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Nanotechnology 22 (2011) 254031 (11pp) doi:10.1088/0957-4484/22/25/254031

Scaling and disorder analysis of local I –V

curves from ferroelectric thin films of lead
zirconate titanate
Peter Maksymovych1,3, Minghu Pan1 , Pu Yu2 ,
Ramamoorthy Ramesh2 , Arthur P Baddorf1 and Sergei V Kalinin1
1
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge,
TN 37831, USA
2
Department of Materials Sciences and Engineering and Department of Physics, University of
California Berkeley, Berkeley, CA 94720, USA

E-mail: maksymovychp@ornl.gov

Received 29 October 2010, in final form 30 March 2011

Published 16 May 2011
Online at stacks.iop.org/Nano/22/254031

Abstract
Differential analysis of current–voltage characteristics, obtained on the surface of epitaxial
films of ferroelectric lead zirconate titanate (Pb(Zr0.2 Ti0.8 )O3 ) using scanning probe
microscopy, was combined with spatially resolved mapping of variations in local conductance
to differentiate between candidate mechanisms of local electronic transport and the origin of
disorder. Within the assumed approximations, electron transport was inferred to be determined
by two mechanisms depending on the magnitude of applied bias, with the low-bias range
dominated by the trap-assisted Fowler–Nordheim tunneling through the interface and the
high-bias range limited by the hopping conduction through the bulk. Phenomenological
analysis of the I –V curves has further revealed that the transition between the low- and
high-bias regimes is manifested both in the strength of variations within the I –V curves
sampled across the surface, as well as the spatial distribution of conductance. Spatial variations
were concluded to originate primarily from the heterogeneity of the interfacial electronic barrier
height with an additional small contribution from random changes in the tip–contact geometry.
(Some figures in this article are in colour only in the electronic version)

Electron transport through wide bandgap semiconductors and
nearly insulating materials has been thoroughly investigated
to optimize the quality of gate dielectrics in transistors
and develop viable high-k alternatives to SiO2 [1, 2].
The recent resurgence of interest in such materials at
nanoscale dimensions has been stimulated in large part by
the phenomenon of resistive switching [3], where electronic
conductance is altered by current and/or electric field, allowing
implementation of non-volatile memory and logic [4] on a
variety of length scales. Resistive switching in binary oxides
is believed to arise from ionic motion in an applied electric
field. In more complex ternary oxides, electron transport can
be modulated by the order parameters, such as spontaneous
polarization [5–7], magnetization [8] and strain, enabling a rich
variety of intrinsic nonlinear transport phenomena.
3 Author to whom any correspondence should be addressed.
The common feature of wide bandgap oxides is small
band dispersion, low carrier mobility and an inherently large
density of shallow and deep levels in the bandgap. This is
particularly true for ternary oxides, which may exhibit disorder
on A, B and oxygen sublattices [9]. Current sensing scanning
probe microscopy, where a metal-coated tip acts as one of
the electrodes in the two-terminal transport measurement,
is emerging as a potent method to investigate electron
transport properties of such materials, because the localization
of the probed volume to less than tens of nanometers
allows one to differentiate between intrinsic and defect-
mediated transport [10, 11]. Examples of new phenomena
discovered and characterized by conducting atomic force
microscopy (cAFM), often in combination with other
types of scanning probe microscopy, include polarization-
controlled tunneling across ferroelectric surfaces [7] and tunnel
junctions [5, 6], local conductivity of ferroelastic domain

0957-4484/11/254031+11$33.00 1 © 2011 IOP Publishing Ltd Printed in the UK & the USA
Nanotechnology 22 (2011) 254031 P Maksymovych et al

Figure 1. (A) X-ray diffraction analysis of the 50 nm Pb(Zr0.2 Ti0.8 )O3 film, representative of all the films studied here. (B) Several I –V
curves obtained on the surface of a 30 nm Pb(Zr0.2 Ti0.8 )O3 film in ultrahigh vacuum at 294 K. The arrows show the direction of the linear
tip-bias ramp. The values on the bottom curve correspond to measured current, while the upper two curves were offset for clarity. (C) Time
dependence of local current measured on two different surface locations at a tip bias of −3.2 V and at T = 300 K. (D) Schematic band
alignment and bending of the Pt-tip/PZT/La(Sr0.3 Mn0.7 )O3 junction and the equivalent circuit diagram (parallel capacitance ignored). PZT is
assumed to be n-doped in this case.

walls in multiferroic oxides [12], filamentary conduction
through perovskite oxides [13], heterogeneity and breakdown
of ultrathin dielectrics [14], local manipulation of two-
dimensional electron gas at perovskite interfaces [15] and local
variations in catalytic activity of ionic membranes for fuel
cells [16].
Despite the numerous advantages of cAFM as a local
technique and a large amount of experimental work on the
subject to date, relatively few attempts have been made to
quantify and systematically analyze the cAFM data, and to
answer the fundamental question of the dominant conduction
mechanism. The difficulties in data interpretation arise due
to a large number of unknown parameters in the cAFM
experiment, such as the tip shape and contact area, the
dielectric structure of the contact, and even the tip material.
The localized nature of the measurement may further limit
the applicability of conventional 1D semiconductor models
for metal–semiconductor interfaces, as recently demonstrated
for the analysis of space-charge-limited conduction in polymer
films [17]. Moreover, many parameters of the material itself,
such as the doping and dopant profile, trap and surface state
density, the type of traps or effective electron mass, may not be
known or reliable [18].
In this paper, we present a statistical analysis of local I –V
curves that aims to differentiate between candidate conduction
mechanisms behind local conductivity through a ferroelectric
semiconductor PbZr0.2 Ti0.8 O3 (PZT) films grown epitaxially
on La0.7 Sr0.3 MnO3 (LSMO) oxide electrodes on a SrTiO3
substrate. We have combined local current–voltage ( I –V ) and
d I /dV measurements with variable-temperature statistics to
identify the transport-limiting mechanism behind the local I –
V curve. Our analysis is reminiscent of works on macroscopic
capacitor measurements that relied on differential transport
characteristics [19, 20]. However, the key distinction here is
an emphasis on the temperature dependence, on the one hand,
and on spatially resolved analysis of the transport properties,
on the other. Systematic analysis of variations within I –
V curves obtained at different locations has also revealed
coherent features that have been attributed to local changes in
the interfacial electronic barrier height.
Experiments were carried out in a customized ultrahigh
vacuum atomic force microscope (VT STM/AFM, Omicron)
using Pt-coated cantilever tips (Mikromasch, CSC37). The
I –V measurements were performed at a pressure of
3 × 10−10 Torr after transferring the sample from ambient
without any subsequent treatment, using a variable-bandwidth
current preamplifier (FEMTO DPLCA-200) with a noise floor
of ∼100 fA at the highest gain setting of 109 V A−1 . The 30
and 50 nm ferroelectric films of Pb(Zr0.2 Ti0.8 )O3 (100) were
grown by pulsed-laser deposition on a low miscut (<0.1◦ )
SrTiO3 (001) substrate, buffered by a 50 nm La0.7 Sr0.3 MnO3
(LSMO) conducting electrode [7]. The crystal structures
of the PZT films have been studied by x-ray diffraction
(XRD) (Panalytical X’Pert MRD PRO). A typical XRD 2θ –
θ scan of PZT films (figure 1(A)) reveals the crystallinity and
crystallographic orientation of the PZT films. The epitaxial
growth was established from the presence of only 00L type
diffraction in the diffraction pattern in the wide scan range. The

2
Nanotechnology 22 (2011) 254031
Table 1. 1D transport equations for the candidate conduction mechanisms in PZT films.
3
Fowler–Nordheim tunneling I = A eff 8π hm
e m Pt
PZT φB
Schottky emission I = A eff A ∗ T 2 exp(− kTe (φB0 − 4πeEε0mεh ))
Low-field migration I = eμn E bulk exp(−E F /kT ), n —dopant volume density,
E F —Fermi level, E bulk —electric field in the bulk of the film
Poole–Frenkel I = eμn E bulk exp(− kTe (E i0 −
2
9εμE bulk
Space-charge-limited (Mott–Gurney law) I = A eff 8L
out-of-plane lattice constant was measured to be ∼4.22 Å for
PZT films (c/a ∼ 1.07), which indicates that the PZT layers
are highly strained on the STO substrates with the c axis along
the (001) direction.
Despite having a relatively large bandgap (>3 eV) and
being as thick as 30–50 nm, PZT films exhibited significant
local conductance in the current range from 1 pA to 100 nA
at a negative tip bias less than −2 V (figure 1(B)). The
conductance strongly depended on the sign of the spontaneous
polarization in PZT as detailed in our earlier publication [7].
In all the experiments presented here, the films were poled
to ascertain upward polarization orientation relative to the
film’s surface. Typical I –V curves (figure 1(B)) were highly
rectifying and exhibited negligible hysteresis between forward
and backward directions of the tip-bias ramp. The conductance
also showed negligible time dependence on the time scales up
to 100 s (figure 1(C)). Finally, acquisition of I –V curves was
not associated with irreversible changes of surface topography
(not shown). Together these measurements indicate that the
electronic state of the probed volume is unchanged in the
course of the measurement, ruling out the scenarios of mixed
electron–ionic transport or effects due to polarization dynamics
(including displacement current) and charge injection during
I –V scans. Parenthetically, a simple estimate of the oxygen
vacancy displacement can be derived from the Nernst–Einstein
equation as  = τ eD E/kT , where τ —diffusion time,
D —diffusion constant, e—electron charge, E —electric field,
k —Boltzmann constant and T —temperature. Using D ∼
10−18 m2 s−1 , conservatively estimated from the data on a
related SrTiO3 [21], the ionic displacement during a 1 s voltage
pulse would be ∼0.4 nm, or only about a unit cell in the electric
field as high as 106 V m−1 at 300 K.
At the same time, the magnitude of local current varied by
almost one order of magnitude across the surface (see below),
implying significant variations of the material parameters
responsible for the interfacial barrier height (the density of
surface states) and the shape of the local tip potential (vacancy
density) across the surface [22]. Analysis of the variability
in I –V curves enables spatially resolved mapping of these
parameters.
As is now well accepted [18, 23], an equivalent circuit
diagram of the PZT film (and related perovskite oxides)
consists of two back-to-back Schottky diodes, one due to the
buried interface between the PZT film and bottom metallic
electrode (La0.7 Sr0.3 MnO3 ) and the other one due to the
top tip–surface junction, separated by a resistor representing
the bulk of the film (figure 1(D)). The electron transport
3
P Maksymovych et al
√ 3/2
2m PZT φB
E 2 exp(− 8π
3he E
)

eE bulk
4π ε0 εh
)), E i0 —trap ionization energy
, L —thickness of the dielectric, V —applied bias
mechanisms can therefore be partitioned into interface-limited
contributions, for example by Schottky emission and Fowler–
Nordheim tunneling, and bulk-limited contributions, such as
low-field migration, Poole–Frenkel hopping and space-charge-
limited conduction (table 1) [24–26].
In the equations given in table 1, e—the elementary
charge, k —Boltzmann constant, ε —low frequency dielectric
constant, εh —high frequency dielectric constant, ε0 —vacuum
permittivity, φB —barrier height, μ—electron mobility (can
be field-dependent), Aeff —effective transport area of the tip–
surface junction, h —Planck constant and m i —electron (hole)
effective mass.
At a given bias polarity, electron transport will be limited
primarily by the reverse-biased interfacial Schottky barrier
(here we assume that it is localized at the tip–surface junction),
but it may also have a strong contribution from the nonlinear
(e.g. Poole–Frenkel) resistance of the bulk. It is common
to attempt to linearize the I –V curves in the normalized
coordinates that correspond to the respective mechanisms.
Here we will assume the abrupt junction approximation for
the metal–ferroelectric contact, making it equivalent to the
standard Schottky model [24]. Therefore the maximum electric
field in the contact region, which factors in the above Fowler–
Nordheim
 and Schottky emission mechanisms, is E m =
2eND
εε0
(V+ Vbi ), where Vbi is the built-in bias due to the
difference between metal and ferroelectric work functions and
the presence of charged species on the surface, etc, ND is
the donor (or acceptor) density (combined shallow and deep
levels) and V is applied bias. This relationship represents
the limiting case when the contact area is comparable to or
larger than the film thickness (the 1D approximation) and the
width of the Schottky barriers is significantly smaller than
the film thickness. Although the properties of the metal–
ferroelectric contacts are still under debate [23], there is indeed
a growing awareness that the Schottky barrier width could be
as thin as several nanometers [18], in part due to an extremely
large density of vacancies in the skin region necessary to
stabilize ferroelectric polarization. On the other hand, the
characteristic diameter of our tip–contact area is ∼40–60 nm,
as judged from the ∼30 nm width of a ferroelectric domain
wall [27], typically observed on the surface of the 50 nm
PZT film (for more details see appendix A in [28]). We
also note that the validity of the above assumption requires
a relatively fast response of the donor and/or acceptor levels
in the ferroelectric (primarily charging/discharging) to applied
bias. While this is not generally the case for PZT [29], our
observation of time-independent conductance on the time scale
Nanotechnology 22 (2011) 254031
Figure 2. Representative I –V curves plotted in coordinates that
linearize the I –V curves due to Fowler–Nordheim (left) and
Schottky emission (right) transport mechanisms. The original curves
are shown in the inset. The electric field at the interface is inferred
within the abrupt junction approximation (see text for details).
of 100 s (figure 1(C)), together with the relatively small thermal
activation energy of ∼0.2 eV (suggesting relatively shallow
levels) supports this assumption. On the other hand, if we were
Figure 3. (A) Temperature-dependent I –V curves averaged over 100–200 random locations across PZT surface at each temperature.
(B) Temperature dependence of current at three values of the tip bias. (C) Arrhenius analysis of average current values at several values of tip
bias. (D) Schottky analysis of the average current values.
4
P Maksymovych et al
to assume a different relationship between applied potential
and electric field at the interface (e.g. E ∝ V ), the ability
of the differential normalized analysis presented below to
distinguish between candidate mechanisms does not diminish
and requires only accounting for the respective changes in the
scaling exponents.
In the abrupt junction approximation, the Schottky
emission mechanism should yield a linear I –V curve in
log(I ) = f (V 0.25 ) coordinates, and Fowler–Nordheim
tunneling in log(I /V ) = f (V 0.5 ) coordinates. As seen
in figure 2, the observed I –V curves are moderately well
linearized using both systems of coordinates, although Fowler–
Nordheim tunneling provides a slightly better linearization.
Local I –V curves are also strongly temperature-dependent
(figure 3(A)), with average local current (extracted from 100
to 200 individual I –V curves acquired on a grid) increasing
exponentially between ∼50 and ∼ 350 K (figure 3(B)). From
the analysis of the temperature-dependent I –V curves using
standard Arrhenius (log(I ) ∼ −φ  B /kT , figure 3(C)) and
Schottky (log(I /T 2 ) ∼ (−[φB0 − 4πeEε0mεh ]/kT ), figure 3(D))
coordinates, it is also evident that the I –V curves cannot
be described by a single activation energy (Arrhenius) or
interfacial barrier height (Schottky) over the whole temperature
range. Indeed, as seen in figure 3(C) there is a marked decrease
of the slope of the I –V curves below ∼150 K in the Arrhenius
coordinates (from 100 to 230 meV at high temperatures to
60–100 meV at low temperatures), and the structure is even
more complicated in the Schottky analysis revealing a similar
Nanotechnology 22 (2011) 254031 P Maksymovych et al

Table 2. Differently normalized conductance for each of the

mechanisms in table 1, within the abrupt junction approximation (see
text).
 3/2
π 2m PZT εε0 φB
Fowler–Nordheim d log I
dV
= V +V
1
bi
+ 34he 2eND (V +Vbi )3/2
tunneling
3
Schottky emission d log I
dV
= 4kT
e
( 8πN2Dε3eε2 ε )1/4 (V + Vbi )−3/4
0 h
−1
Low-field migration d log I
dE
= E bulk 
e3 −0 . 5
Poole–Frenkel d log I
dE
= 1
E bulk
+ 1
kT 4π ε0 εh
E bulk
−1
Space-charge-limited d log I
dE
= 2 E bulk
(Mott–Gurney law)

d log(I )/dV has the following advantages:

Figure 4. (A) I –V curves and their respective derivatives obtained at
294 K using lock-in amplifier detection with an AC modulation of
10 mV at a frequency of 1.2 kHz. The inset shows lock-in derivatives
overlaid on top of numerical derivatives. This procedure was used to
calibrate the output of the lock-in amplifier. (B) d log(I )/dV curves
obtained from four I –V curves (inset) using the lock-in amplifier.
change of the slope below 150 K as well as a smaller, but still
significant, kink at ∼200 K (figure 3(D)).
Thus, conventional analysis of I –V curves does not
yield conclusive assignment of the mechanism, neither by
way of fitting of the bias dependence nor the temperature
dependence of the I –V data. To address this problem,
we turned to current-normalized differential conductance,
d log(I )/dV , as an observable that simplifies the transport
equations and provides a more rigorous test for the candidate
mechanisms. Conceptually, using d log(I )/dV is similar to
several previous works, where instead the field dependence
of d log(I )/d log(E) [19, 20] (or d log(I )/d log(V ) [30])
was proposed as a descriptor of the mechanism. Here
we focus not only on a different functional form of the
differential conductance, but also emphasize its temperature
dependence and spatial variations as key observables to
differentiate between mechanisms. As we will show below,
the bias dependence of differentially normalized conductance
is strongly affected by the built-in field and must therefore be
used with caution.
(1) It can be measured by modulating the applied bias with
a small magnitude sinusoidal AC voltage, filtering the
current signal with a lock-in amplifier and recording
its first harmonic simultaneously with the I –V curve
(figure 4(A)). The obvious advantage of using lock-in is
to increase the signal-to-noise ratio up to 100-fold [31].
d log(I )/dV is then obtained numerically as (d I /dV )/I ,
figure 4(B).
(2) d log(I )/dV is independent of a significant number of
unknown parameters from the transport equations as seen
in table 2.
Simplification of the governing equations is manifested
by the fact that nearly identical d log(I )/dV = f (V )
dependences are obtained for I –V curves that differ by
as much as an order of magnitude in the absolute current
(figure 4(B)), implying a significant contribution of the
prefactor (e.g. contact area) to such a difference. Such
‘normalization’ is also strong evidence to support the
validity of d log(I )/dV as a benchmark observable for
assigning the dominant conduction mechanism. More
examples of the normalization are presented in the last
section of this paper, dedicated to the analysis of the
spatial variations among the I –V curves on the surface.
(3) Temperature and bias dependence of d log(I )/dV provide
a much more robust test for the transport mechanisms
compared to conventional fitting approaches. In particular,
temperature dependence is observed only for Schottky and
Poole–Frenkel mechanisms. Note that, fundamentally,
the temperature dependence of d log(I )/dV in the above
mechanisms arises from the Schottky effect [24], i.e. the
electric-field-induced lowering of the trapping energy (as
in the Poole–Frenkel mechanism) or the interfacial barrier
height (as in Schottky emission). The various properties
of the current-normalized differential conductance are
exemplified in figure 5, where model parameters were
used to calculate I –V characteristics and numerically
compute d log(I )/dV .
To analyze the temperature-dependent behavior of
experimental d log(I )/dV we have sampled 100–200 I –V
curves at random locations on the PZT surface and numerically
evaluated d log(I )/dV for each of them (this was done to
increase the speed of data acquisition at the expense of
increased noise). Subsequently, individual d log(I )/dV curves
were averaged across the ensemble at each temperature,

5
Nanotechnology 22 (2011) 254031 P Maksymovych et al

Figure 5. (A) I –V curves calculated using equations for Fowler–Nordheim tunneling and Schottky emission (see text) using the following
parameters: FN: φB = 0.8 eV, A eff = 314 nm2 , ND = 1021 cm−3 , ε = 30 SE : φB = 0.65 eV, Vbi = 0, ND = 1020 cm−3 , ε = 30,
εh = 6.5 [38], T = 330 K and A eff = 314 nm2 (effective tip radius 10 nm). Inset shows linearization of the calculated I –V curves in their
respective coordinates. The parameters were chosen to approximate experimental current levels and the overall shape of the I –V curves. The
analysis presented in this paper does not depend on the exact choice of these parameters. (B) d log(I )/dV = f (V ) as a function of
temperature for Schottky emission mechanism and temperature dependence of d log(I )/dV at 1.7 V (inset). (C) d log(I )/dV = f (V ) for
various values of built-in field within the Fowler–Nordheim tunneling transport. (D) The exponent of the larger bias linear segment of
d log(I )/dV as a function of built-in potential for Fowler–Nordheim and Schottky emission. In all calculations the sign of the tip bias is
opposite to experimental negative values for convenience.

which significantly reduced the noise level due to digital
differentiation. This experiment was repeated three times, in
the temperature range from ∼90 to 320 K, with the results
shown in figures 6(A)–(C). The following trends are observed:
(1) the exponent α in d log(I )/dV = f (V α ) is the same
and roughly constant when the magnitude of the tip bias
exceeds ∼4 V; (2) the absolute value of d log(I )/dV at each
voltage in this range is temperature-dependent and increases
with decreasing measurement temperature, figures 6(A)–(D)
and (3) α at |V | < 4 V is larger than that at |V | > 4 V and
d log(I )/dV is virtually temperature-independent in this range,
figure 6(B).
A model that fits the observed trends in normalized
conductance is that of two rather than one conductance-
limiting mechanisms and a crossover between the mechanisms
at a certain value of the tip bias. The statistically negligible
temperature independence of d log(I )/dV at low tip bias
|V | < 4 V (figure 6(D)) points to Fowler–Nordheim tunneling
as the most likely interfacial mechanism. On the other hand,
the increase of the magnitude of d log(I )/dV with decreasing
temperature almost unambiguously points to either Schottky
emission or Poole–Frenkel conduction at |V | > 4 V, compare
figures 5(B) and (D). Notably, d log(I )/dV scales as T n ,
with n = −0.8:−1.3 at high bias (figure 6(D)), in excellent
agreement with the anticipated n = −1 (see above). The
crossover between the two mechanisms can be seen not only
from the temperature dependence, but also from the exponent
α . It is particularly apparent for the corresponding curves
at T = 252 K in figure 6(A), T = 291 K in figure 6(B)
and T = 260 K in figure 6(C). In each case, the slope of
d log(I )/dV decreases by 1.2–1.5 units at |V | = 3.5–4 V. The
decrease of the magnitude of the slope by a similar amount is
indeed expected for the crossover between Fowler–Nordheim
tunneling and Poole–Frenkel hopping (figure 5(D)). We can
further rule out low-field migration and space-charge-limited
conduction as contributing at any point of the I –V curve,
simply because the slope of d I /dV is not constant, figure 4(A),
as expected for low-field migration and its magnitude is 4–5,
much larger than unity expected for the Mott–Gurney law.
As the temperature dependence of Schottky emission
and Poole–Frenkel hopping is indistinguishable without a
knowledge of the material-specific constants, one may suggest

6
Nanotechnology 22 (2011) 254031
Figure 6. (A)–(C) Temperature-dependent d log(I )/dV = f (V )
extracted from 100 to 200 I –V curves randomly acquired on the
surface. (A)–(C) represent measurements done on different days and
using different AFM tips. (D) d log(I )/dV as a function of
temperature at specific values of tip bias extracted from (A). Based
on the least-squares fit, the values at −3.3 V scale approximately as
d log(I )/dV ∝ T −0.2±0.1 while those at −7.0 V as
d log(I )/dV ∝ T −0.8±0.1.
that the crossover takes place between Fowler–Nordheim
tunneling and Schottky emission. Both Fowler–Nordheim
tunneling in series with either Schottky emission or Poole–
Frenkel hopping are consistent with our data. In the former
case, the crossover would occur between two mechanisms that
are both interface-limited, while in the latter, the crossover
occurs between the interface and bulk-limited mechanism.
We find the first scenario highly unlikely. In fact, Fowler–
Nordheim tunneling transitions into the Child–Langmuir law
of space-charge-limited conduction at high fields [32]. Also,
the spatially resolved analysis presented below indicates a
different degree of disorder for the low- and high-bias regions
of the I –V curve, indicating a difference in the material
properties that are responsible for each regime. We therefore
conclude that the model that best fits the observations is that of
a Fowler–Nordheim tunneling in series with a Poole–Frenkel-
limited bulk region. The crossover occurs because at a tip bias
larger than 4–5 V in magnitude the resistance of the interfacial
region becomes significantly smaller than that of the bulk
region. A similar crossover was suggested to occur for silicon
oxide thin films [33] as well as other insulators [20], although
to our knowledge local transport measurements have not yet
been discussed in this context. Our conclusion regarding the
involvement of the bulk-limited conductivity is also supported
7
P Maksymovych et al
by the relative increase of the overall conductivity of the 30 nm
PZT film compared to a 50 nm PZT film grown by the same
methods [7].
The absolute values of the exponent α ranges from
−2.5 to −3 for the low bias, interfacially limited region
of the I –V curve, and from −1.2 to −1.5 for the high-
bias region and low-temperature I –V curves below ∼200 K.
These values are significantly larger than the expectation for
the Fowler–Nordheim tunneling (−1.42), Schottky emission
(−0.75) and Poole–Frenkel hopping (−0.66) in the abrupt
junction approximation (in the case of a linear relationship
between electric field and applied potential E ∝ V , the values
would be ∼−1.9 for Fowler–Nordheim tunneling and −0.5
for Schottky emission). We believe that the reason for this
discrepancy is the value of the built-in potential that factors into
the total applied field (see table 2) and can be very large (up to
2 V) for PZT films and other ferroelectrics in vacuum [7, 36].
Indeed, estimating the value of d log(I )/dV as a function of
built-in field reveals a very strong dependence of the numerical
value (figure 5(D)) and in Fowler–Nordheim tunneling the
slope can be well in excess of −2.2. Furthermore, as seen in
figure 5(C), the d log(I )/dV cannot be simply characterized by
a single exponent, but rather the slope significantly increases
with decreasing tip bias and can even become as high as −5.
Intriguingly, the sign of the deviation from the expected values
at zero built-in field points to the sign of the built-in potential.
In our case, observation of the consistently large values reveals
that the built-in potential has an opposite direction from the
applied bias relative to the bottom electrode. This is consistent
with the observed shift of the ferroelectric hysteresis loop,
where the ferroelectric switching is induced at smaller positive
tip bias compared to negative tip bias [7].
According to our analysis, the temperature-dependent
low-bias conductance between 250 and 330 K should
correspond to Fowler–Nordheim tunneling. This mechanism in
its original inception describes field emission of electrons from
the metal surfaces [34] and is indeed a largely temperature-
independent mechanism, because of the negligible thermal
broadening of the Fermi distribution function in the metal from
0 to 300 K. This was recently observed for a ultrathin tunnel
junction of SrTiO3 [35], which is electronically similar to PZT.
However, electron tunneling from the metal electrode into the
insulator’s conduction band (or hole into the valence band)
can be mediated by empty (or filled) trap states energetically
located in the bandgap of an insulator, in the so-called trap-
assisted tunneling [34]. The Fowler–Nordheim tunneling
equation in this case is modified by a field-independent
Boltzmann term, exp(−ϕi /kT ) [35], where ϕi is the trapping
energy. We estimate ϕi to be approximately 0.2 eV based on
the Arrhenius fit. Note that, because the electron’s escape from
the trap is not field assisted in this case [33], d log(I )/dV is still
temperature-independent despite the temperature dependence
of current itself.
One key advantage of scanning probe microscopy is the
ability to resolve the variations of the observables across the
surface. In the case of cAFM, a spatial resolution of ∼10 nm
can be readily achieved. Here we use the spatial correlations of
the I –V curves to judge the onset of the crossover between two
Nanotechnology 22 (2011) 254031 P Maksymovych et al

Figure 7. (A) Statistical distribution of I –V curves based on an array acquired on a 30 × 30 grid with a resolution of 10 nm, plotted as a 2D
histogram. (B) Individual histograms at several values of tip bias.

Figure 8. Spatial distribution of current as a function of increasing negative tip bias. The pseudocolor maps represent log(I ) as a function of
tip position on a 28 pixel × 30 pixel grid with a spatial resolution of ∼10 nm. The colorbar scale is log(I × 10−1 nA).

mechanisms, which supports the conclusions derived above
using the temperature dependence of the current-normalized
differential conductance. This analysis can be eventually
extended for systematic mapping of the material properties that
enter the corresponding transport equations.
Spatially resolved analysis of the variations among the I –
V curves was based on 900 I –V curves acquired on a 30 × 30
grid of points with a pixel resolution of ∼10 nm. Figure 7(A)
shows an average I –V curve, which was plotted as a histogram
of observed current values at each bias value. The magnitude of
current varies by ∼1 order of magnitude across the PZT surface
(figure 7(B)), most likely due to inherent electrostatic disorder
in the film [36, 37], with the logarithm of current following
approximately a Gaussian distribution (figure 7(B)). What is
rather striking, however, is that the standard deviation is bias-
dependent and there is a relatively abrupt crossover from

8
Nanotechnology 22 (2011) 254031 P Maksymovych et al

Figure 9. Spatial distribution of: (A) reverse current at −3.9 V; (B) the respective d log(I )/dV values (d log(I )/dV was numerically obtained
from the I –V curves, then fitted with fourth-order polynomial to calculate the values at −3.9 V); (C) reverse current at −3.9 V normalized by
the current values at −5.5 V for each I –V curve and (D) scaling exponent α of d log(I )/dV as a function of bias, obtained by fitting
d log(I )/dV in the bias range from −3 to −4.5 V (approximate window of interfacially limited conductance). The x and y axes in each case
are pixels (with a resolution of ∼10 nm) and the colorbars are the mapped values in their respective units.

wider distributions at V > −3.5 V to significantly narrower
distributions at V < −3.5 V, figures 7(A) and (B) (from
σ = 0.28 at −5.5 V to σ = 0.47 at −2.8 V). Furthermore,
the variations between I –V curves are not random, but rather
exhibit strong correlations across the surface, figure 8. In the
low-bias region from −2.3 to −2.8 V, spatially coherent and
discrete regions of enhanced conductance (∼30 nm diameter)
are clearly visible (figure 8). Between −2.8 and −4 V, these
‘hot-spot’ features begin to blend in with each other and with
the surrounding areas, effectively disappearing. For −4 to
−6 V, the spatial distribution of conductance is significantly
more uniform than in the low-bias region and it is also
distinct because the surface areas that exhibited different
conductivity, e.g. the left versus right half of the image,
become approximately similarly conducting. The observed
variation of the disorder with tip bias is consistent with a
crossover between two mechanisms, particularly since the tip
bias corresponding to the narrowing of the current distribution
is nearly identical to the value where the exponent α is reduced
(figures 6(A), (C) and (D)). The coherent and distinct features
in the low-bias range may signify either extended defects or
defect gradients at the interface or surface, the origin of which
is subject to further investigation. The effect of these defects
on the overall conductance diminishes with increased bias, as
the bulk-limiting mechanism (and apparently more uniform
distribution of the relevant bulk parameters) becomes more
dominant at high bias.
To gain more insight into the origins of the observed
disorder, we have carried out two types of numerical analysis
on the data in figure 8: (1) simple normalization, where the
current at a chosen bias (−3.9 V in figure 9) was divided by
the current value at another bias value (−5.5 V in figure 9(C))
and (2) d log(I )/dV analysis in the low-bias region (from
−2 to −4.5 V) which we assigned to interfacially limited
conductance. d log(I )/dV was first numerically calculated for
each pixel, then fitted to a fourth-order polynomial, and then
the absolute values of d log(I )/dV (at −3.9 V in figure 9(B)),
as well as the exponent α were calculated from the fit.
The goal of simple normalization, I (−3.9 V)/I (−5.5 V),
is to reveal whether the disorder originates from the bias-
independent terms of the corresponding transport equations.
These include the prefactor (e.g. contact area), as well as zero-
eφ 0
field barrier-height terms, such as in exp(− kTB ) the Schottky
emission equation. Normalization should reduce the strength
of the disorder and change its spatial pattern if its origin is
bias-independent. The comparison of panels in figure 9(A)
(current) versus figure 9(C) (normalized current) reveals that
the disorder pattern does remain after normalization. However,
its details are slightly altered, particularly at the top and bottom
of the map. Upon careful examination one can see that the map
in figure 9(A) has several ‘streaks’ crossing the image (also
seen in figure 8 at −2.35, −2.52 V). These streaks clearly
manifest changes in the tip–contact geometry (e.g. contact
area) along the fast x axis of the scan, so that along the slow-
scan y axis the consecutive lines are abruptly different from
each other. We can therefore infer that changes revealed in
simple normalization, as well as the corresponding disorder,
originates from the tip–contact effects.

9
Nanotechnology 22 (2011) 254031
Figure 10. 2D histograms of the data from figure 9, revealing
significant correlation between: (A) reverse current (measured at
−3.9 V) and d log(I )/dV ; (B) unambiguous anti-correlation
between reverse normalized current and d log(I )/dV and (C) lack of
observable correlation between reverse current and scaling of
d log(I )/dV with applied bias (scaling exponent α extracted as
described before). Scale bar in each case is counts.
The spatial analysis of d log(I )/dV has likewise turned
out to be very informative. It is easily seen that the
spatial variations of the absolute magnitude of d log(I )/dV
in figure 9(B) reveal the same overall pattern as figures 9(A)
and (C), albeit in an anti-correlated fashion—the magnitude of
d log(I )/dV is smaller in the regions of higher current. At
the same time, the scaling of d log(I )/dV with bias (exponent
α in d log(I )/dV = f (V α )) is spatially heterogeneous, but
without a clear pattern, and with little correlation to the patterns
10
P Maksymovych et al
in figures 9(A)–(C). These trends are confirmed by the 2D
histograms in figure 10: d log(I )/dV spatially anti-correlates
with the raw current (figure 10(A)), exhibits a much cleaner
anti-correlation with the normalized current (figure 10(B)),
while α does not exhibit any significant correlation with the
raw current.
The spatial correlation between d log(I )/dV and the
absolute current yet again emphasizes that not all disorder
originates from prefactors in the transport equation, such
as the contact area. However, a stronger correlation of
d log(I )/dV with normalized current (figure 10(B)), both of
which eliminate the prefactor, compared to that of d log(I )/dV
with the raw current (figure 10(A)) confirms our earlier
conclusion that the prefactor contributes some of the disorder,
particularly in the lower half of the image. We can even assert
that normalizations ‘recover’ some of the intrinsic features,
such as two clear depressions at the bottom of the map in
figure 9(B).
At the same time, the lack of significant spatial correlation
of the exponent α with the disorder pattern observed in the
current identifies that the spatially correlated variations in
d log(I )/dV originate primarily from the (near) zero-field
terms, such as the interfacial barrier height in the Fowler–
Nordheim equation, rather than the changes in the built-in
field (which would change the exponent, figure 5(D)). It is
straightforward to assert that changing the barrier height does
indeed shift the magnitude of the d log(I )/dV = f (V ) curve,
but has a smaller effect on its exponent. Furthermore, the
higher barrier yields a higher absolute value of d log(I )/dV
and a lower value of current, which explains why d log(I )/dV
is anti-correlated with both the raw and normalized current
values (figure 10). Finally, within our approximations for the
electric field at the interface and 1D transport equations, the
absolute values of d log(I )/dV in figure 9(B) are consistent
with Fowler–Nordheim tunneling, a built-in bias from −1.5
to −2.5 V, total donor/acceptor density of 1024 –1026 m−3
and zero-field barrier height from 0.4 to 0.8 eV. In the
future, macroscopic characterization of the film properties
(particularly the respective trap distributions and response
times), combined with more detailed mapping of the I –V
curves, can help in making these estimates more accurate.
In summary, we have identified the dominant conduction
mechanisms behind local I –V curves through a 30 nm film
of PbZr0.2 Ti0.8 O3 using a combined analysis that relies on
the use of current-normalized differential conductance and
spatial variations of the I –V curves across the surface.
The observed transport characteristics are consistent with a
model where I –V curves are interfacially limited by trap-
assisted Fowler–Nordheim tunneling at low bias and bulk
limited by Poole–Frenkel hopping at high bias, with a
crossover near −4 V. As the temperature is lowered, the
experimentally detectable conductance shifts into the high-
field regime, eventually dominated by Poole–Frenkel hopping
below ∼200 K. Spatially resolved analysis of the I –V
curves has further revealed that the two mechanisms exhibit
significantly different degrees of disorder. The disorder, in
turn, originates partly from the changes in the interfacial
barrier height and partly from the changes in the contact
Nanotechnology 22 (2011) 254031
area. The two effects can be reasonably well separated using
differential conductance. The methodology presented here is
applicable to any wide bandgap semiconductor or polymer
material, as well as to a variety of transport mechanisms
provided their functional form is known. We therefore
envision that the systematic analysis of normalized I –V
curves will shed new light on the rapidly growing number
of local transport experiments on wide bandgap oxides and
enable more quantitative characterization of their dielectric and
interfacial properties and phase transitions, many of which are
relevant to applications in information technology and energy
harvesting and storage.
Acknowledgments
Research was conducted at the Center for Nanoscale Materials
Sciences (PM, MP, APB, SVK), sponsored at the Oak
Ridge National Laboratory by the Division of Scientific User
Facilities, US Department of Energy. The work at Berkeley
is partially supported by the SRC-NRI-WINS program as well
as by the Director, Office of Science, Office of Basic Energy
Sciences, Materials Sciences Division of the US Department
of Energy under contract no. DE-AC02-05CH1123.
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