ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 86 (2005) 217–227

www.elsevier.com/locate/solmat

Electrical characterization and Poole–Frenkel

effect in sol–gel derived ZnO:Al thin films
R. Maity, S. Kundoo, K.K. Chattopadhyay
Department of Physics, Jadavpur University, Kolkata 700 032, India
Received 7 April 2004; accepted 5 July 2004
Available online 11 September 2004

Abstract

Electrical properties of ZnO:Al thin films, prepared by sol–gel dip-coating technique were
studied in the range of 0.32% to 1.62% Al concentrations in the films. Room temperature
electrical conductivity was found in the range of 0.08 to 1.39 S/cm for different aluminium
concentrations in the films. I–E characteristics of the films at a constant temperature showed
non-linearity, while non-linearity becomes more and more pronounced with increase in
temperature and this could be explained by Poole–Frenkel model of thermionic emission.
Presence of adsorbed oxygen and excess Al atoms at grain boundaries is assumed to be the
cause of this effect. These atoms produce defect levels, which trapped electrons and created a
potential barrier across the grain boundaries. In the presence of an external field, the barrier
height was attenuated, resulting in the thermionic emission of electrons from the trapped level
to the conduction band. The trapped potentials (ft ) were calculated for different doping
concentrations in the films. The thermoelectric power (TEP) measurement confirmed the n-
type nature of the films and the room temperature Seebeck coefficient was found to be

91.65 mV/K.
r 2004 Elsevier B.V. All rights reserved.

Keywords: Zinc oxide; Sol–gel; Electrical transport; Poole–Frenkel effect

Corresponding author. Tel.: +91-33-473-4044.

E-mail address: [email protected] (K.K. Chattopadhyay).

0927-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2004.07.008
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218 R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227

1. Introduction

ZnO thin films are technologically important materials due to its wide range of optical
and electrical properties. These characteristics have made ZnO thin films very adequate
for several promising applications in solar cells [1–4], gas sensors [5,6], transducers [7,8],
luminescent materials [9], transparent conductors [10–12], heat mirrors [13,14],
semiconductor heterojunctions [15,16], etc. ZnO thin films have been prepared by
many techniques such as thermal evaporation [17], chemical vapour deposition [18,19],
RF-magnetron sputtering [20], spray pyrolysis [12,21], pulsed laser deposition [4,22], etc.
Pure ZnO is an unstable material due to the adsorption of atmospheric oxygen, which
decreases the conductivity and modifies its surface morphology [23]. To stabilize the
material against such changes, doping is necessary and this purpose was achieved by
adding several dopants of group III elements such as indium [24], boron [25], aluminium
[23,26], etc. and also with group VII element like fluorine [27].
In this report, aluminium-doped zinc oxide (ZnO:Al) thin films were deposited on
glass substrates by the sol–gel process, which is a low cost and easier technique for
coating on a large area. Carrier transport mechanism in Al- doped ZnO (ZnO:Al)
thin films has been studied in detail. The experimental data support that the
transport mechanism in the ZnO:Al films was dominated by Poole–Frenkel model of
thermionic emission [28]. On the other hand, other transparent conducting oxides
films like antimony-doped tin oxide [29] and fluorine-doped tin oxide [30] have
shown Poole–Frenkel effect dominated electrical transport.

2. Experimental

2.1. Sol preparation

Zinc acetate (Zn(CH3COO)2  2H2O) and isopropyl alcohol (Pri–OH) were taken
as starting materials to coat ZnO thin films on glass substrates by sol–gel method.
Initially, 0.85 mol/l of zinc acetate was dissolved into isopropyl alcohol. Since zinc
acetate has low solubility in isopropyl alcohol, diethanolamine (DEA) ([DEA]/
[Zn2+]=1.5) was added to obtain a transparent solution and to keep the solution
stable for dip-coating process. Aluminium nitrate (Al(NO3)3  9H2O) was taken as
dopant to achieve Al doping. Then the resultant solution was stirred keeping the
temperature at 70 1C for 1 h. The atomic ratio of Al/Zn in the initial solution was
varied from 0.32% to 1.62%. Distilled water ([H2O]/[Zn2+]=14) and acetic acid
([H+]/[Zn2+]=2) were added for better stability of the solution and to avoid
gelation or precipitation [31]. The pH of the solution was kept about 7.0. Lastly,
stirred solution was aged for half an hour.

2.2. Film deposition

For dip coating, initially the glass substrates were thoroughly washed with mild
soap solution and distilled water. Then the ultrasonically cleaned glass substrate was
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R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227 219

dipped vertically into the solution and withdrawn at a speed of 8 cm/min to coat the
solution on the substrates with the required material. The coated substrate was dried
at room temperature for 10 min and heated at 150 1C for 10 min in open atmosphere.
This process was repeated for 3–5 times for getting a desired thickness. Finally, the
film was heated at 250 1C for 1 h. The thickness of the film was measured by cross-
sectional SEM and found to be 0.8 mm.

2.3. Characterization

Structural characterization was carried out by the X-ray diffraction (XRD)

analysis. This was performed by a X-ray diffractometer (Philips PW 1730/10) using
the CuKa (1.5406 Å) radiation operating at 30 kV, 20 mA with a normal y–2y
scanning. The electrical characterization was basically done by conventional four-
probe method using Keithley electrometer (Model 6514) for voltage measurement
with an external current source. For all electrical measurements we have used silver
paste for ohmic contact.

3. Results and discussion

3.1. Structural properties

Fig. 1 shows the XRD pattern of ZnO:Al films deposited on glass substrate for
0.97% of Al using DEA as the stabilizer. In XRD pattern, no peak of aluminium
nitrate was observed due to small amount of doping. The peaks were identified to
originate from (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3) and (1 1 2) reflections of
hexagonal (JCPDS-05-0664) ZnO crystal structure (a ¼ b ¼ 3:249 A ( and
(
c ¼ 5:205 A). Selected area electron diffraction (SAED) pattern (not shown here)
(002)
(101)
Intensity (arb.units)

(100)

(103)
(102)

(110)

(112)

10 20 30 40 50 60 70
2θ (deg.)
Fig. 1. XRD pattern of a typical ZnO:Al thin film.
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220 R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227

also showed the characteristic spots with the lattice spacing (d) values of 2.81, 2.25,
1.91, 1.62 and 1.463 Å which correspond to the (1 0 0), (1 0 1), (1 0 2), (1 1 0) and
(1 0 3) reflections, respectively, of hexagonal ZnO crystal.

3.2. Electrical measurements

Thermoelectric power (TEP) of the film was calculated by measuring the thermo
e.m.f. with cold junction keeping at room temperature, while hot junction
temperature was varied. TEP measurement indicated negative value of Seebeck
coefficient, which confirmed the n-type nature of the ZnO:Al films. The variation of
Seebeck coefficient (S) with temperature for the film with Al percentage 0.97 is
shown in Fig. 2. The room temperature Seebeck coefficient was found 
91.65 mV/
K. From the slope of the plot near room temperature, we have calculated the Fermi
energy (Ef ), which was found around 277 meV for 0.97% of Al doping.
The temperature dependence of electrical conductivity (s) of Al-doped ZnO films
were studied in the temperature range of 300–500 K. All the electrical measurements
were carried out in vacuum condition (10
3 Torr). Fig. 3 shows the ln s vs. 1/T
plots for different Al-doping concentrations which is similar to that reported by
Jimenez-Gonzalez et al. [23]. The conductivity of ZnO:Al films decreased as the value
of 1/T increases at higher temperature (T4300 K), suggesting a thermally activated
conduction in this temperature range. The conductivity can be expressed in the
simplest form
s ¼ s0 expð
E a =kTÞ; (1)
where Ea is the activation energy, which corresponds to the energy difference
between the donor level and the conduction level, s0 is a temperature independent
factor.

-0.05

-0.10
S (mV/K)

-0.15

-0.20

-0.25

-0.30
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8

1000/T (K-1)
Fig. 2. Seebeck coefficient vs. temperature plot for 0.97% Al doping.
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R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227 221

6
5 0.97% Al
4 0.65% Al
0.32% Al
3
1.62% Al
2
lnσ

1
0
-1
-2
-3
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

103/T (K-1)
Fig. 3. ln s vs. 1000/T plots of ZnO:Al films for different Al concentrations.

Room temperature conductivity (sRT) increases from 0.12 to 1.39 S/cm when
percentage of Al increases from 0.32 to 0.97 S/cm, but further increase of Al
percentage (1.62) decreases the conductivity to 0.08 S/cm. The increase in electrical
conductivity brought in by the Al doping can be explained as follows:
The concentration of free charge carriers in ZnO increases by the aluminium
doping because aluminium has one valance electron more than zinc. We may
consider that aluminium substitutes the zinc atom or it occupies interstitial sites. In
both cases, aluminium acts as a donor. But excess Al doping destroys the crystalline
structure of ZnO, as evidenced by the broadening and decreased intensities of
diffraction peaks in the XRD spectra (not shown here). So, excess Al doping
decreases the conductivity in ZnO films. Eq. (1) was used to calculate the activation
energies. We calculated the activation energies from the slope of the Arhenius plots
of ln s vs. 1/T shown in Fig. 3. Values of Ea, as obtained, were 779, 638 and 781 meV
for Al/Zn atomic ratios as 0.65%, 0.97% and 1.62%, respectively, in the films.
Activation energy decreased with increase in Al percentage upto 0.97%, but further
Al doping increased the value of Ea suggesting either excess Al were not contributing
the electrons or acting as a charge compensator for conduction mechanism. Al may
be situated at the grain boundary regions or interstitial positions in the ionic state
and in both cases they acted as a charge compensator and there by lowering the
room temperature conductivity for higher Al concentrations. This will create more
trapping states, which are contributing in the thermionic emission of the
Poole–Frenkel effect.
Fig. 4 shows the I–E characteristics of ZnO:Al films with Al/Zn atomic ratio
0.97% at different constant temperatures (300, 350, 400 and 450 K). The I–E
curves are non-linear in nature. Non-linearity is significant above 2500 V/m
for temperature of the film being 400 K. This is due to the presence of an
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222 R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227

3
5x10

3
T=300 K
4x10 T=350 K
T=400 K
3x10
3 T=450 K
I(µA)

3
2x10

3
1x10

0
0.0 5.0x10
2
1.0x10
3
1.5x10
3
2.0x10
3
2.5x10
3

E (V/cm)
Fig. 4. I–E characteristics of a 0.97% Al-doped ZnO thin film for different temperatures.

3
10
I(µA)

2
10 T=300 K
T=350 K
T=400 K
T=450 K

1
10
0.0 2
5.0x10
3
1.0x10
3
1.5x10
3
2.0x10
3
2.5x10
E (V/cm)
Fig. 5. Test for Poole–Frenkel model for 0.97% Al-doped ZnO thin film.

electron-depleted layer at the grain boundary and the formation of a potential

barrier. This shape of I–E curve is typical of thermionic emission over the barrier,
explained by the Poole–Frenkel model of thermionic emission. With the increase in
temperature, the curves show more and more deviation from ohmic behavior. Fig. 5
represents a test for Poole–Frenkel model of thermionic emission. The non-linear
behaviour in I–E characteristics is also observed for 0.65% and 1.62% of Al
concentrations shown in Figs. 6 and 7. Inset of Figs. 6 and 7 represent the test of
Poole–Frenkel model. The reason behind the Poole–Frenkel effect shown by ZnO:Al
films may be due to the presence of adsorbed oxygen or dopant aluminium atoms at
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R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227 223

3
5x10

3
10
3
4x10 I (µA)

2 T=300 K
10
T=350 K
T=400 K
3 T=450 K
3x10 1
10
I (µA)

0 1x10
3
2x10
3

E (V/cm)
3
2x10
T=300 K
T=350 K
T=400 K
1x10
3 T=450 K

0
2 3 3 3 3
0.0 5.0x10 1.0x10 1.5x10 2.0x10 2.5x10
E (V/cm)
Fig. 6. I–E characteristics of 0.65% Al-doped ZnO thin film for different temperatures. Inset: the same in
log scale.

3 103
1.0x10
I (µA)

102
T=300 K
2
8.0x10 T=328 K
T=353 K
101 T=378 K

2 0 1x103 2x103
I (µA)

6.0x10 E (V/cm)

2
T=300 K
4.0x10 T=328 K
T=353 K
T=378 K
2
2.0x10

0.0
2 3 3 3 3
0.0 5.0x10 1.0x10 1.5x10 2.0x10 2.5x10
E (V/cm)
Fig. 7. I–E characteristics of 1.62% Al-doped ZnO thin film for different temperatures. Inset: the same in
log scale.
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224 R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227

the grain boundary, which produce defect states. These defect states trap carriers and
thus produce a potential barrier at the grain boundaries. Under the applied field, the
barrier height is reduced and thermal emission of electrons from interfacial states
takes place, increasing the conductivity through the grain boundary.
Mathematically, the expression for current density according to Poole–Frenkel
model can be written as [32]
"
1=2 #
1 57:7 eV
J ¼ AT 2 exp
ft ; (2)
kT 1 d

(we have chosen e2=14.4 eV Å as a conventional unit)where, e1 is the high-frequency

dielectric constant of the film, d is electrode spacing in Å, ft is the depth of the trap
potential well and A is the Richardson constant having a value of 120 A/cm2 K2.
According to Eq. (2), ln (J/AT2) vs. E1/2 will be a straight line and from the
intercept on ln (J/AT2) axis, the trap potential (ft) can be calculated. Fig. 8
represents ln (J/AT2) vs. E1/2 plots at different temperatures for the film with Al/Zn
atomic ratio 0.97%. These values of ft are the energies required to transfer electrons
from the trap level to the conduction band. The values of ft, as obtained are 651, 743
and 804 meV for temperatures 350, 400 and 450 K, respectively. This result shows
that as temperature increases, lower trapping level acts as an effective thermionic
emitter. Fig. 9 shows the similar straight line plots which are obtained from other
films with Al/Zn atomic ratio of 0.65% and 1.62% at temperature 350 K. Values of
ft obtained from the straight line plots, at different temperatures for different
doping concentrations are shown in Table 1 and these values are compared with the
activation energies for the corresponding films. Comparative studies of ft and Ea
from Table 1, show that the trap levels are placed deeper into the bandgap, than the
donor level with respect to the bottom of conduction band. These data are consistent

-16

-17

-18
ln(J/AT2)

-19

-20 T = 300K
T = 350K
T = 400K
-21
T = 450K

-22
10 20 30 40 50
1/2 1/2
E (V/cm)
Fig. 8. ln (J/AT2) vs. E1/2 plots for 0.97% Al-doped ZnO thin film at different temperatures.
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-18

-20
ln(J/AT2)
-22

-24

Al=1.62%
-26
Al=0.65%

-28
10 20 30 40 50
E1/2 (V/cm)1/2
Fig. 9. ln (J/AT2) vs. E1/2 plots for 0.65% and 1.62% Al-doped ZnO thin films at 350 K.

Table 1
Comparison of trapping potentials (ft) and activation energies (Ea) for different Al concentrations and
temperatures

Sample no. % Al Temperature (K) ft (meV) Avg. ft (meV) Ea (meV)

ZO-40 0.65 350 778 938 779

400 959
450 1078
ZO-35 0.97 350 651 732 638
400 743
450 804
ZO-41 1.62 350 776 800 781
375 823

with the band structure indicated by Simmons [33], as in ZnO:Al films donor
concentrations are expected to be higher than that of the trapped charge density.
This argument seems reasonable if we compare the values of Fermi level obtained
from the TEP measurements of our samples. The value of Ef obtained were around
277 meV, smaller than the activation energies (cf. Table 1). This type of band
structure is typical of a non-degenerate semiconducting material with the donors not
fully ionized. Hence a continuous increase in conductivity with temperature was
observed for our ZnO:Al films. Now, to obtain the position of the Fermi level
theoretically, we have equated the number of ionized donor centers (Nd) with the
number of occupied traps (Nt), with the assumption that trapping is effective at all
times (i.e. Ntbn, n=number of electrons in the conduction band). This assumption
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226 R. Maity et al. / Solar Energy Materials & Solar Cells 86 (2005) 217–227

seems reasonable if we consider the relatively low room temperature conductivity of

our films (1.39 S/cm). Calculations from the above argument resulted in the
following expression [33]:


Nd
E f ¼ E d
kT ln ; provided that N d bN t : (3)
Nt
Recalculation of the relative ratio of ionized donor centers to that of trap charge
density (Nd/Nt) from the above equation with the Ef values obtained from TEP
measurement (with T=300 K) gives a value of the order of 106.
Now, ln (J/AT2) vs. E1/2 plot (at a constant temperature) will show two distinct
slopes for the Schottky emission for electrode-limited conduction and Poole–Frenkel
emission for bulk-limited case [34]. In lower voltages region, as the contact resistance
dominates, most of the voltages appear across the contact resistance and very little
across the bulk of the film. In this situation, conduction mechanisms not only bulk
limited but also electrode limited. So in lower voltage, Schottky effect is dominant.
In our case, below 360, 250 and 360 V/cm for 0.65%, 0.97% and 1.62% of Al,
Schottky effect is dominate but above these fields Poole–Frenkel effect dominate.
Stuart [35] observed this type of transition for Al–SiO–Al thin films. Similar
transitions also observed in organic semiconductor films such as copper phthalo-
cyanine and others [36]. The transition from electrode-limited to bulk-limited
conduction will be characterized by a deviation in the slope of ln (J/AT2) vs. E1/2
graph, with increase in field. Hence in higher fields (4360 V/cm), Poole–Frenkel
effect is dominant.

4. Conclusions

Poole–Frenkel effect has been observed in Al- doped ZnO thin films synthesized
by a sol–gel dip-coating method for higher fields (4360 V/cm). This effect is
basically observed due to the trap levels originated from defect levels because of
adsorbed oxygen or Al atoms present in the grain boundary regions. The electron-
depleted layer at the interface produces a potential barrier. When an external electric
field is applied, the grain boundary potential barrier is decreased, which results in
thermal emission of more electrons and enhancement of the current density. With the
increase in temperature the greater deviation from ohmic behavior of the I–E
characteristics at higher fields is observed, which is in good agreement with the above
argument. In the lower fields (o360 V/cm) region, the conduction is related to the
Schottky effect.

Acknowledgements

Two of us (R.M.) and (S.K.) wish to thank the Council of Scientific and Industrial
Research (CSIR), for awarding them a junior research fellowship (JRF) and a senior
research fellowship (SRF) respectively during the execution of the work.
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