WDS'05 Proceedings of Contributed Papers, Part II, 391–396, 2005.

ISBN 80-86732-59-2 © MATFYZPRESS

AFM Study of Hydrocarbon Thin Films

M. Valtr, I. Ohlı́dal
Masaryk University in Brno, Faculty of Science, Brno, Czech Republic.

P. Klapetek
Czech Metrology Institute, Brno, Czech Republic.

Abstract. In this paper atomic force microscope (AFM) study on hydrocarbon

thin films was performed. Thin films were prepared using plasma enhanced vapour
deposition (PECVD) in pulsed regime. The aim was to see whether the surface
roughness of the films changes with the duty cycle. The AFM is a direct measuring
technique for scanning surfaces of samples. From obtained images one can compute
many quantities characterizing the surface. It is shown that the root mean square
(RMS) value of the heights seems to be independent on duty cycle except for region
from 10 to 15 %. Outside of this region the RMS values of the heights vary in the
range from 6,3 to 14,8 nm, while for 10 % it is 96,3 nm and for 15 % it’s 61,7 nm.
Unfortunately also the deposition time, which corresponds to different thicknesses
of the films, was varied. This could be the reason for many times higher roughness
inside the region. Further study of this problem would be needed.

Introduction
Plasma polymerization is widely used technique having many applications [Janča and
Sodomka, 1998; Denes and Manolache, 2004]. Pulsing the discharge is one possibility to control
the chemistry during the deposition [Choukourov et al., 2003].
In this paper we concentrated on the study of the surface morfology of deposited thin films.
Probably most powerfull technique to deal with this problem is the atomic force microscopy
(AFM). It enables us to determine quantities like root mean square (RMS) value of the heights,
autocorrelation length, power spectral density function (PSDF), etc. These quantities have then
significantly influence on optical properties [Ohlı́dal and Vižďa, 1999].

AFM Statistical Characterization of Thin Films

One of the most important parameters of the statistically random rough surfaces is RMS
value of the heights σ. It is defined by the following equation [Klapetek, 2003]
Z ∞
2
σ = z 2 w(z)dz, (1)
−∞

where z denotes value of the height of the irregularity and w(z) is distribution of the probability
density of the heights. RMS value of the heights is only first moment describing statistical
properties in individual points. In order to perform more complete statistics, higher order
moments should emerge. Usually second order moments, which describe mutual interaction of
two points on the surface are sufficient. One of these quantities is the two-dimensional power
spectral density function. It can be written in terms of Fourier transform of the autocorrelation
function [Klapetek, 2003] G(τx , τy )
Z ∞
1
W2 (Kx , Ky ) = G(τx , τy )e−i(Kx τx +Ky τy ) dτx dτy , (2)
4π −∞
where Kx and Ky are components of the wave vectorqof the harmonic component of a certain spa-
tial frequency of the boundary roughness and τ = τx2 + τy2 is the distance between the points

391
 VALTR ET AL.: AFM STUDY OF HYDROCARBON THIN FILMS

z1 (x1 , y1 ) and z2 (x2 , y2 ). Within the AFM measurements we usually evaluate one-dimensional
PSDF, which is given by the following equation
Z ∞
W1 (Kx ) = W2 (Kx , Ky )dKy . (3)
−∞

If we suppose autocorrelation function to be Gaussian[Klapetek, 2003], we obtain for one-

dimensional PSDF

σ2T
W1 (Kx ) = √ exp(−Kx2 T 2 /4), (4)
2 π
where T is the autocorrelation lenght.
It should be emphasized that above definition formulae are valid for surfaces made by
continuous stationary isotropic and ergodic stochastic processes. Moreover we assume the mean
value of the heights to be zero.
An AFM scan consists of a dataset having N × M data points. In order to calculate the
above defined parameters, we have to use corresponding discrete formulae:
M X N
2 1 X
σ = z2 , (5)
N M j=0 i=0 ij

The values of W1 (Kx ) can be calculated by the fast Fourier transform, i.e.
N
2π X
W1 (Kx ) = |P̂j (Kx )|2 , (6)
N M h k=0

where P̂j (Kx ) is the Fourier coefficient of the jth row, i.e.
N
h X
P̂j (Kx ) = zkj exp(−iKx kh). (7)
2π k=0
Function w(z) must be calculated using following formula:

N (z, δz)
w(z) = (8)
N M δz
where function N (z, δz) represents the number of the values of zij lying within the interval
hz − δz/2, z + δz/2i.

Experimental
Thin films were prepared by plasma enhanced chemical vapor deposition (PECVD) tech-
nique in tubular type reactor. A schematic view of the apparatus is in the figure 1. The
horizontally mounted SIMAX° c glass tube was closed by two aluminium electrodes. Distance
of the electrodes was 186 mm and inner diameter of the tube was 77 mm. The apparatus
was pumped out by a rotary pump. Total pressure was measured using Leybold CERAVAC
diaphragm gauge. Gas flows were controlled by Hastings flowmeters. Gases used for deposition
were argon and acetylene. Flow rate of Ar and/or C2 H2 was kept constant at 4 sccm and/or 1
sccm. Corresponding total presure in the apparatus was about 39 Pa. Power was delivered via
matching unit from Dressler CESAR 133 generator operating at 13.56 MHz. Delivered peak
power during deposition was 10 W. The depositions were performed in pulsed regime, where
frequency of the cycles was always 1 Hz and duty cycle varied from 5 to 70 %. Silicon substrates
were located on a glass holder in the middle of the reactor. The deposition time changed from
10 to 40 minutes.

392
 VALTR ET AL.: AFM STUDY OF HYDROCARBON THIN FILMS

Prior to every deposition surface treatment in Ar was performed. Cleaning runned for
5 minutes at 5 W in continuous wave regime. After that deposition was started immediately.
AFM measurements were made with the help of Topometrix Accurex II L device in contact
mode. Scanned area was 20 × 20 µm.

4
1 3
2

8 6

10 9

11 12

Figure 1. Schematic view of the apparatus. 1 - power source, 2 - matching unit, 3 - samples,
4 - SIMAX tube, 5 - rotary pump, 6 - pressure gauge, 7 - glass holders, 8 - Al electrodes, 9 -
flowmeters, 10 - control unit, 11 - Ar cylinder, 12 - acetylene cylinder.

Results and Discussion

The AFM measurements were processed using Gwyddion analysis tool (downloadable from
http://gwyddion.net). It should be mentioned that the Gwyddion program uses in the fitting
procedure well known Marquart-Leveberg algoritm. The results on RMS rougness of the heights
σ and autocorrelation lenghts T are summarized in the table 1. The quantity σAFM was com-
puted directly from AFM data according to formula (5). The rest two quantities were acquired
by fitting experimental data by the least squares method. Experimental PSDF function was
calculated using formula (6) and the fitting function used was Gaussian PSDF function (4)
(σ and T were free parameters). Best fit values are then in the table 1 denoted as σPSDF and
TPSDF . If we compare σAFM and σPSDF we could say that they are in good agreement.
Table 1. The results on RMS roughness of the heights
σ and autocorrelation lenghts T .
duty cycle [%] σAFM [nm] σPSDF [nm] TPSDF [nm]
5 13,9 13,2±0,2 202±6
7 14,8 13,8±0,2 75±2
10 96,3 90,6±0,2 262±2
15 61,7 56,9±0,1 304±2
22 11,8 10,39±0,09 132±3
30 15,3 14,6±0,1 124±3
50 7,0 6,2±0,2 125±11
70 6,3 4,97±0,04 103±2

393
 VALTR ET AL.: AFM STUDY OF HYDROCARBON THIN FILMS

100
σAFM
80 σPSDF

60
σ [nm]

40

20

0 20 40 60 80
duty cycle [%]

Figure 2. Comparison of RMS rougness of the heights computed directly from AFM measure-
ment - σAFM and values obtained by the fitting procedure - σPSDF .

In the figure 2 is the graphical representation of results of RMS roughness of the heights
written in table 1. At first sight we can see that the roughness shows constant dependency except
for duty cycles 10 and 15 %. This discrepancy could have two explanations. The roughness
could be strongly dependent on the duty cycle within this region or there is some correlation
between roughness and film thickness. From ellipsometry, the estimates of film thicknesses were
done and it was seen that this two films were about 350 µm thick, while the thickness of the
rest of the films was about 150 µm. It seems that the film thickness has some influence on the
rougness, but to be really sure, more depositions should have been done.
In order to do more detailed study of the film surface, another quantities have been calcu-
lated. Namely it was the distribution of heights and PSDF function. In the figures 3 and 4 are
plots of these functions for single sample, where duty cycle was 15 %. From the figure 3 one
can see that the mean height of the peaks on the surface is about 219 nm. It can be also easily
seen that the w(z) function is asymetrical towards to higher values, which means that there are
some very high peaks present. Comparison of a measured PSDF with its best fit is ploted in
the figure 4. Furthermore on picture 5 is a 3D image of the sample surface.

Conclusion
The AFM technique is very powerfull tool to characterize surfaces of materials. It enables
us to estabilish quantities like RMS roughness of the heights, autocorrelation length, PSDF,
etc. These parameters strongly influence e.g. optical properties.
Hydrocarbon thin films were examined with this measuring technique and their surface
parameters were evaluated. It has been shown that the RMS roughness of the heights seems
to be almost independent on duty cycle. Values of σ vary in the range from 6,3 to 14,8 nm.
However in the region from 10 to 15 % there is a discrepancy. Further depositions would
be needed to perform more detailed examination of the influence of the film thickness on the
roughness.

394
 VALTR ET AL.: AFM STUDY OF HYDROCARBON THIN FILMS

0.018

0.015

0.012

0.009
w(z)

0.006

0.003

0.000

0 200 400 600 800 1000

z [nm]

Figure 3. Plot of the distribution of probability density of heights. Note that the mean value
is 219 nm.

3.0
AFM data
2.5 fit
PSDF [x10 nm ]
3

2.0
5

1.5

1.0

0.5

0.0

0.00 0.02 0.04 0.06 0.08

-1
Kx [nm ]

Figure 4. Plot of the power spectral density function computed from AFM data together with
the best fit with Gaussian PSDF.

395
 VALTR ET AL.: AFM STUDY OF HYDROCARBON THIN FILMS

Figure 5. 3D image of an sample surface. Hydrocarbon thin film grew for 25 minutes with
these deposition conditions: P = 10 W, QAr = 4 sccm, QC2 H2 = 1 sccm, f = 1 Hz, duty cycle
was 15 %. Note that σAFM = 61, 7 nm.

Acknowledgements. The present work was supported by the Ministry of Education under con-
tract FRVŠ 2005/2181.

References
Choukourov, A., Biederman, H., Slavinska, D., Trchova, M., Hollander, A., The influence of pulse
parameters on film composition during pulsed plasma polymerization of diaminocyclohexane, Surface
and Coating Technology, 174-175, p. 863-866, 2003
Denes, F., S., Manolache, S., Macromolecular plasma-chemistry: an emerging field of polymer science,
Prog. Polym. Sci., 29, 815-885, 2004
Janča, J., Sodomka, L., Plasma-polymerized organosiloxane thin films as selective gas sensors, Surface
and Coatings Technology, 98, 851-854, 1998
Klapetek, P., Characterization of randomly rough surfaces in nanometric scale using methods of modern
metrology, PhD Thesis, Masaryk University in Brno, Faculty of Science, Brno, Czech Republic, 2003
Ohlı́dal, I., Vižďa, F., Optical quantities of multilayer systems with correlated randomly rough bound-
aries, Journal of Modern Physics, 46, 14, p. 2043-2062, 1999

396