Schottky barrier formation using composite of polyaniline

containing iron oxides

H.A. Motaweh and T. G. Abdel-Malik *
Department oI Physics, Faculty oI Science, Damanhour Branch , Alexandria University , Egypt.
* Department oI Physics , Faculty oI Science , University oI Minia , Egypt.
ABSTRACT
A composite oI polyaniline (PANI) containing iron oxides (Fe3O4) with nanometer size was prepared by a chemical
method. The electrical properties oI (PANI-Fe3O4) sandwich structure using ohmic gold and blocking aluminium
electrodes were studied. The current density voltage (J-V) characteristics Ior the device resemble the typical dark
current versus applied voltage characteristic Ior conventional Schottky diode. Electronic parameters have been
calculated using J-V and capacitance voltage (C-V) measurements.
Keywords : Polyaniline (PANI); Electrical properties; Schottky diode; Nanometer materials.

1. INTRODUCTION
Conducting polymers are recently studied intensely Ior their potential characteristics. They are particularly attractive
because oI their widely used as host matrix in the preparation oI nanocomposites, ease and cheapness oI Iabrication,
high electrical conductivity and good environmental stability under ambient conditions. |1|. Among the most
promising conducting polymers , Polyaniline (PANI) has received a great deal oI attention recently because oI its
excellent environment stability in a conducting Iorm, unique redox properties , and high conductivity |2|.
Semiconductor nanoparticles have attracted much interest due to their Iundamental as well as technological
importance |3, 4|. Polyaniline composites containing magnetic nanoparticles (NPs) have invited special attention
recently. Magnetite Fe3O4 particles are evincing interest because (i) Fe3O4 is well characterized, (ii) it is
biocompatible (iii) very inexpensive to produce NPs embedded in polymers |5|. The semiconducting behavior oI the
conductive polymers can be used in device applications |6|. This has opened a new possibility oI replacing
conventional inorganic devices by the organic ones.
Photovoltaic devices oI polyaniline composite containing nanosized semiconductor particles (CdS and Cu2S ) have
been studied|7|. The short circuit current (ISC) and open circuit voltage (JOC) oI these devices were Iound to increase
with the concentration oI CdS in the polymer matrix. The use oI nanocrystals allows great Ilexibility in controlling
the perIormance oI the devices by changing the size, concentration and the material oI the nanocrystals.
Polyaniline has been known to be a p-type semiconductor |8|, making it suitable Ior various applications. Devices
based on Polyaniline have demonstrated potential Ior application such as gas sensors |9,10|, Schottky diodes |11|,
rechargeable batteries |12| and light emitting diodes |13|. In this paper, the current density - voltage (JV) and
capacitancevoltage (CV) measurements oI Al/ PANIFe3O4 / Au structure at room temperature (300K) were used
to estimate the electronic parameters controlling the device characteristics. In general, metal possessing a high work
Iunction, such as Au, gives ohmic contacts, while metal possessing a low work Iunction |14|, such as Al, provides
rectiIying contacts that inIormed p-type behavior Ior the conducting polymer |15,16] in the device.
2. EXPERIMENTAL
PANI-Fe3O4 nanocomposite powder was prepared according to the previously reported in situ precipitation method
|5|. Aniline monomer was distilled under reduced pressure. A mixed solution oI FeCl2.4H2O (1.0 mol.) and
FeCl3.6H2O (1.5mol.) was prepared in water with vigorous stirring at room temperature. The FeCl3.6H2O was
working as an oxidant. A speciIic volume oI aniline was added to the previously mentioned mixed solution. AIter 4
h oI reaction, a solution oI NaOH with careIully controlled pH was added. A black precipitate oI PANI-Fe3O4 was
observed aIter10 h. The resulting composite was poured into water and Iiltered. Each wash step was carried out until
the Iiltrate became clear and colorless. Finally, the insulating polymer composite was washed with distilled water,
methanol, and acetone and dried overnight in a vacuum oven at 50
0
C. More experimental details can be Iound
Organic Photovoltaics IX, edited by Zakya H. Kafafi, Paul A. Lane,
Proc. of SPIE Vol. 7052, 705212, (2008) 0277-786X/08/$18 doi: 10.1117/12.793869
Proc. of SPIE Vol. 7052 705212-1
2008 SPIE Digital Library -- Subscriber Archive Copy
elsewhere 17|. PANI-Fe3O4 was then pressed into cylindrical pellets oI 1.28 cm in diameter and thickness oI 0.30
cm. It has been reported that work Iunction oI PANI lies between 4.1 and 4.28 eV |18|.
Vacuum evaporation oI aluminum on PANI oIten resulted noise in IJ characteristics and hence aluminum Ioil was
used in the Iabrication oI the device. A 45m thick Al Ioil (Al3.7 eV) was used as rectiIying contact with PANI
while10 m thick gold Ioil (Au5.1 eV) acted as Ohmic contact. Epoxy resin was used to seal up the device to
prevent the junction Irom the attack oI moisture and oxygen. Electrical contacts to the specimen were equipped with
copper wires mechanically applied to the metal electrodes oI the specimen using 'Radio Spares thermosetting silver
paint. Current densityvoltage (JV), reverse and Iorward characteristics oI the samples were carried out at room
temperature (300K) using stabilized power supplies and Electrometer (Keithley 610). Forward bias was applied by
supplying negative voltage to Al electrode |19| .Capacitancevoltage (CV) characteristics was perIormed with
HIOKI (3532) LCR meter.

3. RESULTS AND DISCUSSION
Typical set oI JV data oI the device at room temperature (300K) Ior both Iorward and reverse bias conditions is
shown in Fig.1. The results are asymmetric and nonlinear Ior Iorward and reverse directions oI applied voltage. This
suggests that Schottky barrier is Iormed in the PANIFe3O4 nanocomposite sample.
-4 -2 0 2 4
-0.4
0.0
0.4
0.8


J

(

1
0 -
2

A

c
m
-
2

)
V(V)
Fig. 1. Forward and reverse biased J vs. V characteristics
of Al / PAN-Fe
3
O
4
/Au Schottky barrier device at 300K.
The rectiIication ratio oI the junction was evaluated at +1V yielding a value oI 15. The mode oI carrier transport oI
charge Irom the semiconducting polymer (PANI) to metal (Al) over the potential barrier is described by thermionic
emission theory or diIIusion theory or thermionic emissiondiIIusion theory oI metalsemiconductor rectiIication.
The applied Iorward bias and the current based on thermionic emission current can be written as |20|:
) 1 ( } 1 exp
0
=
nkT
eJ
f
J J
where n the ideality Iactor being equal to unity Ior an ideal diode, J0 is the saturation current density and deIined by
) 2 ( exp
2
0
kT
e
b
T A J

=
where the quantities A* , T , e, k and b are the eIIective Richardson constant, temperature in Kelvin, the
electronic charge, Boltzmann constant and the apparent barrier height .
Proc. of SPIE Vol. 7052 705212-2
Under Iorward bias, one can determine - b by plotting ln (J) versus V. From Eq. (1),with voltages larger than a Iew
kT/e , the plot oI ln J versus V, is expected to be straight line whose intercept at V0 gives Js. Fig.2 shows ln (J)
versus V Ior the sample at 300K. It can be seen Irom the Iigure that only Iew points in the low voltage region are in
good agreement with the theory predicted by Eq.1. DiIIiculties will arise iI the diode has a series resistance. The
straight line part oI the plot will then be conIined to a small voltage interval which result in unreliable value oI
barrier height-b. Using the value oI b 0.30 eV as derived Irom the C-V measurements; the values oI ideality
Iactor and the eIIective Richardson constant were Iound to be n1.8 and A* 1.64x10
-8
A cm
-2
K
-2
respectively.
The value oI A* is much smaller than the Richardson constant reported Ior the Iree electron (120 A cm
-2
K
2
). This
indicates that the diIIusion mechanism is more dominant |21|.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
-16
-14
-12
-10
-8
-6
-4
-2
0
L
n

(
J
)
V(V)
Fig.2. Dependence of ln (J) on V for a forward biase
Al/ PAN-Fe
3
O
4
/Au structure at 300K.
According to the thermionic emission theory, the Iorward bias JV characteristics oI a Schottky diode with the series
resistance R can be expressed as
) 3 ( exp
) (
0
nkT
RAJ J e
J J

=
where the RAJ term is the voltage drop across the series resistance oI device.
The Schottky diode parameters n, b, and R were extracted Irom a single Iorward bias JV characteristics using a
method developed by Cheung and Cheung |6|. The parameters oI the structure can be determined Irom the Iollowing
Iunctions using Eq. (3)
) 4 (
) (ln e
nkT
RAJ
J a
aJ
+ =
) 5 ( ) ln( ) (
2
T A
J
e
nkT
J J H


and H (J) is given as Iollows:
) 6 ( ) (
b
n RAJ J H + =
Proc. of SPIE Vol. 7052 705212-3
A plot oI (dV) / (d lnJ) vs. J will be linear and its slope gives RA and nkT/e as the y-axis intercept, Irom this the
values oI n and R will be determined Irom Eq. (4). Shown in Figs.3 and 4 are dV/d (lnJ) and H (J) vs. J Ior the Al/
PANI/Fe3O4 /Au structure at 300K. The parameters oI the structure n, b, and R obtained Irom Cheung and Cheung
Iunctions at room temperature are shown in Table 1.
Table 1. The various parameters oI the Al/ PANI/Fe3O4 /Au structure obtained Irom IV characteristics at 300 K.
The ideality Iactor obtained Irom Cheung Iunctions is higher than that obtained Irom Eq (1) due to the voltage drop
in the high voltage region (at series resistance region) and this causes a non-ideal behavior. The deviation Irom ideal
value (n~2.4) may be either due to accelerated recombination oI electrons and holes in the depletion region or by the
presence oI an interIacial layer |22| which introduces the interIace states located in it and the semiconductor
interIace.
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.0
0.5
1.0
1.5
2.0

d
V
/
d

(
l
n
J
)



(
V
)
J (10
-2
Acm
-2
)
Fig.3. A plot of dV/d (lnJ) vs. J obtained from forward bias current-voltage
characteristicsof the Al/ PAN-Fe
3
O
4
/Au structure at 300 K

J vs J .

J vs J a aJ . ln /

J vs H .
n n R() (eV) R()
1.8 2.4 200 0.30 240
Proc. of SPIE Vol. 7052 705212-4
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.5
1.0
1.5
2.0
2.5
3.0

H

(
J
)

(
V
)
J (10
-2
Acm
-2
)
Fig.4. A plot of dV/d (lnJ) vs. J obtained from forward bias current-voltage
characteristicsof the Al/ PAN-Fe
3
O
4
/Au structure at 300 K
Further inIormation about the properties oI the metal semiconductor contact was obtained Irom the reverse current
measurements. The reverse current can also be used to determine the properties oI the metal semiconductor contact.
It has been observed that, in practical Schottky diodes, eIIects such as leakage, generation oI excess carriers in the
depletion region, tunneling and barrier lowering give rise to voltage dependence reverse currents. The voltage
dependence oI the reverse biased current density can be written as |21|
) 7 ( exp exp
2 / 1
2 *
KT
J
KT
b
T A J

=
where is related to the barrier width.
The linear behavior in plot oI the current density ln J vs. V
1/2
as shown in Fig. 5 indicates that the JV characteristics
are consistent with Eq. (7). The estimated value oI Ior the investigated sample is 0.19 eV V
-1/2
.

-16
-12
-8
-4
L
n

{

J

(

A
c
m
-
2

)

}
V
1/2
r
Fig. 5 .ln J vs. V
r

of the reverse biased for

the Al/ PAN-Fe
3
O
4
/Au structure at 300K.
Proc. of SPIE Vol. 7052 705212-5
1 2 3 4 5
0.5
1.0
1.5
2.0
2.5
C
-
2

(
1
0
1
4
F
2
)
V(v)
Fig. 6. The C
-2
vs. V characteristics of the Al/ PAN-Fe
3
O
4
/Au
structure at f = 100 kHz frequency, at 300K.
The Schottky barrier oI the structure can be Iurther characterized using capacitancevoltage (CV) measurements. It
has been observed that the junction has a speciIic capacitance due to a space charge in the depletion layer. It is
related to the width oI the depletion region and thereIore depends on junction voltage .The measurements oI the
dependence oI the barrier capacitance on the reverse biases were carried out at I 100 kHz Irequency and at
temperature 300 K. Fig. (6) shows that the C
-2
V characteristic obtained is linear which indicates the Iormation oI
Schottky junction |20|.ThereIore, it Iollows a standard MottSchottky relationship:
) 8 (
) / ( 2 1
2
0
2
NA e
e kT J J
C
a

=
where Vd is the built-in potential at zero bias, V is the reverse bias, kT/e is the thermal voltage at 300 K, c0 is the
permittivity oI the Iree space (assumed to have the value oI 3) |21| is the relative permittivity oI polymer, N is the
ionized acceptor / trap concentration and A is the eIIective area oI the diode.
The barrier oI Schottky diode height b is related to the diIIusion potential Vd by the Iollowing relation
) 9 ( ) ln 1 (
N
N
e
KT
J
v
a b
+ + =
It is readily seen that the slope oI a C
-2
vs. J plot gives the carrier concentration N and the intercept gives the built-in
potential Vd (Fig. 5). The built-in potential Ior the Al/ PANI/Fe3O4 /Au structure was calculated to be 0.085V and
the carrier concentration N was 5.68 x10
17
cm
-3
. The value oI N correlate well with the previously published data
|22-23|.
Substituting the values oI N, Vd and NV (assumed to have the value oI 10
21
cm
-3
) in Eq.9, the derived value oI b
was Iound to be 0.30 eV, which coincide with the value obtained Irom the J- V characteristics.
The capacitance oI the depletion layer C0 at zero bias was used to calculate depletion width (W) using:
) 9 (
0
0

A
C =
The value oI C0 is Iound to be - 590 nF which corresponds to a depleting width oI 5.8nm. Hence, the high C0,
low W and b Ior the Al/ PANI/Fe3O4 /Au structure can be attributed to arise Irom the better dopability oI Fe3O4 and
open-structure morphology oI PANI in the presence oI Fe3O4 as dopant |19|.
Proc. of SPIE Vol. 7052 705212-6
4. CONCLUSIONS
Polyaniline (PANI) containing iron oxides (Fe3O4) with nanometer size were used to Iabricate the Schottky device
Al/PANI -Fe3O4 /Au. Current density voltage (JJ) and capacitancevoltage(C-V) characteristics Ior this device
resemble the typical characteristic Ior conventional Schottky diode. The characteristic parameters oI the structure
such as ideality Iactor, series resistance, barrier height, built-in potential at zero bias and depletion width (W) have
been determined Irom J-V and CV measurements.
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Proc. of SPIE Vol. 7052 705212-7