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Novel Method for Polymer Thin Film Preparation: Spray Deposition of Highly Diluted Polymer

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2002 Jpn. J. Appl. Phys. 41 L70

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Jpn. J. Appl. Phys. Vol. 41 (2002) pp. L 70–L 72
Part 2, No. 1A/B, 15 January 2002

2002
c The Japan Society of Applied Physics

Novel Method for Polymer Thin Film Preparation:

Spray Deposition of Highly Diluted Polymer Solutions
Katsuhiko F UJITA∗ , Takamasa I SHIKAWA and Tetsuo T SUTSUI
Department of Applied Science for Electronics and Materials, Graduate School of Engineering Sciences, Kyushu University,
Kasuga, Fukuoka 816-8580, Japan
(Received September 25, 2001; accepted for publication November 22, 2001)

A spray deposition method is proposed as a novel way to prepare organic thin films. In this method, a highly diluted solution
of a functional organic material, such as a π -conjugated polymer, is nebulized into air and concentrated under a controlled
evaporation condition. The resulting aerosol is transported by a carrier gas and deposited onto a solid substrate. We successfully
prepared a thin film of a poly- p-phenylenevinylene derivative from a highly diluted solution at the concentration of 10−4 wt%
and fabricated an electroluminescent device exhibiting surface emission. [DOI: 10.1143/JJAP.41.L70]
KEYWORDS: spray deposition, organic semiconductor, polymer thin film, organic light-emitting diode, π -conjugated polymer

Organic semiconductors are currently extending the poten-
tial of optoelectronics rapidly with applied to light-emitting
devices,1, 2) thin film transistors3) and solar cells.4) A promi-
nent feature of organic semiconductors is the wide variety
of molecular structures based on sophisticated chemical syn-
thesis. In particular π -conjugated polymers are expected to
have broad applicability due to the durability in addition to
the potential for various molecular designs to tune the opto-
electronic properties. They are generally incorporated into the
devices as amorphous thin films, which are prepared by var-
ious methods such as dip-coating, ink-jet printing and spin-
casting. Those methods require a certain extent of solubility
in a volatile solvent for the materials; for example, a con-
centration of around 1 wt% is needed for the spin-casting
method. Although many synthetic chemists have made great
efforts to improve the solubility of various macromolecules
having promising backbone structures,5) a significant number
of them might have been left without investigation of their op-
toelectronic properties simply because they could not be fab-
ricated into thin films. If the requirement of the material con-
centration can be alleviated by two or three orders of wt%, the
organic semiconductors could provide a much wider range of
optoelectronic properties.
We propose a novel method of preparing organic thin films
from a highly diluted solution. Figure 1 shows a schematic
1st chamber 2nd chamber
N2 gas
x-y positioner
heater
nebulizer nozzle
sample
glass substrate
solution
ceramic heater
Fig. 1. Schematic illustration of the spray deposition apparatus.
∗ E-mail
address: katsuf@asem.kyushu-u.ac.jp
illustration of the apparatus used for the method, which em-
ploys spray deposition. The solution is nebulized into air
and made into an aerosol with the particle size of around
10 µm. The aerosol is transported by nitrogen carrier gas from
the first chamber to a nozzle facing a substrate in the sec-
ond chamber. During the transportation, the solution particles
shrink with the evaporation of the solvent. The evaporation
rate can be varied by controlling the temperature of the system
and the spraying rate of the solution. The substrate is held on
a ceramic heater with a thermocouple settled on a computer-
controlled x-y positioner stage. The particles containing the
appropriate amount of the solvent are deposited onto the sub-
strate which is moved at a speed of 1–10 mm/min by the po-
sitioner while keeping the distance from the nozzle constant.
In the present study, one of the most popular π -
conjugated polymers, poly (2-methoxy-5-(2 -ethylhexoxy)-
1,4-phenylenevinylene) (MEH-PPV), was chosen for the
sample and was dissolved in tetrahydrofuran (THF) at the
concentration of 1 × 10−4 wt%. The sample solution was neb-
ulized at the rate of 15 ml/min. The temperature of the first
chamber was set at 40◦ C and that of the substrate was set at
60◦ C. After deposition for 20 min, a homogeneous and con-
tinuous thin film was obtained on a chemically etched glass
substrate (Fig. 2(a)). The atomic force microscopy (AFM)
image of the obtained PPV film taken with Nanopics 1000
(Seiko Instrument) shows a relatively flat surface with a mean
surface roughness of 16 nm (Fig. 2(b)). The thickness of the
film was determined to be 250 nm from another AFM mea-
surement after etching with the AFM tip. The surface rough-
ness of the film and the amount of adhering PPV are strongly
affected by the temperature of the first chamber and the sub-
strate. For example, the surface roughness was more than
30 nm and the transmittance at the wavelength around the ab-
sorption band of the PPV was 30% lower when the tempera-
tures of the first chamber and the substrate were set at 60◦ C
and 40◦ C, respectively, with the other conditions kept con-
stant. This indicates that too-rapid evaporation of the solvent
from the aerosol particles causes the solidification of the so-
lute and, therefore, a rough surface and low adhesion rate.
Under appropriate conditions, some amount of solvent may
remain in the aerosol particles when they adhere on the sub-
strate.
Two types of the MEH-PPV films were prepared under
the above-mentioned conditions on a chemically etched hy-

L 70
 Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 2, No. 1A/B
(a)
100
(b)
Ra 16.4 nm
max 262 nm
5 m
Fig. 2. (a) Micrograph and (b) AFM image of MEH-PPV film prepared by
spray deposition.
drophilic glass substrate and a hydrophobic one treated with
hexamethyldisilazane vapor. The morphology of the two films
observed by AFM was almost identical. If the solvent re-
mained in the aerosol particles sufficiently long to wet the
surface and spread on it, the morphology would be strongly
affected by the surface free energy of the substrate. A film
prepared on a hydrophilic substrate under a slower evapora-
tion condition with the temperature of the first chamber set
at 30◦ C exhibited a noncontinuous islet structure. Under the
appropriate conditions, the remaining solvent would be va-
porized rapidly before the solution spread on the surface. In
order to obtain a continuous smooth film it is suggested that
the amount of solvent contained in the particles must be con-
trolled carefully.
The MEH-PPV films were prepared by the spray deposition
method on indium tin oxide (ITO) transparent electrodes un-
der various conditions. A buffer layer of LiF and an Al cath-
ode were deposited on the polymer films in a vacuum depo-
sition apparatus to fabricate electroluminescent (EL) devices
as illustrated schematically in Fig. 3(a). The device prepared
K. F UJITA et al. L 71
(a)
Al (80 nm)
LiF (0/5 nm)
MEH-PPV (250 nm)
ITO
m
(b)
Fig. 3. (a) Schematic illustration of the prepared EL device structure. (b)
Photograph of the EL device driven at 20 V.
in the above-mentioned condition for the smooth PPV film
showed homogeneous surface emission throughout the entire
device area of 2 mm × 2 mm at the driving voltage of 20 V
(Fig. 3(b)). However, those prepared under other conditions
for the relatively rough films did not emit at all although they
showed similar electric properties with the emitting device.
Figure 4 shows the luminance (L)-applied voltage (V ) and the
L-urrent density (J ) properties of the EL device shown in Fig.
3(b). The turn on voltage and the maximum luminance were
18 V and 3.5 cd/m2 , respectively. These properties were not
as good as those of the reported EL devices fabricated with
spin-cast MEH-PPV films6) since the thickness of the films
obtained using the spray deposition method has not been op-
timized for EL applications yet. It is thus proved that spray
deposition can be used to realize an organic semiconductor
thin film sufficiently homogeneous and durable for applica-
tion to an actual driving device.
In summary, it is found that a novel method of preparing
organic thin films, spray deposition, can be used to realize
an organic semiconductor film applicable to a light-emitting
L 72 Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 2, No. 1A/B K. F UJITA et al.

3.5 diode, using a highly diluted polymer solution with the con-
(a) centration of 10−4 wt%. This method will be a powerful tool
Luminance (cd/m2) 3
for optoelectronic studies of materials of very low solubility
2.5
or pyrolytic organic materials.
2
1.5
1) C. W. Tang and S. A. VanSlyke: Appl. Phys. Lett. 51 (1987) 913.
1 2) C. Adachi, S. Tokito, T. Tsutsui and S. Saito: Jpn. J. Appl. Phys. 27 (1988)
L269.
0.5
3) H. Sirringhaus, N. Tessler and R. H. Friend: Science 280 (1998) 1741.
0 4) N. S. Sariciftci, D. Braun, C. Zhang, V. Srdanov, A. J. Heeger, G. Strucky
0 5 10 15 20 25 30 35 40 and F. Wudl: Appl. Phys. Lett. 62 (1993) 585.
5) for example, S. Tash, A. Niko, G. Leising and U. Scherf: Appl. Phys.
Voltage (V)
Lett. 68 (1996) 1090.
6) D. Braun and A. J. Heeger: Appl. Phys. Lett. 58 (1991) 1982.
10
Luminance (cd/m2)

(b)
1

0.1

0.01
0 1 2 3
10 10 10 10
2
Current density (mA/cm )
Fig. 4. (a) Luminance–voltage and (b) luminance–current density charac-
teristics of the EL device prepared by spray deposition.