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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.
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) 170–173 171
the surface morphology and reveals the presence of a particular thick- (Fig. 1(a–d)). On BCB, the islands show sharp boundaries and a layered
ness of 30 nm, for which islands are the largest. pyramidal growth configuration, like what was observed in previous
works on smooth substrates [11] (Fig. 1(e–h)). For pentacene thickness
2. Materials and methods 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
Parylene-C and BCB were deposited on a thoroughly cleaned glass image size of 5 μm×10 μm and the root mean square (RMS) roughness
surface. Parylene-C (DiX-C, Kishimoto Sangyo GmbH) deposition was car- slightly increases from 7 nm to 8 nm as the pentacene thickness in-
ried out on a substrate maintained at room temperature following a stan- creases from 30 to 60 nm. On BCB, Δz remains around 45 nm, excepted
dard vaporization-cracking procedure. Benzocyclobutene (Cyclotene™ for the 15 nm thick layer, and the RMS roughness evolves between
from Dow Chemicals) was deposited by spin coating and then by curing 4 nm and 7 nm. The exception for the 15 nm thick layer is not significant
for 72 h at 170 °C in air. Pentacene thin films were deposited on these because the peak to valley height depends also on the subjacent layers
substrates by vacuum evaporation at a substrate temperature of 70 °C and on the shape of the tip and the island. These statistical parameters
and an evaporation rate of 0.2 and 0.4 Å/s. Both substrate temperature are commonly used to provide information on thin film topology but
and evaporation rate are of utmost importance for the organization of they only refer to vertical deviation of the surface profile. They do not pro-
pentacene molecules on the surface and they must be carefully controlled vide suitable information on the lateral distribution of the morphological
for reproducible results [11]. islands.
The morphology of the pentacene thin films was studied in an In order to establish the variation of the islands' lateral dimensions,
Amplitude Modulation mode (AM-AFM) using the AFM Solver P-7, calculation of the island size distribution was performed. The island size
“stand alone” Smena-B (NT-MDT, Russia), with typical spring con- was firstly calculated using a segmentation algorithm implemented in
stant k of 22 N/m and tip radius of 10 nm. This mode was shown to Gwyddion modular program for SPM data visualization and analysis
be more appropriate than the contact mode to image soft materials [20]. Fig. 2 presents the results in the case of thicknesses between
such as polymers [17], functionalized surface and biological objects 15 nm and 60 nm. On parylene, an average size of 0.39±0.02 μm,
[18,19], in air. 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.
3. Results and discussion 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
3.1. AFM imaging: island size toward pentacene thickness 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
Fig. 1 reveals that the surface morphology of pentacene consists 60 nm. The largest average size, 0.89±0.03 μm, also occurs for a thick-
in islands with different shapes and structures depending on the ness of 30 nm.
nature of the substrate. On parylene, all the islands present bulk-like
shape with rounded boundaries and a granular rounded structure 3.2. Power spectrum density (PSD) approach
Fig. 1. AFM images of pentacene surface for equivalent thicknesses h= 15, 30, 40 and Fig. 2. Distribution of the island size of pentacene deposited on BCB and parylene-C. Values
60 nm, deposited on parylene-C for (a) to (d) and on BCB for (e) to (h). Scan size were obtained by applying a segmentation algorithm (Gwyddion) on AFM images of Fig. 1.
5 μm × 10 μm. 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
A
performed calculations on large scale images of 10 μm ×10 μm. For each PSDABC ¼ ðC¼1Þ=2 : ð3Þ
1 þ B2 f 2
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
In this expression, A, B and C are the functional parameters. In our
reflecting the roughness contribution from all features of the surface
study, B and C are the relevant parameters. B determines the position of
(Fig. 3). Different analytical models can be used to fit the experimental
the “knee” – transition between low-frequency plateau and sloped part
PSD curves. We applied three different and complementary models:
of PSD – which is related to correlation length representing the “mean
the fractal analytical model (PSDfractal) [24], the ABC model (PSDABC)
grain size”. C is the inverse slope at high spatial frequency range, which
[25] and the superstructure model (PSDsh) [26].
gives the nature of the roughness and is related to different growth
The fractal model provides information on the morphology of rough
mechanisms [30]. The maximum “mean grain size” was 1/B=28.5±
surface, taking into account the concepts of scale and the symmetry ele-
2.9 nm on parylene and 108.5±14.6 nm, on BCB. These low values do
ments. It describes the high-frequency region of PSD which follows
not correspond to the island size measured on the AFM image, due to
inverse power law decay according to the relation:
the high sensitivity of the ABC model to small morphological features.
Indeed, this measurement permits to identify a subjacent structure inside
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 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
where f is the spatial frequency, K is the spectral strength and ν is the
that the growth of the pentacene films on parylene starts by an evapora-
spectral index. Thin film morphology can be quantitatively character-
tion and condensation mechanism (C=2) and evolves to a bulk diffusion
ized by fractal dimension Df given by:
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
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).
M. Iazykov et al. / Surface Science 607 (2013) 170–173 173
of a peculiar thickness of 30–35 nm, and associates it to a mode change in AFM images have presented different pentacene island shapes with
the growth process. the substrate: small and rounded on parylene and large and pyramidal
Finally, the superstructure PSD model makes it possible to charac- on BCB. A detailed PSD analysis of the lateral size of the islands has
terize aggregates (superstructures) formed on the surface. This model been conducted. Three different models have been used to calculate
is a Gaussian function with its peak shifted to a non-zero spatial fre- relevant parameters. The fractal model outlines a difference between
quency [20]: BCB and parylene for the sticking of the pentacene molecules during
deposition. They have a lower probability to move on BCB, leading to a
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 ð5Þ
liar thickness of 30–35 nm, and associates it to a mode change in the
growth process, whatever the substrate. Finally, the superstructure
where τsh and σsh are mean superstructure size and height respec- model confirms the presence of a specific thickness of 30 nm for
tively, and fsh is the shift of the PSD maximum. The τsh values repre-
which islands are the largest on both substrates. This thickness is also
sent lateral size measurements of features on the surface. the one corresponding to the higher OFET mobilities on these systems
Fig. 4 reports parameters obtained from the superstructure model.
[10]. The superstructure model also revealed that the increase of mobil-
τsh1 and τsh2 correspond to the size of the islands and to the size ity for a 30 nm thickness is not related to an increase of the grain size but
of the single grains aggregated inside the islands, respectively.
to an increase of the island size. The size evolution of the islands is not
Fig. 4(a) and (b) show AFM images for a 30 nm thickness of penta- due to an evolution of the size of the grains. It is mostly influenced by
cene on parylene and BCB, respectively. The corresponding τsh1 and
the quantity of the grains which form the superstructures. Consequent-
τsh2 values of Fig. 4(c) are represented by blue sticks in the upper left ly, this study reveals that optimal device performance should be reached
of the image and morphological features – grains and islands – are for the 30 nm thick pentacene layer deposited on BCB.
surrounded by a blue line. One can notice the good agreement between
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