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Carbon films: Structure and microtexture (optical and

electron microscopy, Raman spectroscopy)

Article in Thin Solid Films · July 1983

DOI: 10.1016/0040-6090(83)90333-4

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Thin Solid Films, 105 (1983) 75-96
PREPARATION AND CHARACTERIZATION 75

CARBON FILMS: STRUCTURE AND M I C R O T E X T U R E (OPTICAL

AND ELECTRON MICROSCOPY, R A M A N SPECTROSCOPY)

J. N. ROUZAUD AND A. OBERLIN

Laboratoire Marcel Mathieu, Equipe de Recherche 131 du CNRS, Unit~ d'Enseignement et de Recherche
Sciences, 45046 Orleans Cddex (France)
C. BENY-BASSEZ
Bureau de Recherches Gdologiques et Minidres, Dipartement Miniralogie, Gdochimie, Analyses, B.P.
6009. 45060 Orldans Cddex. and Laboratoire de Spectroscopie lnfra-rouge et Raman, Lille (France)
(Received March 30, 1983; accepted April 15, 1983)

Nearly pure carbon films (150 and 500 ~ thick) were prepared by condensing
carbon vapour in vacuum. They were then heat treated under an inert gas flow from
25 to 2700 °C. The samples were studied comparatively with (1) a conventional
transmission electron microscope (structure and microtexture), (2) a Raman
microprobe (for quantification of the different types of defect by Raman spec-
troscopy) and (3) an optical microscope (for determination of the optical indices).
The carbon films were found to graphitize in five stages. Each stage is characterized
by the release of a given type of defect. Crystal growth occurs first in thickness and
then in diameter. Perfect aromatic layers are formed progressively and the three-
dimensional order improves. Polycrystalline graphite is then obtained. The
graphitization is faster and more complete for thick films (about 500 A thick) than
for thin films (about 150 A).

1. INTRODUCTION

The optical properties of carbonaceous matter were studied first in graphite

crystals 1-3 and then in coals 2°4-6. Measurements have also been attempted on
carbon films as deposited under vacuum 7' s. The refractive index n and the extinction
coefficent k have been calculated from reflectance data. The indices of graphite (a
uniaxial negative crystal) are no = 2.15, k. = 1.42, n, = 2.04 and ke ,~ 0.02 for a
5460 ~, wavelength. For wavelengths ranging from 2000 to 6500 ~, L 2, no and ko
reach maxima near 2600 A and remain nearly constant in the visible spectrum,
except that ko shows a small shoulder near 4300 ~,. The refractive index of carbon
films as deposited under vacuum ranges from 1.9 to 2.7 7.s. Attempts have been
made to correlate the optical constants of coals and graphite to elemental analysis
and X-ray diffraction data 2'5'6. For coals of increasing rank 4, no = 1.7-2.1 and
ko = 0.02-0.7.
Until recently, variations in the optical properties of carbonaceous materials
(during coalification, carbonization and also graphitization) were attributed to a
progressive growth of the aromatic planar structures, i.e. to polymerization. This
assumption was demonstrated to be erroneous by results from X-ray diffraction9-11

0040-60901831$3.00 © ElsevierSequoia/Printedin The Netherlands

76 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

and transmission electron microscopy (TEM) studies ~2-~4. These studies have
shown that during the coalification and the carbonization processes the basic
structural units (BSUs) are polyaromatic molecules less than 12 rings in diameter,
either single or piled up in parallel in twos or threes. Only their mutual arrangement
in space changes.
Raman spectra have been recorded on samples as different as graphite 15-2~,
carbon fibres ~9, chars ~9'2~ and coals 2°'2~. Two bands were observed. One was
attributed to the E2s mode of graphite (1580 cm - ~). The other band (I 350 cm - ~) was
attributed to various kinds of defect. The spectra were interpreted by comparing
X-ray diffraction data ~s -~g, electronic properties ~9, elemental analysis 2° and IR
results 21. Almost none of the samples (except single-crystal graphite) was pure
carbon. Thus they exhibited a low degree ofcrystallinity and were rich in functional
groups. Furthermore, these samples were selected at random and the studies are not
complete and systematic. It is difficult to interpret the results. In the present paper,
the samples chosen were carbon films because they are nearly free of heteroatoms,
i.e. of functional groups. A series of experiments was carried out on the same set of
film samples and the data were analysed to form a consistent picture of the evolution
of the structure and microtexture of these films during heat treatment. The films
were prepared by condensing carbon vapour on a suitable substrate under vacuum.
The as-deposited films were heat treated from room temperature to 2700 °C. Two
series of films, thick and thin respectively, were studied first by means of an optical
microscope. The transmittance and reflectance were measured for various wave-
lengths in the visible spectrum. The films were then studied by TEM, i.e. selected area
electron diffraction (SAED), the tilted dark field mode and the lattice fringe
technique (to determine the structure and microtexture). Finally, the Raman spectra
were taken on the same areas of the films.

2. SAMPLING

The carbon films were prepared by condensing carbon vapour on alkali halide
cleavages in a 10- ~ Torr vacuum. Carbon was obtained by fast evaporation (0.1-
l0 s) of two graphite electrodes presenting a poor electrical contact. The substrate
was then dissolved in water and the portions of the carbon films which floated were
picked up on carbon grids. The grids were prepared by heating pieces of cotton at
2500 °C ~4. The as-deposited films were mainly made of carbon but also contained
small amounts of impurities such as hydrogen, helium, CO, CO2 and H 2 0 22°23
They were heat treated inside a furnace under argon flow (heating rate, 20 °C m i n ~;
residence time at the maximum temperature, 15 min). The samples were heated in
100 °C steps from room temperature to 2700 °C but the steps were restricted to 30 °C
when the properties varied too quickly.
Several grids were covered with the samples and heat treated simultaneously
for study by means of Raman spectroscopy and electron microscopy. The same film
was later transferred onto glass slides to be studied by optical microscopy and
Raman spectroscopy: such a transfer is effected by putting the grids covered with the
carbon film between two glass slides and compressing the two slides; the carbon film
sticks perfectly flat to the slide whereas the grid is broken and blown away. The flat
portions obtained were I0--100 ttm in diameter.
C FILMS: STRUCTURE AND MICRO'tEXTURE 77

Two series of carbon films were examined: thick films (about 500 A) obtained
by a rather long evaporation (10s); thin films (about 150.~) for which the
evaporation lasted less than 1 s.

3. EXPERIMENTAL DETAILS

3.1. Optical microscopy

A Leitz Orthoplan microscope equipped with an MPV 1 microphotometer was
used to study the optical constants. An appropriate filter yielded nearly monochro-
matic light (i. = 5460 ~). Interference filters were used to obtain a continuous
variation in ,;. (precision better than _+30 ,~). The transmittance (objective, 4 0 x ;
numerical opening, 0.70) and reflectance (objective, 50 x ; numerical opening, 0.85)
were measured at ncar-normal incidence on surfaces of area 20-150 ~m 2.
The refractive index N of an absorbing medium is expressed in a complex form:
N = n - ik = n( - ix)
where n is the real refractive index, k is the imaginary part of the index, i.e. the
extinction coefficient, and ~ = k/n is the absorption index.
The transmittance T, the reflectance R and the thickness e of the carbon films
are computerized to obtain n and k (by successive iterative calculations24-26). The
computer program takes account of the partial reflection of the incident beam on the
glass slide which is encountered first and also of the multiple reflections inside the
carbon film. A priori estimates of n and k are used to calculate R and T for a given
value of e. Values for AR = R~cas-Rca~ and AT = T~cas- T~ l are used to calculate
An and Ak. New values of n = n + An and k = k + Ak are then introduced in the
computer program. The iterative calculations are repeated until AR and AT reach a
value lower than 10 -3. Various thicknesses e were tested but solutions were
not always obtained when e was chosen too large or too small. Moreover, some of
the solutions obtained were not relevant when n and k were either smaller than the
values for glass or higher than those for graphite. Finally, the thickness range was
limited to values which produced a good fit within the complete range of heat
treatment temperatures H T T : 400 A < e < 600 ,~ for the thick films and 100 ,~ <
e < 200 ,~ for the thin films. For such thicknesses, the curves obtained by plotting
the optical indices versus H T T keep the same shape whatever the thickness. They
were only translated along the ordinate and their peaks were located at the same
HTT. However, tentative measurements of the film thickness were carried out to
obtain experimental values. The thickness of the as-deposited films was evaluated by
means of an interferometer to be about 500 ,~ for the thick films and slightly less than
150/~ for the thin films. These values are close to those corresponding to the limiting
reliability of the method but they are consistent with the curves of Cosslett and
Cosslett 7 in which the thickness of the as-deposited film was plotted against its
optical density. The method of Cosslett and Cosslett is considered to be reliable 22 if
the film is prepared in a vacuum better than 10 -4 Tort and is deposited onto
substrates far enough away from the carbon source (more than 10crn). The
preparation of our samples meets these conditions. Unfortunately, measurements
by intefferometry become inconsistent on heat-treated samples. However, the film
thickness can be assumed to stay constant below H T T = 2120°C. At H T T >/
78 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

2290 “C, electron and optical micrographs show some corrosion effects. The data
become irrelevant and will not be presented here. Figure l(a) shows the etch pits in a
corroded film with many steps; the setting of the aromatic layers inside the steps is
imaged in Fig. l(b) (002 lattice fringes).

Fig. 1. Etch pits in a carbon film heat treated at 2290 “C: (a) bright field; (b) 002 lattice imaging.

For all HTT, the errors were estimated by taking AT/T z (T,,, - Tmin)/(Tm,, +
Tmin) and AR/R z (R,,,- R,,,)/(R,,,+ R,& The mean AT/T and AR/R values
were both found to be about 2% for thick films whereas AT/T = 2% and AR/R =
4.5% for thin films. Ae/e z 11% was found for thick films. This value was deduced
from transmutance measurements. Similar values can be assumed for thin films
since the geometry of the electrodes relative to the substrate was similar. For the
thick films, An&, varied from 1% to 5%, whereas AkJk, ranged from 10% to 15%.
C FILMS: STRUCTURE AND MICROTEXTURE 79

To determine final values of no and ko, a thickness of 500 ]~ was chosen. For the
optical parameters no and ko of the thin films (e ~ 150 A), the errors are of the same
order of magnitude.

3.2. Conventional transmission electron microscopy

All the TEM modes were used 27 such as SAED for following the progressive
graphitization process and observation of the 002 lattice fringes for measuring the
number N of parallel aromatic layers in a stack, the diameter L of a perfect layer and
the diameter L, of a distorted layer. The diameter L, was also evaluated by using the
less usual 11 dark field mode 14' 2a. Since the aromatic layers which are biperiodic in
structure (turbostratic structure) are in slight rotational disorder, moir6 fringes
develop. Similarly, the crystallites which develop also remain rotated and moir6
fringes appear. The diameter of the layers can thus be approximated to the size of the
area which exhibits a homogeneous moir6 pattern. The 002 lattice fringe images are
periodic and can be used as objects in a laser beam optical bench to obtain their
optical diffraction pattern. Densitometric recordings of the patterns were carried
o u t 29.

3,3. Raman spectroscopy

Raman spectra were obtained by means of a molecular optical laser examiner
(MOLE) microprobe. A laser beam (,~.o = 5145 ~) falls at normal incidence on a small
area of the carbon film (a few square micrometres, i.e. about 10-13 g). This area is
then observed by means ofa Leitz Orthoplan optical microscope. The scattered light
is polychromatic, appearing at frequencies v0 + Av. The Av values are characteristic
of the vibrations of the molecules or phonons of the sample. The spectra were
smoothed and computerized to obtain the area and the centre frequency of the
bands.

4. RESULTS (THICK FILMS)

4.1. Optical data

4.1.1. Monochromatic light (2 = 5460/~)
The aromatic layers which form the carbon films are approximately parallel to
the film plane 14. Thus only the ordinary refractive index no and the corresponding
extinction coefficient k° can be determined. They are plotted versus H T T in Fig. 2. At
room temperature no (Fig. 2(a)) is nearly equal to the value for graphite (2.15). no
reaches the graphite value at H T T = 800 °C. It remains nearly constant throughout
the total heat treatment except for four minima observed respectively at 950 °C (no =
1.7), 1375 °C (n°= 1.9), 1670°C (no = 2.0) and 2020°C (no = 1.85). The variations
in k. are similar (Fig. 2(b)): k° has a value of 0.4 at room temperature, increases
slowly to 0.6 at 800 °C and remains nearly constant above this temperature, but it
too shows four minima at 850-950 °C, 1375 °C, 1670 °C and 2020 °C respectively.
For H T T > 2020 °C, ko increases rapidly towards the graphite value.
4.1.2. Wavelength dependence of n° and k. in the visible spectrum (4000-7000/[)
Transmittance and reflectance data were plotted versus HTT. The shape of the
curves does not change with wavelength, i.e. peaks appear at the same heat
treatment temperatures. For all HTT, the transmittance is minimum and the
80 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

nO
REFRACTIVE
INDEX

2,15 • ."-graphite
2,0

950
HTT
1,~=
0 500 1000 1500 2000 °C
(a)

IEXTkoINCTION
OEFFICIENT ko
1,42

1,0
I ...... graphite/

i
/
l

/
/

0,5 ~ / '
900 2020

HTT
0 500 1000 1500 2000 'C
(b)
Fig. 2. Optical parameters at 2 = 5460 A plotted vs. HTT (e = 500 A): (a) ordinary refractive index no:
(b) ordinary extinction coefficient ko.

rio (mean values)

. . . . 2 5 °C
2,0 ¸

~ ~ . ~ _ . 2 0 2 0 O c

1,5
(a) 4000 5(~00 60'00 7()00 "
' n O [mean values)

2.2

2,0- -'--------~--.... 2 1 2 0 °C

1,8 40'00 50'00 60'00 70"00"

(b)
Fig. 3. Computerized ordinary refractive index no us. wavelength ~. in the 4000-7000 ~, range (e = 500 ~):
(a) at room temperature and 2020 "C; (b)at 2120 ~C.
C FILMS: STRUCTURE AND MICROTEXTURE 81

reflectance is maximum between 4350 and 4500/~. no was calculated to be maximum

at about 4400/~, (Fig. 3) whereas ko increases progressively although a change in
slope is visible at about 4400 ~,; after this change the slope is smaller.

4.2. Electron microscopy data

At room temperature, broken and folded films give oblique SAED patterns, i.e.
SAED patterns (Fig. 4(b)) similar to fibre patterns (sketched in Fig. 4(a)). They show
002 arcs and faint l0 and l 1 lines without hkl modulations (sections of 10 and I 1
cylinders). We conclude that the films are constructed mainly of aromatic layers
arranged in a turbostratic structure, i.e. piled up in parallel but rotated at random.
These layers are parallel to the plane of the film. As HTT increases, higher 001 orders
appear (Figs. 4(c)-4(e)) up to 008 at 1500 °C. This indicates that the aromatic layers
become less distorted. Up to 2020 °C the film remains turbostratic since no hkl
modulations are visible (Fig. 4(c)). At HTT > 2020°C, 10l and Ill modulations
appear and become progressively sharper and more intense as graphitization
progresses (Figs. 4(d) and 4(e)). Figure 4(e) (HTT = 2290 °C) shows already sharp hkl
reflections characteristic of polycrystalline graphite. Above 2290 °C, single crystals
of graphite appear and become the main component of the films at HTT = 2500 °C
(Fig. 4(0). Thick carbon films can be thus classified as graphitizing carbons.
002 dark field images show bright areas less than 10/~, in size visible in the folds
only. This demonstrates firstly that the as-deposited film is mainly aromatic and
secondly that the aromatic layers are parallel to the film plane. Below 500 °C no 002
lattice fringes are clearly visible because either the film is not entirely aromatic or
single layers are the main component. Above 500 °C, the images show small stacks of
two to three parallel fringes less than 10/~ long, e.g. at 800°C (Fig. 5(a)). We
conclude that thick carbon films are constructed, like any other carbons t2-14, of
polyaromatic molecules less than twelve rings in diameter, single or piled up in
parallel in twos or threes and forming BSUs. Below 1600°C, such units show a
noticeable mutual misorientation but are nearly parallel to the film plane. Adjacent
structural units are associated with tilt and twist boundaries (see Fig. 8(a) below) to
form larger distorted layers (Fig. 5(b)) with a characteristic zigzag texture 12-14.
As heat treatment progresses, the number N of parallel layers increases (Fig. 5).
Figure 6 shows the values of N measured in lattice fringe micrographs for various
heat treatment temperatures. At first N is nearly constant (2-3) (Fig. 5(a)), then
increases gradually from 3 to 12 (Fig. 5(b)) and finally varies more sharply to reach
30 (Fig. 5(c)). Any further measurement of N becomes impossible because the Bragg
condition is stricter. Above 1670 °C the wrinkled layers suddenly stiffen (Fig. 5(c)),
causing the disappearance of the BSUs. They are replaced by layers still distorted on
a larger scale but with a larger radius of curvature. Layers with long-range stiffness
and perfection are obtained only at HTT > 2020 °C (Fig. 5(d)).
In the patterns obtained by optical diffraction on the 002 lattice fringe images,
every scattered beam corresponds to the spacing of one pair of fringes and
consequently to doo2 29. All these beams contribute to the formation oftwo arcs (Fig.
7). The half-opening of the arc corresponds to the variation in the twist fl (Fig. 8(a)).
Its width corresponds to the variation Ado02 in the interlayer spacing door Both
were measured by densitometry recording. The width of the densitometer slit was set
at its maximum for measuring fl (Fig. 8(b)) and at its minimum for measuring the
82 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

C d

!1'(I L
I!, 112

e , o
f

, o

e. •

~ : O "

~. ~ .

Fig. 4. Progressive graphitization: (a)sketch of an oblique Debye-Scherrer pattern; (b} oblique SAED
pattern ofa turbostratic film; (c)-(f) SAED patterns at (c) 1670 :C, (d) 2120 :C, (e) 2290 ::C and (f) 2500 ~C.

interfringe spacing spreading ADoo 2 (Fig. 8(c)). The twist fl was chosen as the
halfwidth at half-maximum of the curve and ADoo2 was chosen as the width at half-
maximum of the curve• Although not precise, these measurements are nevertheless
clear enough to show that some fringes exist at 300 °C. Even if this is not clearly
visible in the lattice fringe images, a shoulder is observed in the densitometry curves•
C FILMS: STRUCTURE AND MICROTEXTURE 83

Fig. 5. Progressive graphitization (002 lattice fringe images) showing the increase in the number N of
parallel layers in a stack and progressive occurrence of perfect aromatic layers (see (d)) as HTT increases:
(a) 800 °C; (b) 1510 °C; (c) 1810 °C; (d) 2120 °C.
 84 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

30

I
20~

10

___1_
HTT
0 500 1000 1500 20'00 °CL

Fig. 6. The number N of parallel layers in a stack plotted vs. H T T .

a b C

d e f . . ~ :~

g ~ h ~ i

Fig. 7. Optical diffraction patterns of 002 lattice fringe images: (a)309:'C: (b)511 :C; (c)950~C;
(d) 1210 C ; (e) 1375' C; If) 1385 ~C; (g) 1520 ~C; (h) 1815' C; (i12020 "C.
C FILMS: STRUCTURE AND MICROTEXTURE 85

Z 0"

slit

(b)

{a) tc)
Fig. 8. (a) Degree of misorientation of BSUs; (b), (c) densitometry recordings of optical diffraction
patterns (see Fig. 7), showing (b) the twist fl and (c) the inteffringe spacing spreading ADoo2.

For the same reason, fl and ADoo2 have to be expressed in arbitrary units, fl and
ADoo2 are plotted versus HTI" in Figs. 9(a) and 9(b). The two curves can be compared
with the optical diffraction patterns (see Fig. 7). Figure 9(a) shows a large variation in
fl as a function of HTT. fl becomes negligible after 2020 °C. The curve shows a very
sharp minimum at 1375 °C. ADoo 2 (Fig. 9(b)) decreases progressively as HTT rises
from 500 to 2000 °C with a sharp maximum at 1375 °C. The average value/~oo2 of
the interfringe spacing also decreases progressively as HTT increases indicating a
decrease in aToo2. However, the radial intensity profile of the arcs is asymmetric for
small angles. This indicates an asymmetric distribution of the inteffringe spacings as
already observed in other carbons a°. As long as the material is turbostratic, the
minimum of Doo2 corresponds to the minimum of doo2, i.e. to 3.44/~. There is no limit
for maximum/~o02, i.e. no largest interfringe spacing (either inside a single BSU or
between two adjacent units). Even if the magnification of the microscope cannot be
considered as fully reliable, doo 2 max can be said to range from 6.3 J~ (at 500 °C) to
3.7 JL(at 1810 °C) and do02 from 4.7 to 3.5 J~.
The diameter L= of the carbon layers was obtained by measuring the area of
molt6 fringes homogeneous in direction and in period in 11 dark field micro-
graphs. If 7 is the rotational angle, the period B is equal to dl t/y. For the samples
heat treated at high temperatures, the smallest period Bml. was always equal
to 15-25/~ (Y < 40)• For a turbostratic structure, the sets of molt6 fringes are easily
visible if the diameter of the layers is much larger than Bet,. If it is of the same order
of magnitude, only short sets of individual fringes can be seen. The length of the
fringes is thus indicative of the diameter L,, as illustrated in Fig. 10(a). In this figure
only short individual fringes are seen, about 30-60/~ long. Moir6 fringes are better
defined when the proportion of pairs of layers acquiring the AB graphite order
increases (Fig. 10(b)). However, there are no grain boundaries visible below 2120 °C.
They appear suddenly at 2290°C (Fig. 10(c)). Simultaneously the histogram of
crystallite size broadens and the average value of L= increases rapidly. Although the
material is subjected to corrosion above 2290 °C, the crystallite size can still be
measured because the moir6 fringes are still evident even in the presence of the etch
86 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

TWIST

40

30

20 1375

10

HTT
0 500 1000 1500 2 0 0 0 ~C
(a)

•O002
arbit, rar y
untts
30"

20"

10

1385 ~ .

HTT
0 560 10'00 lS'00 20'00 °c'
(b)
Fig. 9. (a) Variation in the twist fl plotted es. HTT; (b) variation in the interfringe spacing spreading
ADoo 2 t,s. HTT.

pits (Fig. 1 I(a)). When the crystallite itself becomes distorted (Fig. 1 l(b)) or at a grain
boundary (Fig. 1 l(c)), the fringes are deflected.
In Fig. 12, La is plotted versus HTT. It is first nearly constant (30-60 ,~,) (Fig.
10(a)), then it increases gradually from 60 to 400/~ (Fig. 10(b)) and finally more
sharply up to I lam (Fig. 10(c)) (the change in scale on the right-hand side of the figure
should be noted).

4.3. Raman spectroscopy data

For all samples the Raman spectra were smoothed graphically (Fig. 13). Then
C FILMS: STRUCTURE AND MICROTEXTURE 87

• 3UUA.

~ N ~ A

Fig. I0. Growth of the layer diameter L, ( I I dark field images): (a) 1610 ~C; (b) 1990 ~C; (c) 2290 ~C.
88 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

Fig. 11. Thick carbon film heat treated at 2650 :C (11 dark field): (a)etch pit; (b), (c) deflection of the
moir~ fringes (b) in a fold and (c) at a grain boundary.

two types of decomposition were attempted by computer based on a two-band

hypothesis and a three-band hypothesis respectively. Figure 14(a) shows the two-
band decomposition, the sum of which is represented by the smoothed curve. The
residue, i.e. the difference between the calculated curve and the experimental curve, is
represented in the lower part of Fig. 14(a). In Fig. 14(b) the spectrum is decomposed
into three bands and the same convention is used. A visual comparison between
Figs. 14(a) and 1,t(b) (the lower parts) shows that the residue is negligible only when the
spectrum is decomposed into three bands near 1580, 1500 and 1350 cm-1. This
solution has thus been chosen.
For every H T T the following two ratios were calculated: the area of the
1350 c m - 1 band to the sum of the areas of the 1350, 1500 and 1580 c m - 1 bands; the
area of the 1500 cm - 1 band to the sum of the areas of the 1350, i 500 and 1580 cm- 1
C FILMS: STRUCTURE AND MICROTEXTURE 89

bands. The sum of the 1350, 1500 and 1580 cm - ~ band areas represents the total area
of the spectrum. The ratios were called the "specific areas" of the 1350 c m - 1 and
1500 cm - 1 bands respectively. For some heat treatment temperatures (25, 511,703,

La
L.a (MOSTFREQUENT
VALUES] / t"
}Jm
2000" A - 1,0

1500 • 0,75

'°°°1 / .0,5

.0,25

tooo lS'OO 20'00 2goo °C" o

Fig. 12. The layer diameter L, plotted vs. HTT: the left-hand curve corresponds to the left-hand scale, the
right-hand curve to the right-hand scale.

iNTENSI
(arbl
rerVTY
t unlll) ~1~ -

2esooc

- - ~ ~ 2120°c
_ 1815°C
_~._ _ ~o°c

~1,17SoC

WAVE N U ~ R
noo n~o ~ ,ebo ~ ,'too c~ -I

Fig. 13. Smoothed Raman spectra of thick carbon films for various temperatures.
90 J. N. ROUZAUD, A. OBERLIN, t". BENY-BASSEZ

O,6C

O.gC

Y
z
z 3.~0 /
/
/ \
0.2S
1

(a) ,/

i • ~,1,
r\

O.BC
/
3.6:,

r-

S.~'

(.2% (

. . . . ,~ • ...... _.
•. : f i r 2 ~$,]. 72xi. ~2q:~. ~:bT. ~c$S. ~" . '" . . ." . :(.. 7 i,.

(b) I -:
Fig. 14. Computerized decomposition of a R a m a n spectrum: la)decomposition into two bands; (b)
decomposition into three bands (same conditions as in (a)).

1610 and 2120 C) several spectra were taken from various areas of the sample.
The error bars show the distribution of the values for a given heat treatment
temperature. Around these temperatures the error bars were postulated to remain
the same for the temperatures at which only one spectrum was obtained. The
resolution of the spectra is low. However, it can be noted that (1) the error bars are
small which indicates good reproducibility of the data, (2) the error bars are smaller
than the amplitude of the peaks and (3) the same features were found by Raman
spectroscopy for the same temperatures as by optical and electron microscopy.
C FILMS: STRUCTURE AND MICROTEXTURE 91

Therefore the curves deduced from the Raman spectra can be assumed to be
significant.
In Fig. 15(a) the ratio of the 1350 c m - t band area to the total area of the
spectrum is plotted v e r s u s HTT. It shows two sharp minima at 850 and 1375 °C. In
Fig. 15(b) the specific area of the 1500 c m - t band is plotted v e r s u s HTT. This is the
main band at room temperature, its area representing 60% of the total area while the
areas of the other two bands are equal. After a marked initial decrease the 1500 cm - 1
band exhibits a broad maximum in specific area at 700-800 °C and then a sharp
maximum at 1375°C followed by a sharp minimum at 1385°C. Finally, above
1410 °C, the specific area of this band decreases abruptly and disappears at 1670 °C.

1350 crn 1 RAMAN band

(specific area)

50

40

30

20

10 1375
'~ HTT
0 560 10'00 1500 2000 pc w
(a)
1 5 0 0 c m -1RAMAN band
70" {specific area)

50" 1 5

4O"

30. ]

20

10
• HTT
0 500 1000 1500 2(~0 o(~
(b)
Fig. 15. Specific areas of Raman bands plotted vs. HTT: (a) ! 350 c m - i band; (b) 1500 cm - t band.

The area of the 1580 c m - t band shows a general tendency to increase. It

becomes the only band between 2120 and 2500 °C. Besides its variation in intensity,
it also exhibits a variable wavenumber shift with a marked maximum (above 1600
c m - t) between 1200 and 1400°C.

5. DISCUSSION AND CONCLUSION

Because thick carbon films are graphitizing carbons they can be expected to
exhibit a steady decrease in the twist fl, in the inteffringe spacing Doo2 and in the
92 J. N. R O U Z A U D , A. OBERLIN, C. BENY-BASSEZ

spreading ADo02 of the spacing with heat treatment. In Fig. 16 the full curves
represent fl (curve a) and ADoo 2 (curve b). Within the range of maximum reliability
(1000-2000 °C) of the 002 lattice fringe technique, the two curves show, as expected,
a general decrease. However, the decrease is interrupted abruptly in the 1300-
1500 °C range where the curves become antisymmetric: fl shows a sharp minimum at
1375°C immediately followed at 1385~C by a sharp maximum whereas ADoo2
shows a sharp maximum followed by a sharp minimum. Both the antisymmetry and
the peculiar shape of the curves can be explained by the removal of peculiar
interstitial defects (either between the layers or between two superimposed BSUs}.
Interstitial defects act as a coupling between two superimposed aromatic layers or
BSUs. In contrast, other defects concentrate at the tilt and twist boundaries of two
adjacent BSUs (defects in the plane of the carbon film). They provide coupling along
the plane of the film. Shear stresses are generated by these two nearly perpendicular
couplings. They are in equilibrium which remains stable as long as defects do not
move. When a sudden release of interstitial defects occurs, in-plane shear stresses
prevail. The resultant of the stresses is no longer negligible. The twist therefore tends
to decrease whereas the interlayer spacing tends to increase. This happens near
1375'~C. The system can be compared either with strings acting along two

..... ..........i i .....i ...... :

13r~ 13~ HTT
0 500 10'00 1500 20'00 °C"
Fig. 16. C o m p o s i t e d r a w i n g for c o m p a r i n g the d a t a from electron m i c r o s c o p y ( - - ) , Raman
s p e c t r o s c o p y (- - -) a n d optical m i c r o s c o p y {- • • ): curve a, twist/~; curve b, interfringe s p a c i n g s p r e a d i n g
ADoo2; curve c, specific area of the 1350 cm - ~ b a n d ; curve d, specific area of the 1500 cm - ~ b a n d ; curve e,
e x t i n c t i o n coefficient ko.
C FILMS: STRUCTURE AND MICROTEXTURE 93

perpendicular directions or with coupled oscillators. In both cases, any decoupling

induces a counteraction causing damped out oscillations, i.e. first a decrease in//and
an increase in ADooz, then a sudden increase in ~ and a decrease in ADoo2. When the
stresses have relaxed,//and ADoo 2 come back to their expected values and decrease
steadily again. Above 2020 °C nearly all the defects have disappeared.
In Fig. 16, the full curves correspond to the electron microscopy data. They can
be compared with the broken curves which correspond to the Raman bands.
The full curve a (twist//) is similar to the broken curve c (1350 cm-1 band area)
whereas curve b (ADoo2) has to be compared with curve d (1500 c m - 1 band area).
Therefore it can be concluded that the 1350 cm - 1 band is due to the in-plane defects
located between adjacent BSUs which are responsible for the existence of tilt and
twist boundaries. By the same reasoning, it can be concluded that the 1500 cm-
band can be attributed to interstitial defects, either between the layers or between
BSUs, which are responsible for the occurrence of ADoo2. The shift of the 1580 cm -
band is probably also due to interstitial defects. The maximum shift is observed
between 1210 and 1410°C.
By assuming that the 1350 c m - t band is entirely due to in-plane defects
whereas the 1500 c m - ~ band is entirely due to interstitials, the two broken curves c
and d can then be compared for all HTT. As expected, they are antisymmetric from
room temperature to above 1500 °C.
To conclude, five stages can be recognized between room temperature and
2700 °C as follows.
At room temperature, a maximum number of interstitials (probably hetero-
atoms) is found. Thus the 1500 cm-~ band is the strongest (Fig. 16(d)), i.e. the
occurrence of single layers is favoured. Since there can be many single layers, N is
minimum and no 002 lattice fringes can be seen. The interstitiais that have the lowest
activation energy are easily removed from room temperature to H T T = 850-
950 °C. Clearly visible BSUs can thus develop. They can be seen at 500 °C and above.
N increases to 2 or 3 at the most.
More energetic interstitials are released at H T T = 850--950 °C (the maximum
in the 1500 cm- 1 band found at H T T = 700-800 °C was not taken into account
because all the other parameters indicate a value ranging from 850 to 950 °C).
Subsequently, N increases gradually. Lo remains stable since the in-plane defects
between two adjacent BSUs are still frozen in.
The most energetic interstitials are removed at H T T = 1375°C causing
damped out oscillations in the interlayer spacing. They disappear entirely at 1670 °C
(the 1500 crn - 1 band disappears). N increases drastically, but L, does not change
since only interstitials are removed but not in-plane defects.
A first series of in-plane defects are removed at the tilt and twist boundaries at
H T T ranging from 1500 to 1670 °C. The layers begin to stiffen partially whereas the
local tilt and twist boundaries, i.e. the BSUs, disappear. They are replaced by large
stacks of layers with a large radius of curvature. The intensity of the 1350 c m - t band
(Fig. 16(c)) decreases steadily beyond 1500°C. It tends drastically to zero above
2120 °C. L. increases gradually (see Fig. 12). Simultaneously, the triperiodic order
appears and develops slowly (see Fig. 4).
A second series of in-plane defects are removed in the 2120-2500 °C range. The
aromatic layers become entirely stm anta perfect and L, increases rapidly (see Fig.
94 J. N. ROUZAUD, A. OBERLIN, C. BENY-BASSEZ

12). The degree of graphitization (see Fig. 4) also increases rapidly (graphitization in
the strict sense of the word).
The same stages and steps can be recognized in the curves of optical properties
such as ko (Fig. 16, curve e). This curve is similar to that for the ! 350 cm i Raman
band area, i.e. it is antisymmetric to the curve for the 1500 cm i Raman band area.
The minima in ko can be explained by the maxima in the 1500 cm 1 band area, i.e. by
the decrease in the compactness of the film due to the increase in AD002.
Partial data have already been published for thin carbon films 14.31. The same
samples were used in the present work for obtaining additional electron microscopy
results and Raman spectra and for determining their optical properties. However,
only few samples were available and their optical parameters were also less precise
than those of the thick films (their representative points were more erratic).
Therefore they are discussed here only for comparison.
Unlike thick carbon films, thin carbon films are amorphous at room
temperature al and correspondingly their refractive index is low (1.6 instead of 2). In
amorphous materials, neither a twist ~ nor an interlayer spacing spreading ADoo 2
can be defined; it is only possible to recognize defects of unknown origin either in the
film plane or along the normal to the film. Raman spectra show experimentally that
the 1350 cm - ~ band is the strongest (it represents 60~'o of the total area). It can be
concluded that the major defects are in the film plane (twist-like or tilt-like defects)
and are maintained to H T T = 2000 ':C. In contrast, the defects along the normal to
the film are few at room temperature (25°o of the total area). They become negligible
just above room temperature (about 10°/0) and remain so while H T T increases to
1000°C. Although different from thick films, thin films are also graphitizing
carbons 14. However, they graphitize later and less completely than thick films. The
hk bands of their SAED patterns modulate only at 2130 °C (2020 °C for thick films).
Single crystals of graphite are never observed, only polycrystalline Debye-Scherrer
patterns (due to the smallness of the crystallite diameter La). Despite this delay in the
graphitization process, thin films behave like thick films and five stages can be also
recognized for them as follows.
The aromatization of the films occurs first and is completely over at 1000 °C3t.
BSUs oriented in a direction nearly parallel to the film plane are clearly visible. At the
end of this stage, the Raman spectra and optical properties are similar for the two
kinds of film. The amounts of interstitial and in-plane defects seem to be.similar for
both of them.
A second stage corresponds to a moderate increase in N (between 1000 and
1400 °C) from 2-3 to 12. La remains stable since the defects between adjacent BSUs
are still frozen in.
Interstitials are released at about 1400°C. This release is over at 1980°C as
indicated by the disappearance of the 1500 c m - I band. N can then increase
drastically up to 30.
The removal of the in-plane defects (tilt and twist boundary defects) begins
above 1980 °C. Thus La increases gradually whereas the intensity of the 1350 c m - 1
band decreases drastically. During this stage, the triperiodic order begins to occur.
The last increase in L, corresponds to the final removal of all the in-plane
defects in the range 2340-2700 °C. The layers are entirely stiffand perfect. The degree of
graphitization increases.
C FILMS: STRUCTURE AND MICROEEXTURE 95

The delay observed in the graphitization of thin films is probably due to their
amorphous nature at room temperature which is probably responsible for the
occurrence of more stable interstitial and in-plane defects in thin films.
In conclusion, when the graphitization of thin and thick carbon films was
studied by means of three combined techniques (conventional TEM, use of an
MOLE Raman microprobe and optical microscopy), five stages of evolution were
recognized. Each stage is characterized by the removal of a given type of defect.
lnterstitials are removed during the first three stages, the second and third stages
also being characterized by increases in the number N of parallel layers per stack.
This increase is first slow, then fast, whereas the crystallite diameter L, remains
constant. The last two stages are characterized by the removal of in-plane defects.
Thus L, increases slowly first and then more rapidly when the aromatic layers
become straight. The triperiodic order can thus develop.

ACKNOWLEDGMENTS

The authors acknowledge J. Lafait (Laboratoire d'Optique, Universit6 Paris

VI) and J. Moureton (Centre de Calcul, Universit6 d'Orl6ans) for optical parameter
computerization, L. Bernstein and M. Allain for interferometry measurements, and
B. de Bettignies (Laboratoire de Spectroscopic Infra-rouge et Raman, Lille) for the
use of the Raman band decomposition program.

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