P-19

Properties of Pentacene Films Prepared by Heated Metal Mesh

Akira Heya and Naoto Matsuo

University of Hyogo, Department of Materials Science and Chemistry, 2167 Shosha, Himeji, 671-2280, Japan
Phone: +81-792-67-4909 Fax: +81-792-67-4885 e-mail: heya@eng.u-hyogo.ac.jp

Bulk-phase pentacene film and novel pentacene based organic semiconductor film were prepared by using heated metal mesh.
In this method, a heated tungsten (W) mesh set between pentacene source and substrate in vacuum chamber. Pentacene
molecules come in contact with a heated W mesh before reaching the substrate and the pentacene molecules can be obtained
the thermal energy on a heated W mesh. As the mesh temperature increased from 23 to 1200°C, the intensity ratio of bulk to
thin-film phase increased from 0 to 9.7. The decomposition reaction occurs notably above 1300°C. The decomposed precursors
were identified to be dihydropentacene, p-distrylbenzene, and 2,2’-dimethyl-1,1’-binaphthalene. These decomposed precursors
are expected as a source of large graphene sheets and graphene nanoribbons.

1. Introduction Pentacene molecules come in contact with the heated W

Organic thin-film transistors (OTFTs) are expected to be mesh before reaching the substrate. For the high mesh
applied to special applications such as flexible displays and temperature, it is expected that a pentacene-based organic
IC tags. Recently, the performance of OTFTs has improved film is formed from the decomposed pentacene precursors.
and is comparable to amorphous silicon TFTs.1) Pentacene In this study, the mesh temperature (Tmesh) dependence
films are prepared by vacuum evaporation2) and horizontal of structural properties was investigated for the formation of
physical vapor deposition.3) For a horizontal physical vapor high-bulk-phase pentacene film and novel pentacene based
deposition, a single-crystal pentacene film is obtained in a organic semiconductor film. To clarify the decomposition
quartz tube.3) It is reported that single-crystal pentacene film reaction of pentacene molecules, the decomposed pentacene
has bulk phase and it shows high mobility of 40 cm2/Vs. precursors were identified.
However, it is difficult to deposit such a film on a large
substrate. Therefore, the pentacene film with a high 2. Experimental
bulk-phase ratio is necessary to realize special applications. The HMD apparatus used in this study is schematically
In addition, carbon-based semiconductors (graphene4) illustrated in Fig. 1. A pentacene source was set in a Mo boat
and so on) are promising candidates as next-generation in a quartz tube. H2 gas (purity 99.9999%) was introduced
semiconductor materials. In particular, graphene from a nozzle with a 6 mm diameter via the quartz tube,
nanoribbons are attracting attention because of the
interesting dependence of electrical properties (metal- or
semiconductor-like characteristics) on the edge shape and
width of nanoribbons.5) Therefore, the formation
technologies for graphene nanoribbons with controlled edge
shape and ribbon width are required for device application.
If a thin film can be deposited using a precursor that
maintains its structure, a compound with a complicated
structure may be formed. In addition, the edge shape and
ribbon width could be controlled by adjusting the precursor
structure and the number of their polymerization reactions.
We propose a deposition method called hot mesh
deposition (HMD). In this method, a heated tungsten (W) Fig. 1. Schematic diagram of HMD apparatus. Pentacene
molecules come in contact with a heated W mesh before
mesh is set between a pentacene source and a substrate in
reaching a glass substrate. A pentacene-based organic film is
the hydrogen chemical transport deposition apparatus.6) formed by the decomposed pentacene precursors.

AM-FPD '13 167

 which had a diameter of 26 mm. To investigate the role of
H2, He gas (purity 99.999%) was used as a reference gas.
The distance between the Mo boat and glass substrate was
115 mm. The distance between the W mesh and glass
substrate was 50 mm. The W mesh (55×55 mm2) with a wire
diameter of 0.03 mm and 50 mesh/inch was heated by
electrical heating. The temperature of the Tmesh was
measured using a pyrometer and was set at RT, 800, 1200,
1300, or 1400 °C by controlling the applied voltage. The H2
and He flow rates were 100 and 5 sccm, respectively. The
gas pressure was 30 Pa. The deposition time was 250 s. The
heater temperature and the Mo boat were 315 °C and 400 °C,
respectively. The mass of introduced pentacene was 5 mg.
The film thickness was measured using a stylus surface
profiler and white light interferometer systems. The
structural property of the pentacene film was investigated by
X-ray diffraction (XRD) analysis and atomic force
microscopy (AFM) observation. The decomposition
temperature was obtained from optical absorption spectra.
The pentacene precursors decomposed on a heated W mesh
was identified at 300 °C in He atmosphere using the film
fabricated on a glass substrate with a Tmesh of 1400 °C by
thermal desorption by thermal desorption gas
chromatography mass spectrometry (GC/MS). The range of
the measured masses was from 10 to 650.
that the thermal energy of pentacene molecule collided to a
heated W mesh was higher than that without contact with a
heated W mesh. In general, the grain size of pentacene is
influenced by nucleation7) and surface migration of
pentacene molecule.8) It is reported that the pentacene
molecules with a high kinetic energy suppress grain growth
by the enhancement of nucleation in supersonic molecular
beam deposition.9) In the case of HMD, the decrease in grain
size can be explained by increase in thermal energy of
pentacene molecules. For the Tmesh of 1200°C, the shape of
these grains is not well known. It implies that this grain
shape relates the growth mechanism by the pentacene
molecules with high thermal energy.
The XRD patterns of pentacene films prepared in H2
atmosphere are shown in Fig. 4. The peaks due to the
thin-film and bulk phases of (00l) planes were observed in
XRD patterns of the prepared sample at lower than
1200°C.10) Above Tmesh of 1300°C, the different diffraction
peak was observed. The peak position, full width half
maximum (FWHM) and the intensity ratio of the bulk phase
to the thin-film phase (IB/IT) are shown in Fig. 5. The both
diffraction peak positions of thin-film and bulk phase were
increased with increasing the Tmesh. It is shown that the angle

3. Results and discussion

The film thickness of pentacene prepared at various
Tmesh in H2 and He atmospheres is shown in Fig. 2. The film
thickness prepared without W meth is also plotted in this
figure. For H2 atmosphere, the film thickness was decreased
from 200 to 70 nm by introducing W mesh. For Tmesh of
room temperature (RT), pentacene molecule deposited on a
W mesh. It is shown that 65% of introduced pentacene
collides with a mesh. When the W mesh was heated, the film
thickness increased because of thermal desorption of
pentacene molecules from a heated W mesh. As the Tmesh Fig. 2. Film thickness of pentacene prepared at various Tmesh
increased from 800 to 1400°C, the film thickness decreased. in H2 and He atmospheres.
It is considered that the absorption property of pentacene
molecule on substrate was decreased by increment of
substrate temperature.
The AFM images of the pentacene films prepared at
various Tmesh in H2 and He atmospheres are shown in Fig. 3.
The dendritic grains were observed in pentacene film
prepared at Tmesh of RT and without mesh. In the case of H2
atmosphere, circular grains were observed at Tmesh of 800
and 1000°C. The pentacene film prepared at 1200°C showed
mesh texture. Above 1300°C, the smooth surface was Fig. 3. AFM images of the pentacene films prepared at various
obtained. It is found that the surface morphology was Tmesh in H2 or He atmosphere. The observed area was 5 × 5
μm2.
changed by temperature of a heated W mesh. It is considered

168 AM-FPD '13

toward substrate decreased. The FWHM shows the variation
of molecular oldering.11) The FWHM of bulk phase was
slightly decreased by increasing the Tmesh. On the other hand,
the FWHM of thin-film phase was increased with Tmesh.
These phenomena are considered to molecular arrangement
from thin-film phase to bulk phase. The IB/IT was increased
by increasing the Tmesh. At a Tmesh of 1200°C, the intensity
ratio of the bulk to the thin-film phase in the (001) plane was
9.7. In general, when the free energy of the growth surface is
low, a bulk phase appears because pentacene films can grow
without interacting with the substrate. In the case of high
thermal energy, pentacene molecules can grow without
interacting with the substrate because the migration length of
pentacene molecules increased.
Fig. 4. XRD patterns of pentacene films prepared at various
Tmesh in H2 atmosphere.
Fig. 5. The (001) peak position, FWHM of peak due to
thin-film phase and bulk phase and the IB/IT as a function of
Tmesh. The values at Tmesh of 0°C show the pentacene film
prepared without W mesh.
The optical absorption spectra of pentacene films
prepared at various Tmesh are shown in Fig. 6. Absorption
peaks due to pentacene were observed in the range from 500
to 700 nm.12) It is considered that the absorption at 400 nm is
related to the tail of the absorption peak due to pentacene
and by-products produced during film formation such as
dihydropentacene at 285 nm.12) The absorption spectrum of
the pentacene film prepared at 1300 °C was different from
that at a lower temperature. The absorption peaks of
pentacene disappeared at 1300 and 1400 °C. It is difficult to
clarify the exact decomposition temperature from the optical
absorption spectra because this measurement is not sensitive
to changes in the film surface. However, it is considered that
the decomposition temperature on a heated W mesh in H2
atmosphere was approximately 1300°C. On the other hand,
no change in the spectra was observed in He atmosphere
even at 1400 °C. It is considered that the decomposition of
pentacene occurred by catalytic cracking reaction using H2
on heated W mesh and the reaction between flying
pentacene molecules and atomic hydrogens in gas phase.
Figure 7 shows the total ion chromatograph of the film
Fig. 6. Optical absorption spectra of pentacene films prepared
on glass substrates at various Tmesh. The films were deposited
by HMD in H2 (a) and He atmospheres (b).
AM-FPD '13 169

Fig. 7. Total ion chromatograph of film formed at 1400°C in
H2 atmosphere. The insert shows the identified precursors.
formed by the decomposed pentacene precursors at 1400 °C
in H2 atmosphere. The identified precursors are shown in
this figure. The peaks due to p-distrylbenzene,
2,2’-dimethyl-1,1’-binaphthalene, hydroxypentacene, and
dihydropentacenedione were observed at scan numbers of
1187-1896, 1960-1973, 2038, 2106-2125, and 2159-2170,
respectively. It is clear that precursors with the maintained
pentacene structure are generated by the decomposition of
pentacene molecules. The precursors with an O atom
(hydroxypentacene and dihydropentacenedione) were
generated by O atoms in the vacuum chamber during the
decomposition or by those in air after deposition. In addition,
low-molecular-weight compounds such as benzene and
toluene were not detected by thermal desorption GC/MS.
Finally, we discuss the possibility of graphene
formation. Under present condition, decomposed precursors
collide with another decomposed precursor 830 times.
However, the pentacene dimer was not observed by thermal
desorption GC/MS. It implies that the decomposed precursor
is not easily polymerized because dihydropentacene dose not
have dangling bonds. Therefore, the collision between
C22H12 precursors is necessary for enhancement of the
polymerization before hydrogenation reaction in the gas
phase. The graphene formation by HMD is expected because
it is reported that graphene sheets are created by Ar gas and
ethanol droplets directly in the gas phase for an
atmospheric-pressure microwave plasma reactor.13)
4. Conclusions
The influences of W mesh temperature on the structural
properties of pentacene films and decomposition reaction
were investigated. The following results were obtained.
1) The shape of crystal grains (dendritic and circular
grains) and the XRD intensity ratio of the bulk phase to
170 AM-FPD '13
the thin-film phase changed with Tmesh. This is related to
the thermal energy of pentacene molecule on growth
surface.
2) As the Tmesh was increased from RT to 1200°C, the IB/IT
was increased from 0 to 9.7 by the enhancement of the
migration of pentacene molecules on the growth surface.
The IB/IT ratio was higher than that of conventional
vacuum evaporation. The technique is expected to be a
novel deposition method for organic materials.
3) The decomposition temperature of pentacene molecules
on a heated W mesh in H2 atmosphere was
approximately 1300 °C. The decomposition is related to
hydrogen because pentacene did not decompose in He
atmosphere in spite of the same Tmesh.
4) The decomposed precursors were identified to be
dihydropentacene, p-distrylbenzene, and
2,2’-dimethyl-1,1’-binaphthalene. Method of
decomposition of pentacene molecules using a heated
W mesh and H2 can be used as a novel deposition
method for organic materials with a complicated
structure.
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