Polythienylenevinylene thin-film

transistor with high carrier mobility

Cite as: Appl. Phys. Lett. 63, 1372 (1993); https://doi.org/10.1063/1.109680
Submitted: 24 February 1993 • Accepted: 28 June 1993 • Published Online: 04 June 1998

H. Fuchigami, A. Tsumura and H. Koezuka

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Appl. Phys. Lett. 63, 1372 (1993); https://doi.org/10.1063/1.109680 63, 1372

© 1993 American Institute of Physics.

Polythienylenevinylene thin-film transistor with high carrier mobility
H. Fuchigami, A. Ysumura, and H. Koezuka
Mitsubishi Electric Corporation, Materials and Electronic Devices Laboratoty, I-I,
Tsukaguchi Honmachi &Chrome, Amagasaki, Hyogo 661, Japan
(Received 24 February 1993; accepted for publication 28 June 1993)
A thin-film transistor (TFT) with high carrier mobility has been fabricated using
precursor-route poly(2,5thienylenevinylene) (PTV) as semiconductor. The carrier mobility
has been determined to be 0.22 cm2/V s, which is in the same level of that of amorphous silicon
TFT. It has also been made clear that the carrier mobility is linearly proportional to the
conversion ratio from the insulated precursor polymer to r-conjugated PTV. The r-conjugation
length is crucial to obtain high carrier mobility in r-conjugated polymer TFT’.

Conducting polymers with n--conjugated double bonds
in their backbone have band structures similar to those of
inorganic semiconductors such as silicon. Semiconductor
devices such as Schottky and heterojunction diodes have
been demonstrated with these polymers.’
Thin-film transistors (TFTs) are one of the most com-
mercially promising applications for deposited semicon-
ducting films.’ It is well known that amorphous silicon
(a-Si) TFTs are used in large-area liquid-crystal displays
where each TFT is arranged at every pixel for switching
liquid crystals. Several hundreds of thousand TFTs with
defect-free have to be fabricated on each panel. On the
other hand, a lot of efforts have been devoted to the fabri-
cation of TFTs with conducting polymers from the stand-
points of low-cost TFT production. Two types of TFT
have been demonstrated, that is, insulated-gate and
Schottky-gate TFTs. Electropolymerized polythiophene3
and poly(p,p’-biphenol),4 precursor-route polyacetylene,5
solvent-soluble poly (3-hexylthiophene) ,6 evaporated olig-
othiophenes,’ and metal diphthalocyaniness have been suc-
cessfully applied to the former type of TFTs. The latter
TFTs have been fabricated by utilizing precursor-route
will report on the fabrication of the TFT with a spun
poly(2,5thienylenevinylene) film synthesized by Murase’s
method14 and on the device characteristics with the same
order of the carrier mobility as a-Si TFT.
The fabricated TFT structure is illustrated in Fig. 1.
Evaporated chromium gate electrode 115 ym wide, 1 mm
long, and 100 nm thick was patterned on a low-alkaline
glass wafer. SiOz (500 nm thick) worked as the gate insu-
lator was electron-beam evaporated onto both the glass and
the gate electrode. The precursor polymer of poly(2,5-
thienylenevinylene) (PTV) was spin coated over the entire
surface from its 2-wt. % dimethylformamide solution. The
spun film was partly removed to make contacts with the
microprobes for electrical measurements. The channel
layer of the PTV-TFT is thought to be extremely thin, and
the PTV film except the channel layer acts as a resistance,
(a)
piJ-v&+ + +Q-CH=CH~

poly ( 1,4-naphthalenevinylene ) ’ and soluble poly ( 3-

alkylthiophene) s. lo
One of the most important parameters to discuss the emiconducting la

device characteristics is carrier mobility. The first TFT

with a conducting polymer, polythiophene, yielded the car-
rier mobility of about 1O-5 cm2/V s.~ In the last several
years, the carrier mobility stayed in the range of 10-s to
10v5 cm’/V s, which was lower by more than two orders
than that (0.1-l cm2/V s) of a-Si TF’I’s.”
There are mainly two approaches to improve .the de-
vice characteristics, that is, the carrier mobility. One ap-
proach is the purification of semiconducting materials to
reduce the carrier scattering by impurities. Lately, Garnier Substrate
et al. have obtained the same level of the carrier mobility as
that of a-Si in the insulated-gate TFT with vacuum- (b)
deposited cr-sexithienyl where the semiconducting material Saurcj I Drain Electrode
,
Semiconducting Layer c
has been purified during evaporation.‘2 The other ap-
proach is to use conducting polymers with large Gale insulator

r-conjunction length. Large- r-conjugation length results

in wide valence and conduction bands, leading to high car-
rier mobility. l3 FIG. 1. Schematic illustration of a fabricated TFT and the conversion
We have selected the second approach to obtain the reaction scheme from the precursor polymer to PTV. (a) Three-
high carrier mobility in organic TFTs. In this letter, we dimensional view of the TFT, (b) cross-sectional view of the TFT.

1372 Appl. Phys. Lett. 63 (IO), 6 September 1993 0003-6951/93/63(10)/1372/3/$6.00 @ 1993 American Institute of Physics 1372
 VG (v) =
400
-20

1.5
N
i$
0 1
z..
--o
-7
0.5

FIG. 2. Channel current (1,) vs drain voltage characteristics of the 0 -5 -10 -15 -20
fabricated TFT at various gate voltages ( Vo). The conversion ratio from
the precursor to PTV was 98%. v,,(=vG) (V)
FIG. 3. Square root of saturated I, vs V,( = F’,,) plots for the TFT. The
threshold voltage ( Vth) of the device is determined to be 3 V by ex-
leading to leakage current under no gate bias.3 The film
trapolating the straight line toward the Vo( = I’,,) axis.
thickness was therefore controlled to be 60-80 nm in order
to reduce the leakage channel current through the PTV
layer only acted as resistance.3 The number of repeating (pinch ofl was also observed under high drain voltage
units of the precursor polymer was determined to be region.
The channel current (I,) of insulated-gate TFTs in
- 1000 by gel permeation chromatography (GPC) using
the saturation region is described as follows:3”7
polystyrene as reference. The precursor film was heated at
200 “C for 5 min under nitrogen stream containing a small IC=/-&,( wh5) (VG- &I”, (1)
amount of hydrochloric acid (HCl) and successively for 85
min under pure nitrogen atmosphere. Reaction scheme is Vth stands for the threshold gate voltage at which the con-
depicted in Fig. 1. During the heat treatment, HCl etfec- duction channel begins to form. W, L, C,,, and p repre-
sent the channel width, the channel length, the capacitance
tively acts as a catalyst for the conversion reaction from the
of the gate insulator, and the carrier mobility in the chan-
precursor to the PTV polymer.‘5 The heat treatment under
nel, respectively. The plots of the square root of the chan-
the existence of HCl fully transformed the precursor to the
nel current against the gate voltage (vo> for the device
r-conjugated polymer, eliminating methanol. A couple of
with interconnected gate-drain electrodes yielded the
indium-tin-oxide (ITO) (100 nm thick) electrodes with straight line in the high drain source voltage VDs region
three fingers worked as source and/or drain electrodes. (see Fig. 3). The carrier mobility was calculated to be 0.22
These were installed by conventional sputtering and pho- cm2/V s from the slope and Eq. ( 1) . The extrapolation of
tolithographic technique as a final step to avoid the corro- the straight line to the V, axis gave the V,, of -3 V. The
sion-of IT0 with HCl. The photolithographic process was carrier mobility obtained is comparable to that of a-Si
conducted with the positive photoresist (AZ1 350, Hoechst TFT. Since the semiconducting layer in our TFT can be
Co. Ltd.). The device so fabricated is an insulated-gate prepared by a simple spin-coating technique, our device
TFI with the channel width of 5 mm and the channel has a great advantage in terms of the low-cost fabrication.
length of 5 pm. The carrier mobility largely depends on the
The measurements of the device characteristics were rr-conjugation length of PTV. The carrier mobility was
carried out in air by using a Yokogawa-Hewlett-Packard
semiconductor analyzer 4145A.
The TPT characteristics with the PTV thin film used
as a semiconductor are shown in Fig. 2. No doping proce-
dure was performed because PTV has an ionization poten-
tial low enough to be automaticallyp doped with oxygen in
air.16 The conductivity of the fully converted PTV was
measured by using the TFT device with floated gate elec-
trode to be in 10-5-10-6 S/cm. The channel current (I,)
flowing from the source to the drain did not increase much
with drain voltages under no gate bias (normally ofi. The 0 20 40 60 80 100
application of negative gate biases greatly enhanced the I,. Conversion Ratio (%)
This enhancement of the Ic is due to the accumulation of
positive carriers inside the semiconductor toward the in- FIG. 4. Carrier mobility vs the conversion ratio of the reaction from the
terface between SiO, and PTV. The saturation of the lc precursor polymer to PTV.

1373 Appl. Phys. Lett., Vol. 63, No. 10, 6 September 1993 Fuchigami et al. 1373
plotted against the conversion ratio of the reaction from
the precursor to PTV in Fig. 4.i8 The intensity ratio of an
IR absorption peak at 1095 cm-’ assigned to C-O-C
stretching mode of the precursor to the peak at 806 cm- ’
attributed to C-H out-of-plane bending mode in thiophene
has been used to evaluate the conversion ratio.” The
former absorption in the precursor decreased with conver-
sion and almost disappeared in the fully converted film,
while the latter peak did not change throughout the reac-
tion.
When the conversion ratio is 4%, the carrier mobility
stayed in the order of lo-’ cm2/V s. The carrier mobility
linearly increased with the reaction to finally reach 0.22
cm2/V s at the conversion ratio of 98% (see Fig. 4). This
result indicates that mobility is proportional to the amount
of semiconducting PTV chains converted from its precur-
sor. As the conversion reaction proceeded, the ~-IT* tran-
sition in PTV appeared to grow in visible absorption spec-
tra, and the absorption edge shifted to lower energy to be
1.7 eV. The appearance and shift of the visible spectra
accompanying with the conversion reaction lead to the en-
largement of the effective r-conjugation length. It is, there-
fore, considered that the effective r-conjugation length en-
hances the carrier mobility of the PTV TIT. ,..
In summary, the TFT with the spun PTV film has been
fabricated and has exhibited the carrier mobility compara-
ble to that of a-Si TFTs. The carrier mobility has been
clearly indicated to be linearly proportional to the conver-
sion ratio. This indicates that the carrier mobility depends
upon the effective n--conjugation length. The TFTs with
conducting polymers used as semiconductors are one of the
most promising alternative to a-Si TFTs.
We would like to thank Mr. Nukui for his assistance in
the TFT fabrication. We also thank Dr. T. Ohnishi of
Sumitomo Chemical Co. Ltd. for his kindness in supplying
the PTV precursor.
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