Trap elimination and injection switching at organic field effect transistor by

inserting an alkane (C44H90) layer

Satoshi Ogawa, Yasuo Kimura, Michio Niwano, and Hisao Ishii

Citation: Appl. Phys. Lett. 90, 033504 (2007); doi: 10.1063/1.2431713

View online: http://dx.doi.org/10.1063/1.2431713
View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v90/i3
Published by the American Institute of Physics.

Related Articles
Physical understanding of negative bias temperature instability below room temperature
J. Appl. Phys. 112, 104514 (2012)
Lg=60nm recessed In0.7Ga0.3As metal-oxide-semiconductor field-effect transistors with Al2O3 insulator
Appl. Phys. Lett. 101, 223507 (2012)
The mechanisms of random trap fluctuation in metal oxide semiconductor field effect transistors
Appl. Phys. Lett. 101, 223505 (2012)
Solution processable carbon nanotube network thin-film transistors operated in electrolytic solutions at various
pH
Appl. Phys. Lett. 101, 223101 (2012)
The suppressed negative bias illumination-induced instability in In-Ga-Zn–O thin film transistors with fringe field
structure
Appl. Phys. Lett. 101, 223502 (2012)

Additional information on Appl. Phys. Lett.

Journal Homepage: http://apl.aip.org/
Journal Information: http://apl.aip.org/about/about_the_journal
Top downloads: http://apl.aip.org/features/most_downloaded
Information for Authors: http://apl.aip.org/authors

Downloaded 29 Nov 2012 to 202.3.77.183. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
 APPLIED PHYSICS LETTERS 90, 033504 共2007兲

Trap elimination and injection switching at organic field effect transistor

by inserting an alkane „C44H90… layer
Satoshi Ogawa, Yasuo Kimura, and Michio Niwano
Research Institute of Electrical Communication (RIEC), Tohoku University, 2-1-1 Katahira, Aoba-ku,
Sendai 980-8577, Japan and Core Research for Evolutional Science and Technology (CREST),
Japan Science and Technology Agency (JST) 4-1-8 Hon-cho, Kawaguchi 332-0012, Japan
Hisao Ishiia兲
Center for Frontier Science, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba-shi,
Chiba 263-8522, Japan
共Received 6 September 2006; accepted 10 December 2006; published online 17 January 2007兲
Recently, it was proposed in the literature that the electron trap on a hydroxyl-containing dielectric
interface of an organic field effect transistor 共OFET兲 hinders its n type operation. The authors
fabricated pentacene and fullerene OFETs with a hydroxyl-free insulating material, a long-chain
alkane, i.e., tetratetracontate 共TTC兲, C44H90 layer coated on the SiO2 dielectric layer. The
displacement current measurements clearly demonstrated that the electron trap of the SiO2 surface
is suppressed by the TTC layer. For a pentacene FET with an Al electrode and SiO2 dielectric layer,
a p type operation was observed, while the operation mode was switched to the n type by the
insertion of TTC on the SiO2 interface. By simple patterning of the TTC layer to produce a bipolar
injection, the authors fabricated an ambipolar pentacene FET with a single kind of metal electrode.
Thus TTC is a good material for the surface modification of a dielectric layer in OFETs. © 2007
American Institute of Physics. 关DOI: 10.1063/1.2431713兴

Recently, the ambipolar operation of organic field effect
transitors 共OFETs兲 has attracted much attention in relation to
light-emitting transistors and a complementary metal-oxide
semiconductor logic circuit.1–4 In this operation mode, the
charges that accumulated at the channel can be switched be-
tween the hole and electron by changing the polarity of the
gate voltage.
Two mechanisms are proposed for explaining the ambi-
polar operation. One is the control of the local Fermi level in
the organic/dielectric interface region as in the case of inor-
ganic semiconductors; the accumulation, depletion, and in-
version of the majority carriers are induced by the change in
the gate bias. The other is the charge injection from the
source and drain electrodes into the organic semiconducting
layer;5 electron injection and hole injection can be switched
by the gate voltage. Although an ambipolar operation is re-
alized for various types of OFETs mainly due to the latter
model,1–4 understanding of the operation mechanism is not
well established.
Very recently, it was reported that the remaining OH
group at the dielectric layer works as an electron trap.4 This
trap effect disturbs the n-type operation of the ambipolar
OFET, especially in the case of the SiO2 dielectric layer
which has been widely used for fabricating the OFETs.
Therefore, the above two models should be examined using
the OH-free dielectric surface. In addition, not only the mea-
surement of the transfer characteristics of the OFET but also
the complimentary method to investigate the charge carriers
accumulated in the channel is also necessary using another
electric measurement.
In this study, a displacement current measurement
共DCM兲 method was performed to explore the mechanism of
the ambipolar operation. We reported the advantages of this
a兲
Electronic mail: ishii130@faculty.chiba-u.jp
technique to investigate the behavior of carriers in the
OFETs.6,7 In order to suppress the proposed trap effect of the
SiO2 surface, a hydroxyl-free material, a long chain alkane,
tetratetracontane 共TTC兲 共C44H90兲 was deposited on the sur-
face. This molecule is well known to form a well-ordered
film,8 and the insertion into an organic/metal interface in-
duces an improvement of the carrier injection properties.9
We revealed that the TTC layer is effective for suppress-
ing the electron trap effect of the SiO2 layer. For the exami-
nation of the ambipolar operation, we investigated the pen-
tacene FET with an aluminum electrode. We found that the
electron and hole injections occur with and without the TTC
layer, respectively. By patterning the TTC layer to combine
both injection modes, we fabricated an ambipolar pentacene
FET with a single kind of metal electrode. The observed
ambipolar operation was discussed on the basis of these two
models.
The structure of the FET fabricated in this study was the
top contact type. A p-type Si共100兲 wafer with resistances
⬍0.01 ⍀ cm was thermally oxidized and used as the sub-
strate of the FET structures. The thickness of the oxide layer
was approximately 100 nm. Pentacene and fullerene 共WAKO
Pure Chemical Industries, Ltd.兲 共99.9% purity兲 were twice
purified by vacuum sublimation. The organic material
共100 nm thick兲 was deposited on the SiO2 substrate, and then
the source and drain electrodes 共Au or Al兲 were evaporated.
The fabricated FETs were quickly transferred to a measure-
ment chamber through a glove box without being exposed to
air. The working pressure during the measurements was on
the order of 10−4 Pa. The DCM measurements were per-
formed with HP4140B by applying a ramp voltage to the
gate electrode with the ramp rate of 0.1 V / s.
Figure 1 shows the DCM curves of the fullerene FETs
with and without inserting a TTC layer 共30 nm thick兲 be-
tween the C60 and SiO2 layers. For the DCM, the source and

0003-6951/2007/90共3兲/033504/3/$23.00 90, 033504-1 © 2007 American Institute of Physics

Downloaded 29 Nov 2012 to 202.3.77.183. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
033504-2 Ogawa et al.
FIG. 1. 关共a兲 and 共b兲兴 Schematic diagrams of the device structures of C60 FET
with and without TTC layer, respectively. 共c兲 DCM results of C60 FET 共gray
circles兲 and C60 FET with inserted TTC layer 共black circles兲. The direction
of the voltage scan is indicated by the arrows. The TTC insertion drastically
improves the horizontal asymmetry, indicating the suppression of the elec-
tron trap on the SiO2 surface.
drain electrodes were grounded and a triangular voltage
wave was applied to the gate electrode. The current through
the device, which is basically proportional to the effective
capacitance of the device Ceff, was measured as a function of
the gate voltage. The details of the DCM were described
elsewhere.6,7,9,10 In the first quadrant of the curve, the dis-
placement current was increased with the increasing gate
voltage. This is due to the electron accumulation current;
during the increase in the gate voltage, electrons injected
from the source and drain electrodes are accumulated in the
device. During the initial stage of the injection, the area of
the charge sheet is formed only under the source and drain.
While the charge sheet is growing at the dielectric interface,
the extension of the area of the charge sheet increases the
Ceff, inducing the peak structure around the shoulder due to
dCeff / dt term.10 After the completion of the area extension,
the Ceff becomes equal to that of the SiO2 layer, leading to a
constant current. In the fourth quadrant, an electron dis-
charge current during the decrease in the gate voltage is ob-
served. In the third and second quadrants, no additional cur-
rent due to hole injection was observed.
In the DCM curve of the C60 FET without the TTC layer,
the current is horizontally asymmetric. The number of accu-
mulated electrons estimated from the numerical integration
of the current for the upper hatched area is much greater than
that of the discharged ones from that of the lower hatched
area. The difference corresponds to the amount of the elec-
trons trapped in the device. The density of the electrons
trapped at the SiO2 interface is approximately 1.5
⫻ 1013 e / cm2. In contrast, the curve becomes almost sym-
metric for the FET with the TTC layer. This result clearly
demonstrates that the coverage of the SiO2 surface with the
TTC layer suppresses the traps on the dielectric surface as
proposed in Ref. 4. The observed trap is not due to the C60
bulk region because the deposition of C60 was performed in
the same batch to fabricate the devices with and without the
TTC.
Next, the effect of the TTC layer on the pentacene OFET
with the Al electrodes was examined. Bipolar injection into
Downloaded 29 Nov 2012 to 202.3.77.183. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Appl. Phys. Lett. 90, 033504 共2007兲
FIG. 2. 共a兲 DCM wave form of pentacene FET with no TTC layer 共solid
lines兲 and 30 nm thick TTC layer over the dielectric surface. By inserting
the TTC layer, the hole injection is switched to electron injection. 共b兲 DCM
curve of pentacene FET in which a bare and TTC-covered SiO2 surface
areas coexist under the source and drain. Both the hole and electron injec-
tion properties are observed, indicating an ambipolar mode.
pentacene layer can be expected because the work function
of Al 关4.28 eV 共Ref. 11兲兴 is between those of the cathode and
anode metals. Figure 2共a兲 shows the DCM curves of penta-
cene FET without and with the 30 nm thick TTC layer. In the
case without the TTC layer, the current increases at the nega-
tive gate voltage, indicating the hole injection. This is a typi-
cal result of the p-type behavior. In the case with the TTC
layer, the current increases on the positive side, indicating
the electron injection from the source and drain. This result
indicates that the insertion of the TTC layer at the dielectric
surface can induce the switching of the injection properties at
the source and drain electrodes. At the present time, the rea-
son for the injection switching is not clear, but the change in
the morphology of the pentacene film and/or the change in
the voltage profile at the pentacene/electrode interface due to
the suppression of the trap at SiO2 surface may be related to
this phenomenon. A further study is currently in progress.
The observed injection switching can be applied to real-
ize the ambipolar operation by simple patterning of the TTC
layer. By using a mask, part of the SiO2 surface was covered
by the TTC layer. Thus, under the source and drain elec-
trodes, the Al/pentacene/SiO2 and Al/pentacene/TTC/SiO2
structures coexist. Figure 2共b兲 shows the DCM of the device
with the partial insertion of the TTC. We observed an in-
crease in the displacement current on both the positive and
negative sides, clearly demonstrating the bipolar injection
into the pentacene layer. Figure 3 shows the transfer proper-
ties of this device. It worked in the ambipolar mode; the
033504-3 Ogawa et al.
FIG. 3. Transfer characteristics of ambipolar pentacene field effect transis-
tors with partial insertion of TTC. 共a兲 p-channel region of the gate bias,
Vth = −6.2 V, VSD = −20 V, ␮h = 4.7⫻ 10−4 cm2 / V s. 共b兲 n-channel region of
the gate bias, Vth = 11.1 V, VSD = + 20 V, ␮h = 1.7⫻ 10−5 cm2 / V s.
operation mode is switched between the p type and n type
depending on the gate polarity. The nominal mobilities
estimated from the saturation current are ␮h = 4.7
⫻ 10−4 cm2 / V s and ␮e = 1.7⫻ 10−5 cm2 / V s. The value of
␮h is less than that of the conventional values of the hole
mobility of the pentacene FET. This is probably due to the
high contact resistance at the Al/pentacene interface. This
ambipolar operation is due to bipolar injection from the elec-
trodes by partial insertion of the TTC. This method is very
simple and does not need any complicated handling of fine
mask patterns. In the simplest case, the mask for the deposi-
tion of the source and drain electrodes is sufficient for the
TTC deposition. Actually, we can fabricate an ambipolar
FET by first depositing the TTC and then the Al second
through the same mask. Because the direction of the deposi-
tion source of the two materials is slightly different, the edge
region of the deposited TTC layer is slightly shifted from
that of Al, inducing the coexistence of areas with and without
the TTC layer. The device showed a similar ambipolar prop-
erty as in Fig. 3.
Finally, we shortly discuss the alternative model of the
ambipolar mode due to the accumulation-inversion model. In
Downloaded 29 Nov 2012 to 202.3.77.183. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Appl. Phys. Lett. 90, 033504 共2007兲
the DCM results of the unipolar C60 and pentacene FET
共Figs. 1 and 2共a兲, respectively兲, the current increase due to
the charge accumulation occurred only for the unipolar gate
voltage. It should be noted that our measurement is very
slow 共13 min for 1 cycle, 0.1 V / s兲. It is probably slow
enough to observe the carrier generation in the organic layer
due to thermal excitation. However, no current increase due
to inversion was observed. This result indicates that the
accumulation-inversion model is not plausible for intrinsic
organic semiconductors because of the extremely low den-
sity of the thermal carriers.
In summary, we investigated the surface modification of
the SiO2 layer in OFETs with an alkane molecule, TTC. In
order to realize a stable n-type operation for ambipolar
mode, surface modification should improve two factors: One
is the suppression of carrier traps on the dielectric surface
and, the other, the effective carrier injection. Concerning the
former, we found that the insertion of the TTC effectively
suppresses the electron traps on the SiO2 surface suggesting
the wide applicability of TTC for that purpose. Concerning
the latter factor, we found that the insertion of the TTC layer
can switch the injection property at source and drain
electrode/pentacene interface from hole injecting to electron
injecting. In addition, by simple patterning of the TTC layer
to make both injecting natures coexist, an ambipolar opera-
tion was realized. It is not clear whether the observed injec-
tion switching is a general phenomena or specific to Al-
pentacene system. A further study is in progress. The TTC is
very easy to make by vacuum vapor deposition and a well-
ordered molecular orientation in comparison with other ma-
terials such as the self-assembled monolayer. Thus the TTC
is a good material for the surface modification of the dielec-
tric layer in OFETs.
1
A. Dodabalapur, H. K. Katz, L. Torsi, and R. C. Haddon, Appl. Phys. Lett.
68, 1108 共1996兲.
2
C. Rost, S. Karg, W. Riess, M. A. Loi, M. Murgia, and M. Muccini, Appl.
Phys. Lett. 85, 1613 共2004兲.
3
T. Yasuda, T. Goto, K. Fujita, and T. Tsutsui, Appl. Phys. Lett. 85, 2098
共2004兲.
4
L. L. Chua, J. Zaumseil, J. F. Chang, E. C. W. Ou, P. K. H. Ho, H.
Sirringhaus, and R. H. Friend, Nature 共London兲 434, 194 共2005兲.
5
T. Li, J. W. Balk, P. P. Ruden, I. H. Campbell, and D. L. Smith, J. Appl.
Phys. 91, 4312 共2002兲.
6
S. Ogawa, Y. Kimura, H. Ishii, and M. Niwano, Jpn. J. Appl. Phys., Part 2
42, L1275 共2003兲.
7
S. Ogawa, T. Naijo, Y. Kimura, H. Ishii, and M. Niwano, Jpn. J. Appl.
Phys., Part 1 45, 530 共2006兲.
8
K. Seki, N. Ueno, U. O. Karlsson, R. Engelhardt, and E. E. Koch, Chem.
Phys. 105, 247 共1986兲.
9
N. Abiko, K. Sugi, T. Suenaga, Y. Kimura, H. Ishii, and M. Niwano, Jpn.
J. Appl. Phys., Part 1 45, 442 共2006兲.
10
S. Ogawa, T. Naijo, Y. Kimura, H. Ishii, and M. Niwano, Appl. Phys. Lett.
86, 252104 共2005兲.
11
H. B. Michaelson,J. Appl. Phys. 48, 4729 共1977兲.