,
Pennsylvania 16802
(Received 12 August 1988; accepted 9 November 1988)
As the technology for diamond film preparation by plasma-assisted CVD and related
procedures has advanced, Raman spectroscopy has emerged as one of the principal
characterization tools for diamond materials. Cubic diamond has a single Raman-active first
order phonon mode at the center of the Brillouin zone. The presence of sharp Raman lines
allows cubic diamond to be recognized against a background of graphitic carbon and also to
characterize the graphitic carbon. Small shifts in the band wavenumber have been related to
the stress state of deposited films. The effect is most noticeable in diamond films deposited
on hard substrates such as alumina or carbides. The Raman line width varies with mode of
preparation of the diamond and has been related to degree of structural order. The Raman
spectrum of hexagonal diamond (lonsdaleite) is distinct from that of the cubic diamond and
allows it to be recognized.

I. INTRODUCTION range of a few micrometers. Power at the sample surface

The metastable synthesis of crystalline diamond films
from energized hydrocarbon gases or plasmas mixed with
an excess of hydrogen has been achieved.1"4 Development
of such films for application as semiconductors, hard coat-
ings, IR-transmitting films, substrates, and other purposes
requires a rather precise characterization of the material.
Particularly it is important to identify the diamond structure,
and to assay regions of graphitic carbon and noncrystal-
line and hydrogen-rich tetrahedral carbons (diamond-like
carbons).
Graphitic carbon and other sp2 bonded amorphous car-
bons are strong Raman scatterers in spite of their intense
optical absorption. Likewise, diamond and related carbons
have strong and easily identifiable Raman spectra. Raman
spectroscopy has much to offer as a nondestructive charac-
terization tool.5'6 With microfocus instruments individual
small regions in a heterogenous film can be examined. As
will be shown in this paper, Raman spectra provide a large
amount of structural and phase information.
It is the purpose of this paper to present Raman spec-
tra of a wide variety of natural and synthetic diamonds and
associated carbons, and to interpret these spectra in terms
of the characterization of diamond films.
II. EXPERIMENTAL
A collection was made of natural diamonds, synthetic
diamonds and diamond films, diamond-like carbons, crystal-
line graphites, and noncrystalline carbons of various kinds.
The idea was to have a broad collection of materials so that
the reproducibility of spectra from sample to sample could
be assessed.
Raman spectra were measured on an Instruments SA
Ramanor U-1000 spectrometer. Excitation was by means
of the 514.5 nm line of an argon ion laser with an output
power in the range of 100 to 500 mw. The instrument is
equipped with a microscope with a focal spot size in the
was about 10% of the initial laser power. For the graphite
spectra, multiple scans were collected and co-added in the
instrument control computer. Good spectra of diamond
could be collected with a single scan. Slit widths were set
manually with the spectral slit width carefully adjusted to
be less than the intrinsic width of the Raman lines being
measured.
In general, no sample preparation was necessary. Be-
cause the microscope attachment uses a 180° scattering
geometry, direct measurement of films, crystal faces, cut
surfaces, and fresh fracture surfaces was possible.
III. RAMAN SPECTRA OF CARBONS
A. Diamond
Diamond belongs to the face-centered cubic lattice
with space group Fdbm. There are two carbon atoms in the
primitive unit cell and thus a single triply degenerate first
order phonon with symmetry T2g. From the selection rules
of factor group Oh, this mode is Raman active only; the
diamond structure has no first order infrared absorption.
The first order band appears as a single sharp line at
1332 cm"1 (Fig. 1). It is the characteristic diagnostic fea-
ture for diamond. The Raman spectrum of diamond has
been observed many times and its polarization properties
and temperature dependence have been carefully examined
by Solin and Ramdas.7 There is a sharp two-phonon line at
2450 cm"1 and its temperature dependence,7 line width,8
and resonance scattering9 have been observed. The two-
phonon line did not appear in spectra obtained with the
microfocus instrument. For a more detailed discussion of
the lattice dynamics of the diamond structure, see Lax.10
B. Graphite
Graphite consists of stacked sheets with the carbons
within the layers arranged in a two-dimensional network of

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 D. S. Knight and W. B. White: Characterization of diamond films

dividual sheets and the other is a shear mode of the two

FIG. 1. Raman spectrum of natural diamond, showing reference band
and absence of other background features.
regular hexagons. The aromatic character of the hexagonal
rings is reflected in the short carbon-carbon distances,
142 pm, within the hexagonal sheets compared to 335.4 pm
between the layers. The space group is P63/mmc with
4 carbon atoms in the primitive hexagonal cell." Some struc-
ture analyses have suggested C6mc (P63mc) as the space
group of graphite,12 but the various spectroscopic measure-
ments have all been interpreted on P62/mmc symmetry.
The first order phonons of graphite can be classified in
factor group D6h of space group P62/mmc (Table I). The
mode symmetries given in Table I agree with those of
Mani and Ramani13 and with Tuinstra and Koenig.14 The
calculation is based on the placement of two carbons on
the 2 (b) sites and two carbons on the 2 (c) sites of the
space group following the conventions of the International
Tables for Crystallography. Other authors have given dif-
ferent symmetry assignments, probably because of differ-
ent placement of the carbon atoms on the equipoints of the
space group.
Two Raman active modes are predicted, both vibrat-
ing in the plane of the sheets. One is a stretching of the in-
TABLE I. Classification of the normal modes of graphite.
adjacent sheets in the unit cell. The stretching mode should
occur at high wavenumbers and be largely independent of
the stacking sequence. The shear mode has been observed
at low wavenumbers but is broadened and lost by disorder
in the stacking sequence. If the lower symmetry-space
group were correct, the absence of a center of symmetry
would make the two infrared bands Raman active. No evi-
dence for these bands has been reported.
Because of the weak interlayer bonding, graphite crys-
tals are subject to disorder along the c-axis while at the
same time the strong intralayer carbon-carbon bonding
maintains a high degree of order within the individual car-
bon sheets. At the limit is a condition known as turbostratic
stacking in which there is random relative orientation of suc-
cessive layers. These crystallographic characteristics strongly
influence the features seen in the vibrational spectrum.
The Raman spectrum of natural single crystal graphite
shows the main features (Fig. 2). There is a sharp intense
band at 1580 cm"1 which has been assigned to the pre-
dicted E2 C-C stretching mode.14'15 The feature at 2710-
GRAPHITIC CARBON
1580
Polycrystalline Graphite
2710
576
Highly Oriented
Pyrolytic Graphite
2719

NT Acoustic Vibrations Selection rules

0 580
0
0
2 Inactive
0 Natural Graphite Crystal
2 Raman (x2 - y2,xy)
2724
0
1 IR,Ellc
0
0
1 IR,E±c 500 1000 1500 2000 2500 3000
(x,y)
0 Wavenumber
FIG. 2. Raman spectra of crystalline graphites.

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 D. S. Knight and W. B. White: Characterization of diamond films

2724 cm ' is a two-phonon band taken to be 2 X 1357, 1343

the band that appears in the spectrum of polycrystalline
graphite. The 1357 cm"1 band itself has engendered con-
AMORPHOUS CARBON
siderable debate in the literature. It does not appear
in large grain single crystals but does appear in well-
crystallized graphites with small particle size. It is assigned
to a first order phonon at the M point, the 1000 zone
boundary, of the hexagonal Brillouin zone1415 (see Koster16
for nomenclature). The small particle size of the polycrys-
talline graphites causes a breakdown of the k = 0 selection Glassy Carbon
rule, allowing the M-point phonon to contribute to the
Raman scattering. The line is narrow and of considerable 2680 2924
intensity because the optic branch is very flat across the
M point.17 Nemanich and Solin18 have described the sec-
ond order phonon of the zone center Raman line which oc-
curs as a weak but sharp band at 3248 cm"'.

C. Disordered sp2 carbons

What is of interest to the characterization of diamond Diamond-Like Carbon
films are the various non-diamond carbon structures that
are sometimes deposited as part of the film. The discussion
of the vibrational spectrum of graphite is a convenient ref-
erence point.
Many measurements have been made of the Raman
spectra of disordered polycrystalline and noncrystalline
graphitic carbons (by graphitic, we here mean that the car-
bon atoms are three-coordinated and are bound by sp2 type
hybrid orbitals), and Raman spectroscopy has become one
of the preferred tools for the characterization of these car-
bons.19"31 The pair of bands at 1357 and 1580 cm"1 are the
most diagnostic features and are sometimes designated the
D band and G band, respectively. Line width and D/G
intensity ratio both vary depending on the structure of the
carbon (Fig. 3). There are also small shifts in the wave-
number of these bands.26 The highly disordered carbons
such as charcoal and coke have very broad bands whereas
the lines are more narrow in glassy carbon and also in the 500 1000 1500 2000 2500 3000
polycrystalline graphites. In addition to the D and G bands, Wavenumber
a second first order zone boundary phonon appears at FIG. 3. Raman spectra of various noncrystalline, mainly graphitic,
1620 cm"1 in some carbons and may have the effect of carbons.
seeming to shift the wavenumber of the G band. The sec-
ond order phonon at 2700 cm"1 becomes a doublet at 2700
and 2735 cm"1.22 the second order lines relate to the stacking disorder along
Of the many attempts to relate features in the Raman the crystallographic c-axis.25
spectrum to structure, one of the most comprehensive is There is some confusion in the literature over the dis-
that of Lespade et al.,29 who identified four "graphitiza- tinction between structural order and particle size. The in-
tion indices": (i) the wavenumber of the G band, (ii) the tensity of the M-point zone boundary line relates to the
band width of the G band, (iii) the D/G intensity ratio, particle size14 and would presumably appear in the spectra
and (iv) the band width of the second order phonon at of small crystallites even if they were perfect crystals. The
2700 cm"1. All of these parameters correlate to some ex- line broadening, especially the broadening of the G band,
tent with other measures of carbon structure such as the relates to disorder within the carbon sheet. Stacking dis-
diamagnetic susceptibility and the d002 x-ray diffraction order of the sheets themselves would relate to vibrations
line. It has been claimed that the first order Raman lines along the c-axis, but these do not appear in the Raman
relate to structural order within the carbon sheets whereas spectrum. The model for Raman scattering of graphite by

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 D. S. Knight and W. B. White: Characterization of diamond films

Lespade, Al-Jishi, and Dresselhaus25 contains a coherence
length and a line width as fitting parameters.
Figure 4 shows the relation of ID/IG to graphite par-
ticle size for Tuinstra and Koenig's14 original data plus
such additional data as could be gleaned from the litera-
ture. A least squares regression produces the power func-
tion shown on the figure. The inverse relation between
particle size and intensity ratio is rigorous to the statistical
limitations of the data.
The width of the G band and the D/G intensity ratio
were measured for all graphitic carbons examined in this
study (Table II). Although the data are too sparse to pre-
sent as a map, to a rough approximation line width and in-
tensity ratio appear to be independent variables. Glassy
carbons, amorphous carbons, and crystalline graphites all
plot into distinct regions in terms of these two variables.
The graphitic carbon in the diamond films appears to have
1000
"5
the smallest particle size and be the most disordered of the
carbons examined.
D. Diamond-like carbon
The diamond-like carbons are amorphous carbon films
often formed from dehydrogenation of organic materials.
They are characterized by a high hardness and often con-
tain a certain amount of hydrogen. See Woollam et al.22
for an extensive bibliography.
The Raman spectra of diamond-like carbons (Fig. 3)
consist of a distinctive broad band which seems to contain
several overlapping components lying between the two
graphite bands and at higher wavenumbers than the dia-
mond band. Similar spectra have been observed by Wada
et al.33 and Ramsteiner et al.34
The question concerning the structure of diamond-like
carbon is whether these materials contain some percent-
age of tetrahedrally coordinated carbon atoms. Calculated
Raman spectra from analysis of multi-atom physical mod-
els of the structure suggest that the percentage of tetrahe-
dral carbon is small,35 a conclusion also reached by Wada
et al.33 The Raman spectra of the four diamond-like carbons
examined are distinctly different from any of the graphitic
carbons and support the idea that diamond-like carbon is
structurally distinct. There was an insufficient number of
specimens to investigate the range of variations that might
appear in the spectra.

100
IV. PHASE CHARACTERIZATION OF
DIAMOND FILMS
A. Diamond and non-diamond carbon
The sharp Raman line at 1332 cm"1 is the characteris-
tic signature of the diamond structure but the scattering ef-
ficiency is only 9 x 10~7 cm"'/sr, whereas the scattering
efficiency for graphite is 500 x 1O~7.33 Because the intrin-
FIG. 4. Literature data relating particle size to band intensity ratio. Cir- sic Raman intensity of the graphite spectrum is 50 times
cles, Ref. 14; triangles, Ref. 19; squares, Ref. 25; diamond, Ref. 20. that of the diamond spectrum, the Raman spectrum is a
very effective means of detecting percentage levels of
graphitic carbon in diamond films but is not a sensitive test
TABLE II. Band shape parameters for various graphitic carbons.
for diamond in the presence of other types of carbon. This
Specimen AvG (cm ')
is illustrated in Fig. 5, which shows the Raman spectra
ID/IG
of a sequence of films prepared with different ratios of
Natural graphite crystal 0 13 methane to hydrogen. The spectrum of the film prepared
HOPG 0 13 with 2% methane is dominated by the bands of graphitic
Pyrolytic graphite 0.07 23 carbon, and it would not be possible from the Raman
High purity, fine-grained graphite 0.11 18
spectrum alone to prove that diamond was present. As the
Polycrystalline graphite 0.20 28
Glassy carbon A 0.91 79 methane concentration is lowered, the diamond line gradu-
Glassy carbon B 1.32 61 ally comes to dominate the spectrum.
Burnt wood 0.77 107 The spectra presented in this investigation were all
Coke 0.76 99
Diamond film (2% CH4) 1.45 115
obtained with a microfocus Raman spectrometer so that
Diamond film (1.5% CH4) 1.23 141 the effective sampling area is on the order of 1-2 pirn in
Diamond film (1.0% CH4) 1.13 187 diameter. This means that one can examine individual
diamond crystals which in these films tend to be 10 to

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 D. S. Knight and W. B. White: Characterization of diamond films

1332

1574
1%CH4
80 Torr
990'C

750 1250 1500 1750 500 1000 1250 1500

1333

1.5% CH4 0.5% CH4

40 Torr 80 Torr
970°C 980'C
°_

520 520

500 750 1000 1250 1500 1750 500 750 1500 1750

FIG. 5. Raman spectra of several diamond films on silicon substrates, showing improved quality with depositional conditions. The band at 520 cm ' is
due to the silicon substrate.

20 /u.m in linear dimension. Likewise one can examine grain
boundaries and other features on the diamond films.
Raman spectra were measured on a suite of natural dia-
monds including gem quality diamonds, several examples
of ballas diamonds (a translucent coarsely polycrystalline
diamond usually found as spheres a few mm in diame-
ter36), and several examples of carbonado (a black poly-
crystalline diamond with interlocked crystallites in the
1-20 /xm size range.37'38 One of the ballas diamonds was
sectioned and a careful grain-by-grain traverse made across
the surface. Except for the Raman line width and for the
occasional occurrence of a satellite band discussed in the
section on hexagonal diamond, all spectra were identical.
The diamond spectrum shown in Fig. 1 may be taken as
the prototype.
The full width at half maximum varies with the type
of diamond sample. Some representative data are shown in
Fig. 6. The narrowest diamond line was produced by a
General Electric Company high pressure diamond with a
width of 1.7 cm"1. Natural diamonds including gem qual-
ity and polycrystalline diamonds tend to have widths in the
range of 2 cm" 1 . The lines of the CVD diamond films
range from rather broad down to widths comparable to
natural diamonds. The width of the line is sensitively de-
pendent on the conditions of film growth. All of these mea-
surements were made with a spectral slit width of 0.75 cm"1
(75 fim) so that the results represent true line shapes un-
modified by slit functions.
B. Intensity and film thickness
The intensity of the diamond Raman line increases lin-
early with thickness of the diamond film (Fig. 7). The
thickness was measured with a Talley Surf profilometer on
a series of films prepared by masking off a portion of the
substrate so as to produce a sharp edge. The intensity was
measured by drawing a base line along the scattering back-
ground and measuring the peak count rate above the base
line. The fact that the plot does not go through zero is sim-
ply an artifact of baseline construction. At the greatest
thickness measured, the plot remains linear. It must even-
tually level off when the film thickness becomes greater
than the focusing depth of the laser beam. Although the
beam is converging as it emerges from the objective lens

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 D. S. Knight and W. B. White: Characterization of diamond films

PEAK WIDTH

Full Width at Half Max 30,000

9 0 0 ° 1% CH 4 60 Torr
7.4 cm" 1

w
20,000

3
o
o
9 8 0 ° .5% CH4 60 Torr
5cm" 1
10,000

GE Diamond 1.7 cm"'
1315 1320 1325 1330 1335 1340 1345
WAVENUMBER
FIG. 6. Raman line shapes for various diamonds and diamond films.
Full width at half maximum is given on each spectrum.
of the microscope, it produces Raman scattering from the
full film thickness and indeed the lines of the silicon sub-
strate appear on all of these spectra.
The absolute position of the thickness-intensity plot
depends on laser power and other instrumental parameters.
A well-defined diamond band was measured on a 0.6 ptm
film in another experiment.
V. HEXAGONAL DIAMOND
A. Theoretical considerations
In the course of their research on high pressure dia-
mond, Bundy and Kasper39 succeeded in preparing a hex-
agonal form of diamond. They assigned the structure to
space group P63/mmc, but the structure is not to be con-
fused with graphite. Although there are layers of carbon
atoms in a 2H stacking, all carbons are 4-coordinated.
Hexagonal diamond, also known by the mineral name,
lonsdaleite, is related to the 3C packing in cubic diamond
by the shift of one carbon layer along the 111 planes. Hex-
agonal diamond has the same relation to cubic diamond as
I
10 20
1350
FILM THICKNESS {y.m)
FIG. 7. Relation of the 1332 cm"1 Raman line intensity to film thickness.
earlier.40 Three Raman-active modes are predicted. Two of
these, Alg and E2g, correspond to the triply-degenerate
stretching mode of cubic diamond, here split into a compo-
nent vibrating in the plane of the hexagonal layers and a
component vibrating perpendicular to the layers. Unlike
graphite, the bonding strength of hexagonal diamond is
comparable parallel and perpendicular to the hexagonal
layers and the wavenumber separation between the Alg and
E2g modes is expected to be small. In analogy to wurtzite,
the third Raman band of Elg symmetry is a shear mode that
would be expected to occur in the low wavenumber re-
gion. Like cubic diamond, the hexagonal diamond struc-
ture has no first order infrared absorption.
TABLE III. Classification of the normal modes of hexagonal diamond.
NT Acoustic Vibrations Selection rules
Alg 1 1 Raman: x2 + y2\z1
A2g 0 0
0 0
B2g 1 1 Inactive
Eig
1 1 Raman (yz, xz)
1 1 Raman (x2 — y2,xy)
E2S

the wurtzite form of ZnS has to the sphalerite form of ZnS Alu 0 0
in the structurally similar zinc sulfide polymorphs. A2u 1 z 0
Bu 1 1 Inactive
The normal modes of hexagonal diamond were classi- B2u 0 0
fied among the irreducible representations of factor group Eu 1 (x,y) 0
D6h (Table III). The classification of the inactive B2g and E2u 1 1 Inactive
Bu phonons are interchanged from an analysis published

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 D. S. Knight and W. B. White: Characterization of diamond films

B. Occurrence of hexagonal diamond NATURAL DIAMOND CHIP

The Raman spectra of hexagonal diamond powder pre-
pared by a shock loading technique (Fig. 8) exhibit a single
band which varies in wavenumber from particle to particle
from 1315 to 1326 cm"1. These bands are broad and are 1332
superimposed on a luminescence tail. There is no evidence
for the predicted band splitting and there is no real evi-
dence for the predicted low wavenumber band although the
faint broad line near 300 cm"1 is suggestive (Fig. 8).
The Raman spectra of cut faces on natural diamond
sometimes show a satellite band (Fig. 9). The satellite
band occurs at 1319 wavenumbers but has the same line-
width as the main diamond line at 1332 wavenumbers.
Comparison of band positions suggests that some of these
diamonds contain small regions of hexagonal diamond. 1319
The satellite has been observed on single crystal diamond
1250 1500
KAVENUMBER

HEXAGONAL DIAMOND
[SHOCK LOADED]

2. 3

1315 1320 1325 1330 1335 1340 1345 1350

WAVENUM8ER

FIG. 9. Satellite band on cut face of diamond chip.

250 S00 750 1000 1250 1500

WAVENUMBER and on polycrystalline diamond (ballas) but only on cut
surfaces. It is hypothesized that the shearing action during
cutting has transformed some of the cubic diamond to hex-
agonal diamond. The geometry of the hexagonal regions is
unknown and the possibility that they are clusters of stack-
ing faults should be investigated.
No evidence for hexagonal diamond has been found in
the Raman spectra of any of the CVD films examined, but
the intensity of this band is so weak it would be difficult to
see on the films which already have a low intensity of the
1332 cm"1 band.

VI. STRESS STATE OF DIAMOND FILMS

The first order phonon mode of cubic diamond is a re-
250 50D 750 1000 1250 1730
markably invariant feature. Spectra were compared from
WAVENUMBER a suite of natural diamonds, polycrystalline natural dia-
FIG. 8. Raman spectra of hexagonal diamond powder (DuPont Corp. monds, synthetic diamonds prepared at high pressure, and
shock-loaded diamond). a wide range of synthetic diamond films made by several

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 D. S. Knight and W. B. White: Characterization of diamond films
depositional processes including plasma excitation, and hot
wire filament excitation. In nearly all cases, the diamond
line occurred exactly at 1332 cm"1.
The exceptions were diamond films deposited on hard
substrates such as alumina, tungsten carbide, silica glass,
or SiAlON (Fig. 10). On these substrates, the diamond
films gave Raman bands that were shifted in the range of
4-13 wavenumbers, with both positive and negative shifts
being observed (Table IV). The diamond line for films de-
posited on soft substrates such as silicon were exactly at
the expected 1332 cm"1 position.
The wavenumber of the diamond Raman line is known
to increase with pressure.41"44 Using the pressure depen-
dence curve of Sharma et al.,A1 it is possible to interpret
the small wavenumber shifts as internal stresses in the
films brought about by mismatch between diamond film
and substrate. These values also are listed in Table IV. The
negative shifts have to be interpreted as films in tension
and the positive shifts as films in compression. Much
smaller shifts in the Raman spectrum of silicon on silica
were observed by Zorabedian and Adar45 and were also in-
terpreted as due to local stress.
VII. CONCLUSIONS
Raman spectra have been measured on a variety of
natural and synthetic diamonds, diamond-like carbons, and
graphitic carbons in order to test the applicability of
Raman spectroscopy as a characterization tool for synthetic
diamonds. The diamond line is a reliable indicator of the
presence of diamond and with a microfocus Raman spec-
trometer, the diamond signature can be observed from
grain to grain on a deposited film. Graphitic carbon has a
distinctly different Raman spectrum which is more intense
than the diamond spectrum, allowing a small amount of
graphitic carbon to be recognized in diamond films. Many
of the investigations of the relationship between measured
1332
1345
DIAMOND ON ALUMINA
NATURAL DIAMOND
500 7S0 1000 1250 1500 1750
WAVENUMBER
FIG. 10. Raman line shift for diamond film on alumina substrate. Natu-
ral diamond spectrum is given for reference.
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TABLE IV. Stress-induced Raman lineshifts in diamond films.
Substrate v (cm"1) \v (cm"1) Stress (GPa)
Alumina 1345 + 13 + 5.5
1328 - 4 -1.7
Tungsten carbide 1327 - 5 -2.1
1328 - 4 -1.7
1328 - 4 -1.7
SiO2 glass 1337 + 5 +2.1
SiAlON 1336 + 4 + 1.7
spectral parameters and the structure state of graphitic car-
bon have been evaluated.
The diamond line exhibits changes in line width that
have been related to degree of structural order. In some cut
diamonds a satellite line appears which has tentatively
been assigned to regions of hexagonal diamond formed
during the cutting process. There are small shifts in the
wavenumber position of the diamond line when the dia-
mond films are deposited on hard substrates. These have
been correlated with stress state in the diamond.
Overall, the Raman spectrum has proved to be one of
the most versatile signatures of synthetic diamond. Raman
spectroscopy is a nondestructive measurement and this is en-
hanced by the ability to use microfocus Raman for examin-
ing grain structure within small areas of a diamond film.
ACKNOWLEDGMENTS
The following individuals are thanked for the loan
of carbon materials: Peter Bachmann, Andrzej Badzian,
Theresa Badzian, William Drawl, and Ronald Weimer for
CVD diamond films; Peter Thrower for graphites and
amorphous carbons; D. Snell for ballas diamond; Miles
Bailey (Dupont Corp.) for hexagonal diamond powder;
Peter Koidl (Fraunhofer-Institute fur Festkorperphysik) for
diamond-like carbon; and R. C. DeVries (General Electric
Co.) for high pressure diamond. Appreciation is extended
to Russell Messier and other members of the Diamond Re-
search Group for helpful discussions and encouragement.
This work was supported by the Office of Naval Research.
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