Surface Science 607 (2013) 170–173

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Surface Science
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Atomic force microscopy analysis of morphology of thin pentacene films deposited on

parylene-C and benzocyclobutene
Maksym Iazykov a, Mohsen Erouel b, Jacques Tardy b, Valeriy A. Skryshevsky c, Magali Phaner-Goutorbe b,⁎
a
Université de Lyon, Laboratoire de Physique, Ecole Normale Supérieure de Lyon, 46 allée d'Italie 69364 Lyon cedex 07, France
b
Université de Lyon, Institut des Nanotechnologies de Lyon UMR 5270, Ecole Centrale de Lyon, 36 avenue Guy de Collongue, 69134 Ecully, France
c
Institute of High Technologies, Kiev National Taras Shevchenko University, 64 Volodymyrska, 01601, Kiev, Ukraine

a r t i c l e i n f o a b s t r a c t

Available online 12 September 2012 This paper reports on an atomic force microscopy (AFM) investigation of the surface of pentacene films deposited
onto parylene-C and benzocyclobutene (BCB), two polymers dedicated to organic field effect transistors (OFETs).
Keywords: A thorough grain analysis was carried out by power spectral density (PSD) on pentacene films of different thick-
AFM nesses (ca. 15–60 nm). PSD spectra of experimental AFM images were analyzed by using fractal, ABC and super-
Pentacene structure models. These approaches permitted to explain the difference of the pentacene morphology on the two
Growth mode
substrates and to illustrate structural specificities related to change in the growth mode. Superstructures larger for
OFET
PSD
the pentacene on BCB than for the pentacene on parylene were revealed. On both substrates, larger superstruc-
Roughness tures occurred for 30 nm thick pentacene layers. This thickness also corresponded to the highest field effect
Grain size mobility in top gate OFETs parylene/pentacene deposited on BCB. The superstructure model applied on the PSD
curves showed that the increase of mobility for a 30 nm thickness was not related to an increase of the grain
size but to an increase of the island size.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction more recently surface morphology on a nanoscopic scale [12]. The

For the last two decades, organic field effect transistors (OFETs) have
been attracting considerable interest thanks to their promising applica-
tions in low cost, large area and flexible electronics. They include the
OLED display active matrix driving [1], sensors [2], electronic circuits
[3] or RFID [4]. Among the large number of available organic semicon-
ductors, pentacene has been thoroughly studied in the past and still
remains the p-type semiconductor exhibiting the highest hole mobility.
Transistors can be processed in two configurations, namely bottom gate/
top contacts and bottom contacts/top gate configurations [5]. In the
OFET devices, the conductive active channel is located very close to the
gate insulator–semiconductor interface. Almost all charge carriers have
been found within the 4–5 molecular layers [6,7]. In the case of penta-
cene, it corresponds to a thickness of about 6–8 nm. Hence, channel
formation in bottom gate transistors, is definitively related to organic
semiconductor initial growth. Considerable literature devoted to
pentacene growth on dielectric surfaces pointed out the influence
on transistor performance of dielectric roughness [8], surface energy
and hydrophobic behavior [9], dielectric permittivity [5,10,11] and
⁎ Corresponding author. Tel.: +33 4 72 18 62 32; fax: +33 4 72 18 60 90.
E-mail addresses: Maksym.Iazykov@ens-lyon.fr (M. Iazykov),
Mohsen.Erouel@ec-lyon.fr (M. Erouel), Jacques.Tardy@ec-lyon.fr (J. Tardy),
Skryshevsky@yandex.ru (V.A. Skryshevsky), Magali.Phaner@ec-lyon.fr
(M. Phaner-Goutorbe).
highest mobility has been observed for a channel thickness ranging
between 30 and 70 nm. Lower thickness may cause some device insta-
bilities whereas higher thickness leads to degraded device performance
due to increased parasitic resistance and bulk effects. In a previous
work, we reported on the stability of parylene-C/pentacene top gate
transistors [13]. Pentacene was deposited onto BCB planarized glass sub-
strate and an optimum pentacene thickness of 30 nm was also observed.
In this configuration, the channel was located on top of the pentacene
layer beneath the parylene surface. A number of previous works reported
some correlations between surface morphology of pentacene, micro-
structures and transport properties of bottom gate transistors [14–16].
It was shown that the effective mobility of the carriers decreases with
the presence of traps and grain boundaries. In so far as, a fully dense
film cannot readily be created by pentacene film growth via island
mode, the lateral extension of the islands should be the largest to limit
grain boundaries. The lateral size of the islands is then crucial for device
performance and mostly depends on the deposition process, the sub-
strate nature and the growth mode.
This article reports an AFM investigation of pentacene deposited
onto parylene-C and benzocyclobutene (BCB). The morphology of the
pentacene surface has been studied for thicknesses ranging from 15 to
60 nm. Our objective is to analyze precisely the evolution of the size of
islands during growth to find the morphology corresponding to the
optimal performance of the OFET device. Thus, a power spectral density
(PSD) analysis of the lateral size of the islands has been performed. It
demonstrates an influence of the initial pentacene growth mode on

0039-6028/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.susc.2012.09.001
 M. Iazykov et al. / Surface Science 607 (2013) 170–173
the surface morphology and reveals the presence of a particular thick-
ness of 30 nm, for which islands are the largest.
2. Materials and methods
Parylene-C and BCB were deposited on a thoroughly cleaned glass
surface. Parylene-C (DiX-C, Kishimoto Sangyo GmbH) deposition was car-
ried out on a substrate maintained at room temperature following a stan-
dard vaporization-cracking procedure. Benzocyclobutene (Cyclotene™
from Dow Chemicals) was deposited by spin coating and then by curing
for 72 h at 170 °C in air. Pentacene thin films were deposited on these
substrates by vacuum evaporation at a substrate temperature of 70 °C
and an evaporation rate of 0.2 and 0.4 Å/s. Both substrate temperature
and evaporation rate are of utmost importance for the organization of
pentacene molecules on the surface and they must be carefully controlled
for reproducible results [11].
The morphology of the pentacene thin films was studied in an
Amplitude Modulation mode (AM-AFM) using the AFM Solver P-7,
“stand alone” Smena-B (NT-MDT, Russia), with typical spring con-
stant k of 22 N/m and tip radius of 10 nm. This mode was shown to
be more appropriate than the contact mode to image soft materials
such as polymers [17], functionalized surface and biological objects
[18,19], in air.
3. Results and discussion
3.1. AFM imaging: island size toward pentacene thickness
Fig. 1 reveals that the surface morphology of pentacene consists
in islands with different shapes and structures depending on the
nature of the substrate. On parylene, all the islands present bulk-like
shape with rounded boundaries and a granular rounded structure
Fig. 1. AFM images of pentacene surface for equivalent thicknesses h= 15, 30, 40 and
60 nm, deposited on parylene-C for (a) to (d) and on BCB for (e) to (h). Scan size
5 μm × 10 μm.
171
(Fig. 1(a–d)). On BCB, the islands show sharp boundaries and a layered
pyramidal growth configuration, like what was observed in previous
works on smooth substrates [11] (Fig. 1(e–h)). For pentacene thickness
in the range 15–60 nm, the surface topology remains roughly the same.
On parylene, the peak to valley height Δz remains around 60 nm for an
image size of 5 μm×10 μm and the root mean square (RMS) roughness
slightly increases from 7 nm to 8 nm as the pentacene thickness in-
creases from 30 to 60 nm. On BCB, Δz remains around 45 nm, excepted
for the 15 nm thick layer, and the RMS roughness evolves between
4 nm and 7 nm. The exception for the 15 nm thick layer is not significant
because the peak to valley height depends also on the subjacent layers
and on the shape of the tip and the island. These statistical parameters
are commonly used to provide information on thin film topology but
they only refer to vertical deviation of the surface profile. They do not pro-
vide suitable information on the lateral distribution of the morphological
islands.
In order to establish the variation of the islands' lateral dimensions,
calculation of the island size distribution was performed. The island size
was firstly calculated using a segmentation algorithm implemented in
Gwyddion modular program for SPM data visualization and analysis
[20]. Fig. 2 presents the results in the case of thicknesses between
15 nm and 60 nm. On parylene, an average size of 0.39±0.02 μm,
0.37±0.07 μm, 0.36±0.032 μm, 0.43±0.06 μm and 0.39±0.015 μm
was obtained for respective thicknesses of 15, 20, 35, 40 and 60 nm.
The average size reaches a higher value of 0.51±0.05 μm for a thickness
of 30 nm. The same behavior was observed on BCB, with larger island
sizes of 0.66±0.06 μm, 0.59±0.04 μm, 0.72±0.01 μm, 0.64±0.04 μm
and 0.76±0.04 μm for respective thicknesses of 15, 20, 35, 40 and
60 nm. The largest average size, 0.89±0.03 μm, also occurs for a thick-
ness of 30 nm.
3.2. Power spectrum density (PSD) approach
Further improvement in grain analysis was provided by power spec-
tral density (PSD). Spectra were calculated from typical images of
10 μm × 10 μm focusing on coverage from 15 nm to 60 nm. The PSD
function provides a more complete description of the surface revealing
both vertical and lateral morphological changes. This approach based
on the decomposition of the surface profile into its spatial wavelengths
permits to compare the roughness data taken over various spatial fre-
quency ranges. Thus, the PSD spectrum contains information about
two major aspects of the surface roughness, in other words, the varia-
tions of height from an average plan, and the lateral distance over
which this variation occurs.
Studies are usually performed using the one-dimensional (1D)
power spectral density which takes into account the surface profiles
measured along the AFM fast-scan direction [21].
The 1D-PSD is sufficiently representative to describe isotropic sur-
faces such as ours [22,23]. Then, whether it is a good approximation or
not depends on the scale of the measurements. Thus, we deliberately
Fig. 2. Distribution of the island size of pentacene deposited on BCB and parylene-C. Values
were obtained by applying a segmentation algorithm (Gwyddion) on AFM images of Fig. 1.
The maximal size of the islands is obtained for a thickness of 30 nm.
172 M. Iazykov et al. / Surface Science 607 (2013) 170–173
Fig. 3. 1-D PSD spectra of the pentacene films deposited on BCB for different equivalent
thicknesses.
performed calculations on large scale images of 10 μm ×10 μm. For each
sample, measurements were made on five different AFM images repre-
sentative of five different areas of the surfaces.
The PSD function extends over a large spatial frequency bandwidth
reflecting the roughness contribution from all features of the surface
(Fig. 3). Different analytical models can be used to fit the experimental
PSD curves. We applied three different and complementary models:
the fractal analytical model (PSDfractal) [24], the ABC model (PSDABC)
[25] and the superstructure model (PSDsh) [26].
The fractal model provides information on the morphology of rough
surface, taking into account the concepts of scale and the symmetry ele-
ments. It describes the high-frequency region of PSD which follows
inverse power law decay according to the relation:
K the islands, which can be related to the size of small terraces on the top of
PSDfractal ðf ; K; vÞ ¼ ð1Þ
f vþ1
where f is the spatial frequency, K is the spectral strength and ν is the
spectral index. Thin film morphology can be quantitatively character-
ized by fractal dimension Df given by:
1 of 35 nm and changes in an evaporation and condensation mechanism
Df ¼ ð6−vÞ: ð2Þ
2 for higher thicknesses [30]. Thus, the ABC model highlights the presence
Fig. 4. AFM images of a 30 nm thick pentacene deposited (a) on parylene and (b) on BCB. Lines correspond to islands and grain sizes, τsh1 and τsh2 obtained with the superstructure
PSDsh model. Scan size 5 μm × 2.5 μm. (c) Distribution of the τsh1, grain size and τsh2 island size, calculated with large scale images (10 μm×10 μm).
The calculated fractal dimensions of experimental pentacene films Df
are close to 2.5 which corresponds to Brownian fractal structure [27].
The fractal strength was found higher on pentacene/parylene than on
pentacene/BCB, indicating a higher roughness of the parylene compared
to the BCB. The average fractal dimension of pentacene on parylene of
2.58 ±0.10 is slightly higher than those on BCB of 2.47±0.11. Under
the modified ballistic deposition model, pentacene molecules reaching
the substrate are in strong interaction with it and have a low probability
to move [28]. The small difference between the two Df values might
be significative of a higher free motion of pentacene on BCB than on
parylene. It leads to a better organization of the pentacene molecules
on the BCB than on the parylene. This is in good agreement with previ-
ous results where pentacene molecules were organized in monolayers
on BCB and multilayers on parylene [29].
The ABC-model describes all spatial frequency regions of the experi-
mental PSD curve and is represented as follows [25]:
A
PSDABC ¼
ðC¼1Þ=2 : ð3Þ
1 þ B2 f 2
In this expression, A, B and C are the functional parameters. In our
study, B and C are the relevant parameters. B determines the position of
the “knee” – transition between low-frequency plateau and sloped part
of PSD – which is related to correlation length representing the “mean
grain size”. C is the inverse slope at high spatial frequency range, which
gives the nature of the roughness and is related to different growth
mechanisms [30]. The maximum “mean grain size” was 1/B=28.5±
2.9 nm on parylene and 108.5±14.6 nm, on BCB. These low values do
not correspond to the island size measured on the AFM image, due to
the high sensitivity of the ABC model to small morphological features.
Indeed, this measurement permits to identify a subjacent structure inside
grains [29]. Values of the C parameter are in the range 2.12–3.14 for
pentacene on parylene and 1.26–2.03 for pentacene on BCB. It means
that the growth of the pentacene films on parylene starts by an evapora-
tion and condensation mechanism (C=2) and evolves to a bulk diffusion
mechanism (C=3) for layers thicker than 30 nm. As for the pentacene
on BCB, the growth begins by a viscous flow mode (Cb 2) until a thickness
 M. Iazykov et al. / Surface Science 607 (2013) 170–173
of a peculiar thickness of 30–35 nm, and associates it to a mode change in
the growth process.
Finally, the superstructure PSD model makes it possible to charac-
terize aggregates (superstructures) formed on the surface. This model
is a Gaussian function with its peak shifted to a non-zero spatial fre-
quency [20]:
h i
2 2 2 2 2 better organized layer. The ABC model highlights the presence of a pecu-
PSDsh ðf ; τ sh ; σ sh ; f sh Þ ¼ πσ sh τsh exp −π τsh ðf −f sh Þ
where τsh and σsh are mean superstructure size and height respec-
tively, and fsh is the shift of the PSD maximum. The τsh values repre-
sent lateral size measurements of features on the surface.
Fig. 4 reports parameters obtained from the superstructure model.
τsh1 and τsh2 correspond to the size of the islands and to the size
of the single grains aggregated inside the islands, respectively.
Fig. 4(a) and (b) show AFM images for a 30 nm thickness of penta-
cene on parylene and BCB, respectively. The corresponding τsh1 and
τsh2 values of Fig. 4(c) are represented by blue sticks in the upper left
of the image and morphological features – grains and islands – are
surrounded by a blue line. One can notice the good agreement between
the two parameters and the two structure sizes. These two parameters
are well-adapted to characterize the size of our structures. Fig. 4(c) pre-
sents the two parameters obtained for different equivalent thicknesses
of pentacene. From 15 to 30 nm, the size of the islands increases from
780 nm to a maximal value of 1100 nm. For thicknesses above 30 nm,
it decreases progressively to a minimum value of 596 nm. However,
the τsh2 parameter, characteristic of the grain size, remains roughly
around 300 nm, whatever the pentacene thickness. The same trend is
also observed in the case of pentacene on BCB. The superstructure size
evolves from a τsh1 value of 1.27 μm to 1.56 μm for a 30 nm thickness
and then falls linearly down to 1.03 μm. Similarly, the τsh2 parameter re-
mains around a value of 440 nm, for all thicknesses (Fig. 4(c)).
The superstructure model confirms that the islands reach a larger
width for the thickness of 30 nm on both substrates. However, it
shows that the enlargement of the islands is mostly due to an increase
of the quantity of grains composing the islands. In addition, we showed
in previous work, that for this critical thickness of 30 nm, the surface
energy reaches its minimal value corresponding to a better organization
of pentacene molecules on both substrates [29]. We also showed that
parylene/pentacene top gate transistors exhibited highest mobility
for a pentacene thickness around 30 nm [13,29]. In former papers, we
evidenced that highest device performance was clearly correlated to
large islands, optimized surface energy and very smooth growth surface
[11]. All the data, along with abundant literature in this field, demon-
strate a strong correlation between surface smoothness, grain size and
2D-growth with high performance devices. The novelty brought out in
this paper is the analysis of the island structure which shed new light
on the relationship between pentacene growth and device mobility.
Above 30 nm, the crystal organization is different (transition from or-
thorhombic thin film phase to triclinic bulk phase) and the width of
the islands decreases leading to a vertical extension. Large islands and
ordered molecule arrangement in the islands are determinant factors
to induce high mobility of the OFETs. Consequently, the optimal device
performance should be reached for the 30 nm thick pentacene layer
deposited on BCB.
4. Conclusions
An AFM study of pentacene deposited on parylene-C and BCB focusing
on thicknesses between 15 and 60 nm has been performed in order to
observe the influence of the thickness on the island size and morphology.
173
AFM images have presented different pentacene island shapes with
the substrate: small and rounded on parylene and large and pyramidal
on BCB. A detailed PSD analysis of the lateral size of the islands has
been conducted. Three different models have been used to calculate
relevant parameters. The fractal model outlines a difference between
BCB and parylene for the sticking of the pentacene molecules during
deposition. They have a lower probability to move on BCB, leading to a
ð5Þ
liar thickness of 30–35 nm, and associates it to a mode change in the
growth process, whatever the substrate. Finally, the superstructure
model confirms the presence of a specific thickness of 30 nm for
which islands are the largest on both substrates. This thickness is also
the one corresponding to the higher OFET mobilities on these systems
[10]. The superstructure model also revealed that the increase of mobil-
ity for a 30 nm thickness is not related to an increase of the grain size but
to an increase of the island size. The size evolution of the islands is not
due to an evolution of the size of the grains. It is mostly influenced by
the quantity of the grains which form the superstructures. Consequent-
ly, this study reveals that optimal device performance should be reached
for the 30 nm thick pentacene layer deposited on BCB.
References
[1] S. Ohta, T. Chuman, S. Miyaguchi, H. Satoh, T. Tanabe, Y. Okuda, M. Tsuchida, Jpn. J.
Appl. Phys. 44 (2005) 3678.
[2] A.K. Diallo, J. Tardy, F. Bessueille, Z. Zhang, N. Jaffrezic-Renault, M. Lemiti, Appl.
Phys. Lett. 94 (2009) 263302.
[3] S. De Vusser, S. Steudel, K. Myny, J. Genoe, P. Heremans, Appl. Phys. Lett. 88
(2006) 162116.
[4] E. Cantatore, T. Geuns, A. Gruijthuijsen, G. Gelinck, S. Drews, D.M. de Leeuw Dig,
in: Tech Pap. — IEEE Int. Solid-State Circuits Conf, 49, 2006, p. 273.
[5] D. Braga, G. Horowitz, Adv. Mater. 21 (2009) 1473.
[6] F. Dinelli, M. Murgia, P. Levy, M. Cavallini, F. Biscarini, D.M. de Leeuw, Phys. Rev.
Lett. 92 (2004) 116802.
[7] M. Kikuchi, M. Nakayama, K. Fujiwara, K. Ueno, T. Shimada, K. Saiki, Jpn. J. Appl.
Phys. 42 (2003) L1408.
[8] S. Steudel, S. De Vusser, S. De Jonge, D. Janssen, S. Verlaak, J. Genoe, P. Heremans,
Appl. Phys. Lett. 85 (2004) 4400.
[9] M. Yoshida, S. Uemara, T. Kodzasa, T. Kamada, M. Matsuzawa, T. Kawai, Synth.
Met. 137 (2003) 967.
[10] A.L. Deman, J. Tardy, Org. Electron. 6 (2005) 78.
[11] A.L. Deman, M. Erouel, D. Lallemand, M. Phaner-Goutorbe, J. Tardy, P. Lang, J. Non
Cryst. Solids 354 (2008) 1598.
[12] A. Mosera, H.-G. Flescha, A. Neuholda, M. Marchla, S.J. Ausserlechnera, M. Edlerb,
T. Griesserb, A. Haasec, D.M. Smilgiesd, J. Jakabovice, R. Resel, Synth. Met. 161
(2012) 2598.
[13] K. Diallo, M. Erouel, J. Tardy, E. André, J.L. Garden Appl, Phys. Lett. 91 (2007) 183508.
[14] C. Kim, A. Facchetti, T.J. Marks, Science 318 (2007) 76.
[15] M. Weis, K. Gmucova, V. Nadazdy, E. Majkova, D. Hasko, D. Tagushi, T. Manaka, M.
Iwamoto, Jpn. J. Appl. Phys. 50 (2011) 04DK03.
[16] A. Bolognesi, M. Berliocchi, M. Manenti, A.D. Carlo, P. Lugli, K. Lmimouni, C. Dufour,
IEEE Trans. Electron. Devices 51 (2004) 1997.
[17] A. Knoll, R. Margele, G. Krausch, Macromolecules 34 (12) (2001) 4159.
[18] M.H. Rouillat, V. Dugas, J.R. Martin, M. Phaner-Goutorbe, Appl. Surf. Sci. 252 (5)
(2005) 1765.
[19] D. Sicard, S. Cecioni, M. Iazykov, Y. Chevolot, S.E. Matthews, J.-P. Praly, E. Souteyrand,
A. Imberty, S. Vidal, M. Phaner-Goutorbe, Chem. Commun. 47 (2011) 9483.
[20] Gwyddion modular program for SPM data visualization. This algorithm is based on a
surface triangulation scheme. Knowing the pixel dimension, it becomes possible to
calculate the size for each structure marked by a mask area.
[21] S.J. Fang, S. Haplepete, W. Chen, C.R. Helms, H. Edwards, J. Appl. Phys. 82 (1997) 5891.
[22] A. Turak, J. Heidkamp, H. Dosch, Nanotechnology 21 (2012) 285705.
[23] E. Marx, I.J. Malik, Y.E. Strausser, T. Bristow, N. Poduje, J.C. Stover, J. Vac. Sci. Technol. B
20 (1) (2002) 31.
[24] E.L. Church, Appl. Opt. 22 (1988) 1518.
[25] J.F. Borrull, A. Duparre, E. Quesnel, Appl. Opt. 40 (2001) 2190.
[26] M. Senthilkumar, N.K. Sahoo, S. Thakur, R.B. Tokas, Appl. Surf. Sci. 252 (5) (2005)
1608.
[27] N.K. Sahoo, S. Thakur, R.B. Tokas, Thin Solid Films 503 (2006) 85.
[28] J. Yu, J.G. Amar, Phys. Rev. E 65 (2002) 060601.
[29] M. Iazykov, M. Erouel, R. Villey, E. Souteyrand, V.A. Skryshevsky, J. Tardy, M.
Phaner-Goutorbe, Funct. Mater. Lett. 5 1 (2012) 1250016 (UNSP).
[30] D.G. Stearns, P.B. Mirkarim, E. Spiller, Thin Solid Films 446 (2004) 37.