IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 5, NO.
1, JANUARY 2006
Organic Thin-Film Transistors Using
Pentacene and SiOC Film
Teresa Oh, Member, IEEE
Abstract—Pentacene for organic thin-film transistors (OTFTs)
was deposited on the SiOC film by thermal evaporation. The
transfer characteristic of the pentacene channel as the active
layer is dependent on the chemical properties of a surface-on-gate
insulator. Hybrid-type SiOC film can have all chemical properties
from organic to inorganic properties according to the deposition
condition. Pentacene on SiOC film shows the gradient or normal
growth because of the C=C bond in SiOC film. Normal growth
of pentacene molecules increased the grain size of the surface of
pentacene on SiOC film, and the mobility of OTFTs on SiOC films
prepared with an O2 (BTMSM + O2 ) flow rate ratio of 80% is
2.19 (cm2 V ).
Index Terms—Cross link, cross-link breakage, Diels–Alder reac-
tion, organic thin-film transistor (OTFT), pentacene, SiOC film.
I. INTRODUCTION
O RGANIC materials have attracted increasing attention
in the development of semiconductor technology of
ultralarge-scale integration (ULSI) devices [1]–[4]. The or-
ganic semiconductor pentacene has attracted possible use in
back lighting and flexible display applications. Pentacene is
an organic material used in the flexible organic thin-film tran-
sistors (OTFTs), which can be fabricated at low temperatures.
The density of grain boundaries is one of the key factors to
determine the field-effect mobility. To obtain a large ON/OFF
ratio for the pentacene channel of OTFTs, the active layer
requires low density of carriers and high mobility. Therefore,
the recent reports on OTFTs have mostly focused on the
improvement of field-effect mobility using a self-assembled
monolayer (SAM). In order to reduce the density of grain
boundaries, the active-layer deposition condition should be
optimized to produce the grain size as large as possible, be-
cause the trapped charges at grain boundaries scatter the carrier
transport and reduce the mobility [5]–[11]. Many materials
are used as the SAM, such as cyanoethylpullulan (CYEPL)
[12], polymethylmethacrylate (PMMA) [13], 2-Mercapto 5-ni-
trobenzimidazolem (MNB) [14], and octadecyltrichlorosilane
(OTS) [15]. These materials generally made polycrystralline
pentacene with large grain size and high structural order after
treatment on dielectric, thus improving the mobility. SiOC
film is promising organic insulator, which can replace SiO
insulator, and the final SiOC film is classified into three types,
organic, hybrid, and inorganic properties, by a Diels–Alder
reaction [16], [17]. It is well known that a Diels–Alder reaction
is a powerful method for disconnecting a six-membered ring
Manuscript received June 13, 2005; revised July 30, 2005.
The author is with the School of Electronic and Information Engineering,
Cheongju University, Cheongju 360-764, Korea (e-mail: teresa@cju.ac.kr).
Digital Object Identifier 10.1109/TNANO.2005.858591
1536-125X/$20.00 © 2006 IEEE
23
Fig. 1. Schematic of a pentacene TFT on SiOC film.
system, as the thermal induction in organic synthetic chemistry.
The pentacene precursor is also organic material generated by
synthesis and thermolysis of a Diels–Alder adduct [18]. The
molecular crystallite of pentacene and SiOC film is limited by
the absorption rate of a carbon-related bond and results in a
thermodynamically stable crystal structure. In this study, the
pentacene as an active layer was deposited on SiOC film by
thermal evaporation for all OTFT devices. Gate electrodes and
source and drain contacts were prepared using the conducting
Au. The analysis of the deposited pentacene on the SiOC film
was done by using a field scanning electron microscope (SEM)
and – measurements. We investigated the chemical reaction
mechanism to grow pentacene on SiOC film as gate insulators.
II. EXPERIMENT
A. Preparation and Characterization of OTFTs
As the gate insulator for pentacene-channel OTFTs device,
SiOC thin film was prepared. SiOC film was prepared by an in-
ductively coupled plasma chemical vapor deposition (ICPCVD)
on p-type Si substrate. SiOC film was deposited according to
the various flow rate ratios [16], [17]. The gate dielectric thick-
ness of the SiOC film is about 150 nm. Pentacene was deposited
on SiOC film, as shown in Fig. 1, and the electrodes of the
source, drain, and gate were made by thermally evaporating gold
through a shadow mask. Pentacene was used as a source ma-
terial for the channel of the TFT device. The substrates were
held at 80 C and the pentacene was deposited at 0.1 0.3 nm/s,
with a final thickness of 50 nm. The thickness of the pentacene
was taken on the basis of a thickness monitor during the de-
position. The base pressure was 10 torr in each exper-
iment. The surface of the films was measured using the field
SEM (JEOL, JSM-6700F). After fabrication of the OTFTs and
the ohmic contact devices, the – characteristics were mea-
sured using a semiconductor parameter analyzer HP4155B at
room temperature.
B. Chemical Reaction of Pentacene on Gate Insulator
The electrical characteristics of pentacene thin films are
related to the growth of grains according to the properties of
the gate insulator. It is known that pentacene grows as terraced
24
Fig. 2. Process of pentacene growth during the deposition. (a) Pentacene
molecule. (b) Nucleophilic reaction. (c) Diels–Alder reaction. (d) Perpendicular
growth of pentacene. (e) Pentacene active layer on gate insulator.
dendritic grains on hydrophobic gate insulator, which is aided
for perpendicular growth of pentacene. Fig. 2 shows the process
of the pentacene growth on the gate insulator. The pentacene
C H molecule is small-molecule aromatic hydrocarbon
with five benzene rings fused in a straight line, as shown in
Fig. 2(a). The terminal bond of pentacene C H molecule
of the Fig. 2(b) consists of the C C bond, which is easily taken
as a nucleophilic attack near the gate insulator by plasma-en-
hanced thermal energy, thus resulting in a Diels–Alder reaction
due to the molecular attraction at the gate insulator’s surface.
The terminal bond of pentacene is divided into two groups,
diene and dienophile, as the result of a Diels–Alder reaction
as shown in Fig. 2(d). Fig. 2(e) shows a pentacene active layer
formed perpendicularly on the insulator.
III. RESULTS AND DISCUSSION
Fig. 3 shows the chemical reaction mechanism of SiOC films
in accordance with the increase of O BTMSM O flow
rate ratio. SiOC film has the various properties by nucleophilic
reaction from the substitution reaction of unimolecular S
to substitution reaction of a bimolecular S mechanism
according to the O BTMSM O flow rate ratio. The
chemical structure of SiOC film transformed from a cross-link
breakage structure to a cross-link structure is also defined by the
predominant reaction among the S and S mechanisms.
In the case of the predominant S mechanism, the BTMSM
IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 5, NO. 1, JANUARY 2006
Fig. 3. Chemical mechanism of SiOC film in accordance with the increase of
O =(BTMSM + O ) flow rate ratio.
molecule is enough to fully dissociate in the O BTMSM
plasma state; therefore, there exists a large number of alkyl
group and carbocations which are united with oxygen at the
second transition state. On the other hand, in the condition
of the predominant S mechanism, carbanions formed by
the fully dissociated BTMSM become organometallic carbon
because of the attractive force of the electron donation from
Si as an electron-rich atom. In the middle range between the
S and S mechanisms, SiOC film shows a strong chemical
shift due to a Diels–Alder reaction. A Diels–Alder reaction
as one of the S mechanism needs the carbon double bond
like the C C and C O bonds as dienophile, but the carbon
double bonds are the only functional group produced from the
union of oxygen and carbocation, which is obtained from the
dissociation of alkyl group of BTMSM gas by the plasma-en-
hanced S mechanism. The chemical shift is determined by
the changing of the C H bond strength, which results from the
resonance and inductive effect [16]. The C H bond of C C
bonds condense due to the dominant resonance effect, but the
C H bond of the C C bond elongates because of the result
from the nucleophilic attack of C C bond due to dominant
inductive effect. The condensation of the C H bond causes the
cross-link breakage structure with pores in the film because of
steric hindrance due to the repulsive force between the alkyl
groups. These properties of the SiOC film affect the growth of
pentacene in accordance with the O BTMSM O flow
rate ratio. The grain size depends on the chemical properties
of the surface as one of the important factors to define the
performance of OTFTs, and the large grain size increases the
field-effect mobility of pentacene-based OTFTs.
Fig. 4 shows the SEM images of the pentacene surface in
SiOC films prepared with an O BTMSM O flow rate ratio
of 35%, 60%, 70%, 75%, and 80%, respectively. Fig. 4(a) is the
SEM image of large grains on SiOC film, which has the cross-
link breakage structure produced by a dominant S mecha-
nism, as shown in Fig. 3. SiOC film with an O BTMSM O
flow rate ratio of 35% has strong hydrophobic properties. It
is known that the grain size increases on dielectric with hy-
drophobic properties, as shown in Fig. 4(a) [14]. Fig. 4(b) and
OH: OTFTs USING PENTACENE AND SiOC FILM
Fig. 4. SEM images of pentacene surface films on SiOC prepared with O =(BTMSM + O ) flow rate ratios of: (a) 35%, (b) 60%, (c) 70%, (d) 75%, and (e) 80%.
(c) shows the SEM images with small grains at the pentacene’s
surface grown on SiOC film, which resulted from a nucleophilic
reaction of an inferior S mechanism. SiOC films with an
O BTMSM O flow rate ratio of 60% and 70% are sam-
ples at the region of the chemical shift due to a Diels–Alder
reaction, as shown in Fig. 3. The grain size on SiOC film of
70% is smaller than that on SiOC film of 60%. Fig. 4(b) and (c)
shows two kinds of grain boundary types. One is hole-type, and
the other is solid-line-type. SiOC film of 60% of Fig. 4(b) has
many hole-types due to the nucleophilic reaction of the relative
dominant S mechanism, and SiOC film of 70% of Fig. 4(c)
has a lot of solid line-type due to the nucleophilic reaction of
the relatively dominant S mechanism. Both of these grain
boundaries prevent the carrier transfer and reduce the mobility.
Fig. 4(d) shows the SEM image of pentacene’s surface grown on
SiOC film with an O BTMSM O flow rate ratio of 75%,
which was produced by the cross-link structure by S mecha-
25
nism due to strong inductive effect, as shown in Fig. 3. The SEM
image only shows a few grains of the hole-type, so we can know
that there are different nucleophilic reactions between the S
and S mechanisms. In addition, Fig. 4(e) shows the SEM
image of large grains on SiOC film with an O BTMSM O
flow rate ratio of 80%, because the inductive effect increases
abruptly because of the nucleophilic reaction of organometallic
carbon. The Si–O–C cross-link structure of SiOC film decreases
the density of the grain boundary and the grain size increases
due to the weakened boundary condition. Consequently, it could
be said that the grain size increases in the range of a dominant
S or S mechanism and decreases by the resonance-induc-
tive effect in the middle range of the S and S mechanisms.
In particular, SiOC film due to the organometallic carbon reac-
tion in the S mechanism improves dramatically the density
of the grain boundary and increases the mobility of pentacene
as the active layer.
26 IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 5, NO. 1, JANUARY 2006

Fig. 5. I 0V curves according to the gate voltage increase at OTFTs on SiOC films prepared with O =(BTMSM + O ) flow rate ratios of: (a) 35%, (b) 75%,
and (c) 80%.

Fig. 6. Transfer characteristics of pentacene TFTs on SiOC films prepared with O =(BTMSM + O ) flow rate ratios of 35%, 75%, and 80%. (a) Drain current
as a function of the gate voltage. (b) Square root of drain current as a function of the gate voltage.

Fig. 5 shows the electrical characteristic of pentacene TFTs ticular, the drain current of pentacene TFTs on SiOC films pre-
on SiOC films with various properties ( curves). The pared with an 80% ratio increases dramatically in spite of the
field-effect transistor (FET) characteristics of pentacene TFTs low negative gate electrode bias and rapidly reaches the satura-
on SiOC films prepared with O BTMSM O flow rate ra- tion mode.
tios of 35%, 75%, and 80% show good saturation behavior, but Fig. 6(a) shows the curves of pentacene TFTs on
that of the samples on SiOC films prepared with the ratios of SiOC films prepared with O BTMSM O flow rate ratios
60% and 70% do not show the electrical characteristic. In par- of 35% and 75% at V and 80% at V.
OH: OTFTs USING PENTACENE AND SiOC FILM 27

Fig. 7. Correlation between pentacene growth and the mobility of pentacene TFTs on SiOC film.

As shown in Fig. 6(a), the transfer characteristic of pentacene

TFTs on SiOC films prepared with an 80% ratio is superior
to those of other samples. Fig. 6(b) is the square root of drain
current as a function of the gate voltage. The channel length
is 0.25 mm and the channel width is 1.2 mm. The mobilities
of samples with ratios of 35%, 75%, and 80% are 0.69, 0.57,
and 2.19 cm V , respectively. The mobility of pentacene
TFTs on SiOC films prepared with an O BTMSM O
flow rate ratio of 80% is better than any others. SiOC films pre-
pared with an O BTMSM O flow rate ratio of 80% has
a cross-link structure with low surface energy, which is made
by the organometallic carbon reaction. Therefore, the grain size
increased during the growth of pentacene and improved the elec-
trical properties such as mobility and ON/OFF current ratio.
Fig. 7 shows the correlation between pentacene growth and
the mobility of a pentacene TFT on SiOC film. In Fig. 7(a), the Fig. 8. Chemical mechanism about the grain generation and gradient growth
of pentacene on SiOC film with a cross-link breakage structure.
electrical characteristic of a pentacene TFT on SiOC film pre-
pared with O BTMSM O flow rate ratios of 60% and 70%
is not good because of small grains, as shown in Fig. 4(b) and Fig. 8 shows the chemical mechanism regarding the grain
(c). SiOC film has two kinds of different properties according to generation and gradient growth of pentacene on SiOC film
the peculiar phenomenon of the C-H bond, and the final SiOC with a cross-link breakage structure. The cross-link breakage
film shows the cross-link breakage structure or cross-link struc- structure of SiOC film depends on the alkyl group and strong
ture by the S and S mechanism [16], [17]. Fig. 7(b) shows C C double bond. A C C double bond in SiOC film with a
the schematic diagram for perpendicular growth of pentacene on cross-link breakage structure prevents pentacene from growing
SiOC films with the cross-link breakage structure or cross-link normal to the surface on SiOC film and induces a Diels–Alder
structure. Normal growth of pentacene increases the mobility reaction. Therefore, two double bonds at the terminal of the
due to the high structural order. On the other hand, Fig. 7(c) pentacene molecule become one strong double bond resulting
shows the gradient growth of pentacene on SiOC film. The gra- from a Diels–Alder reaction, and the pentacene molecule
dient growth increase the density of grain boundary, thus re- forms into a declining growth. Therefore, the hole-type grain is
ducing the mobility. formed as shown in Fig. 4(b)–(d).
28 IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 5, NO. 1, JANUARY 2006

IV. CONCLUSION

OTFTs using pentacene on SiOC film were investigated using

SEM. Pentacene growth depends on the chemical properties of
SiOC film. SiOC film originates from the mixed results of the
S and S mechanisms, and, as a result, SiOC film presents
various properties from organic to inorganic. The gradient
growth of pentacene causes the grain size to decrease, thus
reduceing the mobility, because of carrier transport depletion
by the repulsive or attractive force between terminal molecules
of pentacene on the surface of the SiOC film. SiOC film with a
cross-link structure made by the organometallic carbon reaction
of the dominant S mechanism induces perpendicular growth
of pentacene and increases the grain size, and the transfer
characteristic is also superior to any other samples.

Fig. 9. Chemical mechanism about the grain generation and gradient growth
of pentacene on SiOC film with a cross-link structure.
Fig. 9 shows the chemical mechanism about the grain gen-
eration and gradient growth of a pentacene on SiOC film with
a cross-link structure. The proton’s donor of SiOC film by the
dominant S mechanism accepts electrons from the C C
double bond of the pentacene molecule, and then the C C
double bond breaks due to the decrease in the electron den-
sity. Therefore, the strong interaction between SiOC film and
pentacene molecule by dominant the S mechanism need to
be classified from the repulsive force between these molecules
by a Diels–Alder reaction, as shown in Fig. 8. Therefore, the
solid line-type of grain as previously shown in Fig. 4(b) and
(c) is formed. Fig. 9(b) shows the normal growth of pentacene
on SiOC film with a cross-link structure by a balanced nu-
cleophilic reaction at the terminal of the pentacene molecule.
Because the SiOC film becomes a cross-link structure as weak
boundary condition (WBC) with the lowest surface energy, the
carbocation generated from the S mechanism improves the
WBC on the surface by high electron negative oxygen and the
attack of electron-rich Si generated from the S mechanism.
The hole current of the pentacene0channel OTFT device en-
hanced on the surface of SiOC film consisted of carbon with an
electron-deficient group, and the mobility was also increased,
as shown in Fig. 7.
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pp. 595–598, 2004. munication engineering from the Cheju National
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University, Changwon, Korea. She is currently a Professor with the School
of Electronic and Information Engineering, Cheongju University, Cheongju,
Korea. Her research interests include silicon interconnection technology
associated with organic semiconductor device materials and flexible-substrate
technology for an electric paper application.