Metal/semiconductive polymer Schottky device

Rajiv Gupta, S. C. K. Misra, B. D. Malhotra, N. N. Beladakere, and Subhas Chandra

Citation: Applied Physics Letters 58, 51 (1991); doi: 10.1063/1.104441

View online: http://dx.doi.org/10.1063/1.104441
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/58/1?ver=pdfcov
Published by the AIP Publishing

Articles you may be interested in

Polymer/metal hybrid multilayers modified Schottky devices
Appl. Phys. Lett. 103, 193117 (2013); 10.1063/1.4829532

Schottky barrier formation at metal electrodes and semiconducting carbon nanotubes

Appl. Phys. Lett. 94, 093107 (2009); 10.1063/1.3093677

Measurements and modelling of the barrier heights and ideality factors in the metal/conducting polymer
composite Schottky device
J. Appl. Phys. 85, 3671 (1999); 10.1063/1.369732

Field dependent permittivity in metalsemiconducting SrTiO3 Schottky diodes

Appl. Phys. Lett. 66, 697 (1995); 10.1063/1.114103

Semiconductive polymerbased Schottky diode

J. Appl. Phys. 72, 818 (1992); 10.1063/1.351822

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.195.150.201 On: Tue, 14 Oct 2014 04:41:31
 Metal/semiconductive polymer Schottky device
Rajiv Gupta, S. C. K. Mist-a, B. D. Malhotra, N. N. Beladakere, and Subhas Chandra
National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi 110012, India
(Received 12 March 1990; accepted for publication 5 November 1990)
Development of a metal/organic-semiconductor Schottky junction as an alternative to the
metal/inorganic-semiconductor junction is reported. Metal/polypyrrole (PP) junctions
have been prepared with electrochemically deposited doped PP films of different thickness
and various metals (In, Sn, Ti, and Al) as electrodes. The electrical characteristics of
the junction depend upon the work functions of PP and the metal. It has been possible to
prepare Schottky barriers on the PP films with a metal electrode having a work function
lower than that of the polymer. Various physical characteristics of the polymer, work
function, Fermi level, and carrier concentration have been estimated.

Semiconducting polymers are fast replacing the inor- junction have little difference indicating incomplete block-
ganic semiconductors in device fabrication. These poly- ing of the charge carriers at the metal polymer interface.
mers can be easily synthesized and obtained in the form of The Al/PP junction however, appears to be more suitable
thin film.‘q2 Metal/conducting-polymer heterojunctions for the fabrication of Schottky barriers as the 1-V charac-
have been prepared from bulk and thin films.3-6 The ulti- teristics resemble those of inorganic Schottky devices. The
mate use of the metal/polymer junction is in device fabri- shape of the 1-V characteristics is not identical to those of
cation. The device performance is dependent upon the elec- metal/inorganic semiconductor junctions, probably due to
trical characteristics of the junction. The metals, having a high dopant concentration in PP. The rectification ratios
work function lower than that of the p-type polymer, form for junctions with various metals at 0.2 V are listed in
a rectifying contact, while the metals having a higher work Table I. The rectification ratios are well within the range
function form an ohmic contact.7’8 We report the junction observed for other Schottky barrier devices.5 It was also
characteristics of electrochemically prepared polypyrrole found that Hg (work function 4.49 eV) forms an ohmic
(PP) films with different metals. Attempts have been made contact with PP film. Curve 5 shows the I- Vcharacteristics
to estimate the work function, Fermi level etc., of PP from for doped PP film of thickness 14 p with a Sn electrode.
the junction characteristics. The thicker films have a lower breakdown voltage in the
The metal/PP junction consisted of the metal and elec- reverse bias which is similar to inorganic thin films.” A
trochemically deposited PP films obtained by simultaneous thinner polymer film of the order of 3 p appears to be more
polymerization and doping of the pyrrole.“” The PP film suitable for device fabrication. Experiments were also per-
deposition was carried out under isothermal conditions in a formed with undoped PP/metal junctions. No 1-V charac-
single compartment cell with three-electrode structure and teristics could be obtained for undoped films owing to their
by using high-purity solvents. The supporting electrolyte high resistivity ( = 10’ R cm).
and pyrrole monomer were obtained from MS Fluka
Chemie A. G. The PP films were formed on an indium-
tin-oxide coated glass anode having a sheet resistance of
15-20 Q/O and platinum foil was used as the cathode. A
25 c II
standard calomel electrode was used as the reference. The
electrochemical cell solution contained 0.1 M pyrrole
monomer, 0.1 M tetraethylammonium tetrafluoroborate as
the supporting electrolyte, and propylene carbonate as the
solvent. The electro deposition was carried out in an inert
atmosphere at current densities of the order of 2-3 mA/
cm* (at 15 V). Self-supporting films of various thicknesses
could be made by controlling the deposition time. The con-
ductivity of these PP films, as measured by the four-point
probe, was found to be in the range of 5-l 5 R - ’ cm - ‘.
Metal electrodes were deposited on the PP films to make
metal/polymer junctions. The effective junction area was
0.016 cm*. The ohmic contact on the other side of the
junction was made with Electrodag E 502.
The I-V characteristics of the metal/PP planar
Schottky junction with different electrode metals are
25
shown in Fig. 1. Curves 1, 2, 3, and 4 show the 1-V char-
acteristics for doped film of thickness 3 p. It is apparent FIG. 1. Current-voltage characteristics of metal/polypyrrole film planar
that the forward and reverse bias characteristics of Ti/PP Schottky diodes with different metal electrodes.

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
51 Appl. Phys. Lett. 58 (i), 7 January 1991 0003-6951/91 /010051-02$02.00 @ 1991 American Institute of Physics 51
137.195.150.201 On: Tue, 14 Oct 2014 04:41:31
 TABLE I. Various characteristics of metal (Ti, In, Al, Sn)/PP junctions.

Work function’4 Rectification Ideality Barrier

Metal (eV) ratio factor Height (V)
Titanium 4.09 10 10.64 0.50
Indium 4.12 28 10.80 0.53
Aluminum 4.28 50 11.11 0.51
Tin 4.42 30 10.45 0.52
-I 2 -0.8 -0.4 0 0.4 0.8 i.2 1.6
R E V E R S E BIAS V3LTAGE.V

Figure 2 shows In J vs V characteristics for different

metal/PP junctions for 3- and 14-p-thick PP films, where
V is the forward bias voltage and J is the corresponding
current density (amp/cm*). Using the relation
J=Jo exp(qV/nkT),
where Jo, the saturation current, is given by
Jo=A*T2 exp( - qX,/kT),
where A* is the Richardson constant ( 120 A/K* cm2 for a
free electron) and xb is the barrier height. The barrier
height for various metal/PP junctions were calculated and
are listed in Table I. The ideality factor for different
metal/PP junctions were also calculated. The Fermi level
of doped PP (band gap 2.7 eV)9 from the above measure-
ments was estimated to be 0.2 eV above the valence-band
edge.
Figure 3 shows the capacitance-voltage characteristics
of Sn/PP/E 502 configuration. Using standard techniques
the carrier concentrations for the doped and undoped PP
vottogc,v -
FIG. 2. In J vs V for different metal/polypyrrole film configuration.
FIG. 3. Capacitance-voltagecharacteristics of polypyrrole films with Sn
electrode.
were found to be of the order of 1.5 x lo*’ and 5x 10”
cm - 3, respectively. These are in good agreement with the
reported values.‘3
(1) In summary, Sc’hottky barrier devices can be prepared
with electrodeposited conducting polymer films and suit-
able metal electrodes. The carrier concentration appears to
be the main factor controlling the junction characteristics,
and hence, the device performance. The Fermi level and
(2) the carrier concentration of the PP have been estimated.
The work function csf PP has been found to be in the range
of 4.42-4.49 eV. The electrochemically deposited PP films
are rigid and we can be optimistic about fabricating more
complicated devices using these films. These studies could
also be useful in extending and testing the validity of con-
cepts and theories developed for inorganic semiconductors
as applied to the organic semiconductors.
The authors are grateful to Professor S. K. Joshi, Di-
rector, National Physical Laboratory, for the encourage-
ment and interest in this work. Thanks are due to S. S.
Pandey and M. K. Ram. Financial assistance from the
Commission of the European Community is gratefully ac-
knowledged. Thank:; are also due to the referee for con-
structive suggestions,.
‘B. D. Malhotra, N. Kumar, and Subhas Chandra, Prog. Polym. Sci. 12,
179 (1986).
*B. D. Malhotra, S. Ghosh, and R, Chandra, J. Appl. Polym. Sci. 40,
1949 (1990).
3J. Kanicki, Mol. Cryst. Liq. Cryst. 105, 203 ( 1984).
4P. M. Grant T. Tani, W. D. Gill, M. Krounbi, and T. C. Cfarke, J.
Appl. Phys. i2, 869 (1981).
5H. Koezuka and S. Etoh, J. Appl. Phys. 54, 2511 ( 1983).
“S. Miyaguchi, A, Fueki, Y. Sorimachi, and I. Tsubata, Synth. Met. 28,
C691-C695 (1989).
‘S. Miyaguchi, A. Fuel& Y. Kushihi, H. Abiko, and Y. Sorimachi,
Synth. Met. 18, 689 (1987).
‘0. Inganas and I. Lundstrom, Synth. Met. IO, 5 ( 1984/1985).
*T. A. Skotheim, ed., Handbook of Conducring Polymers (Marcel-
Dekker, New York, Base& 1986).
‘“A F. Diaz K. K. Kanazawa, and G. P. Gardini, J. Chem. Sot. Chem.
Commun. 635 (1979).
“C. Weaver, Adv. Phys. 2, 83 ( 1962).
“S. M. Sze Phy.sicsofSemiconductor Devices, 2nd ed. (Wiley. New York,
1981). ’
“I?. Buhks and 1. M. Hodge, J. Chem. Phys. 83, 5976 ( 1985).
14H. B. Michaelson, J. Appl. Phys. 21 536 (1950).

Appt. Phys.
52 is copyrighted
This article asLett., Vol. in
indicated 58,the
No.article.
1, 7 January
Reuse of1991 Gupta et at. Downloaded
AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. 52 to IP:
137.195.150.201 On: Tue, 14 Oct 2014 04:41:31