Impedance spectroscopy studies on polycrystalline BiFeO3 thin films on

Pt/Si substrates
Amar Srivastava, Ashish Garg, and Finlay D. Morrison

Citation: J. Appl. Phys. 105, 054103 (2009); doi: 10.1063/1.3078822

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 JOURNAL OF APPLIED PHYSICS 105, 054103 共2009兲

Impedance spectroscopy studies on polycrystalline BiFeO3 thin films

on Pt/Si substrates
Amar Srivastava,1 Ashish Garg,1,a兲 and Finlay D. Morrison2
1
Materials and Metallurgical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
2
School of Chemistry, University of St Andrews, St Andrews KY16 9ST, United Kingdom
共Received 11 November 2008; accepted 29 December 2008; published online 4 March 2009兲
In this paper, we report on the results of temperature dependent impedance measurements on
chemical solution deposited BiFeO3 thin films on Pt/Si substrates. X-ray diffraction analysis showed
the presence of predominately single phase BiFeO3. The measurements were made in the frequency
range of 100– 107 Hz and between 27 and 250 ° C. Plots between real and imaginary parts of
impedance 共Z⬘ and Z⬙兲 and electrical modulus 共M ⬘ and M ⬙兲 in the above frequency and temperature
domain suggest the presence of two relaxation regimes which are attributed to bulk and grain
boundary responses. Below 150 ° C, both conductivity and real dielectric constant show a steplike
behavior. The frequency independent regions in 10–100 kHz indicate relaxation of the bulk
conduction, while at lower frequency there is a strong frequency dependence associated with the
dispersion toward relaxation of the grain boundary. In contrast, at and above 150 ° C, frequency
independent behavior of dc conduction becomes dominant. The bulk dielectric constant was
estimated as ⬃225, which is close to the values reported in the literature. Estimated grain and grain
boundary conductivity activation energies are 0.28 and 0.81 eV, respectively. © 2009 American
Institute of Physics. 关DOI: 10.1063/1.3078822兴

I. INTRODUCTION were subsequently investigated using impedance analyzer at

various temperatures for the dielectric characterization.
BiFeO3 共BFO兲 is a multiferroic material exhibiting si-
multaneous presence of ferroelectric and magnetic orderings
and has attracted significant amount of interest in the recent II. EXPERIMENTAL DETAILS
years due to its potential in various applications in the fields To deposit BFO films on Pt/ Ti/ SiO2 / Si 共100兲 substrates
of spintronics, data storage, etc.1–3 Bulk BFO possesses a by chemical solution deposition method, precursor solutions
rhombohedrally distorted perovskite structure at room tem- were prepared using 99.9% pure hydrated bismuth nitrate
perature and shows ferroelectric transition with a Curie tem- 关Bi共NiO3兲3 · 5H2O兴 and ferric acetylacetonate which were
perature 共Tc兲 of 1103 K and a G-type antiferromagnetic or- dissolved in glacial acetic acid and 2-methoxyethanol, re-
dering with a Nèel temperature 共TN兲 of 643 K.4 Thin films of spectively, to yield a 0.1 M solution. The solution was spun
this compound have generated much interest in the past few coated on cleaned Pt/Si substrates at 4000 rpm followed by
years following the demonstration of very large polarization drying at 450 ° C for 11 min in air after deposition of each
in epitaxial films of BFO.5 In general, pulsed laser deposited layer. The process was repeated to yield a final thickness of
films of BFO 共Refs. 5 and 6兲 tend to exhibit superior room ⬃300 nm. Finally, the sample was postannealed for 1 h at
temperature ferroelectric and leakage characteristics com- 650 ° C in the nitrogen ambient.
pared to the sol-gel or chemical solution derived films.7–9 The phase analysis of the films was carried out using a
The presence of grain boundaries in the polycrystalline thin Thermoelectron ARL X’TRA grazing angle high resolution
films and the defect structure could be one of the major fac- x-ray diffractometer 共GIXRD兲 in ␪-2␪ mode. Temperature
tors in degradation of ferroelectric and leakage characteris- dependent dielectric measurements were made using HP
tics. While much attention has been paid toward enhancing 4294A impedance analyzer with applied ac voltage of 500
the leakage characteristics and polarization, dielectric studies mV. To facilitate the electrical measurements, 200 ␮m diam-
of BFO thin films have been lacking except a recent report eter Pt top electrodes were sputtered using a shadow mask.
on the epitaxial BFO thin films.10 In this context, a detailed The measurements were made from room temperature to
temperature dependent dielectric study is needed to under- 250 ° C and in a frequency range of 100– 107 Hz.
stand the mechanisms of conduction and to determine the
electrical behavior of bulk and grain boundaries.
III. RESULTS AND DISCUSSION
In this paper, we report on temperature dependent dielec-
tric studies on the polycrystalline BFO thin films prepared by Figure 1 shows the GIXRD pattern of the BFO thin
chemical solution deposition method. The films were charac- films. The pattern shows that films possess a polycrystalline
terized by x-ray diffraction 共XRD兲 for structural analysis and structure with BFO appearing to be the main phase present.
Small amounts of secondary phases such as Bi25FeO39 and
a兲
Author to whom correspondence should be addressed. Electronic mail: Bi2Fe4O9 are present in the samples as evidenced by the
[email protected]. presence of a weak peak at around 2␪ ⬃ 28.8° 共marked as *兲.

0021-8979/2009/105共5兲/054103/6/$25.00 105, 054103-1 © 2009 American Institute of Physics

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054103-2 Srivastava, Garg, and Morrison J. Appl. Phys. 105, 054103 共2009兲

FIG. 1. XRD pattern of the BFO thin films showing all major peaks of BFO
共ICCD Card No. 73-0598兲. FIG. 3. 共Color online兲 Cole-Cole 共Nyquist兲 plot of impedance of BFO films
measured at different temperatures.
However, such phases affect the magnetic measurements
severely11 and may not affect the dielectric measurements to istic frequency maxima 共f max兲. No such peaks were observed
the same extent. at temperatures below 150 ° C in the measured range of fre-
Figures 2共a兲 and 2共b兲 show the variation of real and quency due to the high total sample resistance 共⬎10 M⍀兲.
imaginary parts of impedance 共Z⬘ and Z⬙, respectively兲 with The peak in Z⬙ is seen to shift to higher frequency with
frequency between 150 and 250 ° C. Figure 2共a兲 shows that increasing temperature, indicating decreasing relaxation
the Z⬘ values decrease with increasing frequency as well as time.
temperature. While frequency dependence of Z⬘ indicates di- Nyquist 共or Cole-Cole兲 plots of impedance data at dif-
electric relaxation, its temperature dependence indicates an ferent temperatures are shown in Fig. 3. At room temperature
increase in the dc conductivity of the samples with increas- two poorly resolved semicircular arcs are observed: a small
ing temperature. Figure 2共b兲 shows that at and above arc at high frequency 共inset兲 which is largely obscured by a
150 ° C, the Z⬙ data exhibit Debye-like peaks with character- larger semicircular arc at lower frequency. A series resistance
共Rs = 175 ⍀兲 is added to account for the high frequency in-
tersection of the semicircles with the Z⬘ axis. It is observed
from the plots that while below 150 ° C two semicircular
arcs are prominent; above 150 ° C a single broad semicircle
was observed in the low frequency region with no additional
contribution detected in the high frequency region. Under
such circumstances, at and above 150 ° C, the high fre-
quency semicircle is no longer within the frequency mea-
surement limits due to its decreasing time constant and that
is why more than one semicircle could not be clearly re-
solved in the impedance plot. As semicircle sizes in Zⴱ plots
scale according to magnitude of resistance, in instances
where two responses have greatly differing magnitudes of R
共often by orders of magnitude兲 the more resistive response
dominates entirely making resolution of the less resistive re-
sponse difficult. In such cases electric modulus data, where
semicircles scale inversely to capacitance, are often useful
for resolving the different relaxations.12 The electric modulus
共M ⴱ兲 was calculated from the following equation:
M ⴱ = M ⬘ + jM ⬙ = j␻C0Zⴱ = j␻C0共Z⬘ − jZ⬙兲, 共1兲
where ␻ is the angular frequency 共2␲ f兲 and the geometrical
capacitance is Co = ␧oA / d 共d is the sample thickness, A is
electrode area, and ␧o is the permittivity of vacuum =8.854
⫻ 10−14 F cm−1兲.
From the values of M ⴱ, we calculated the values of M ⬘
and M ⬙ using the relation M ⬘ = ␻C0Z⬙ and M ⬙ = ␻C0Z⬘. Fur-
ther, the values of M ⬘ and M ⬙ were plotted as shown in Fig.
4共a兲 where direction of increasing frequency is also indi-
FIG. 2. 共Color online兲 Variation in the 共a兲 real part of impedance 共Z⬘兲 and
共b兲 imaginary part of impedance 共Z⬙兲 with frequency for BFO films mea- cated. The figure shows two arcs below 150 ° C; this obser-
sured at different temperatures. vation, combined with the Zⴱ data is consistent with an

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054103-3 Srivastava, Garg, and Morrison J. Appl. Phys. 105, 054103 共2009兲

FIG. 4. 共Color online兲 Complex modulus plots of BFO films measured 共a兲 at
different temperatures and 共b兲 at 27 ° C clearly showing two semicircles. FIG. 5. 共Color online兲 Z⬙ and M ⬙ plots vs frequency at temperatures 共a兲
Arrow in 共a兲 shows the direction of increasing frequency and the inset in 共a兲 below 150 ° C and 共b兲 at and above 150 ° C 共Z⬙ is plotted on logarithmic
shows the equivalent circuit. scale兲.

equivalent circuit comprising two parallel RC elements and

Combined imaginary impedance and modulus 共Z⬙ and
resistor-inductor all placed in series as shown in the inset in
M ⬙兲 spectra versus frequency for all temperatures are shown
Fig. 4共a兲. The subsequent data analysis is based on this
in Figs. 5共a兲 and 5共b兲. In the plots shown for temperatures
equivalent circuit model. Here, the low frequency arc corre-
below 150 ° C 关Fig. 5共a兲兴, the Z⬙ spectra do not show any
sponds to the R2C2 response and the high frequency arc cor-
clearly defined features in the measured frequency range 共the
responds to the R1C1 response. For clarity, Fig. 4共b兲 shows
R1C1 relaxation appears as an inflection in the 10 kHz
the complex modulus plot of data collected at 27 ° C which
range兲. The M ⬙ spectra, however, clearly show two features:
is fitted with two semicircles, one at low frequency and an-
the first is a peak associated with R1C1 which occurs at
other at higher frequencies, clearly indicating the presence of
⬃5 kHz and shifts toward higher frequencies with increas-
two relaxations. The idealized response of the equivalent cir-
ing temperature; the second is an inclination with f max
cuit is shown along with the experimental approximation
⬎ 107 Hz which is associated with resonance of the measur-
used to extract R and C values. As described later, the series
ing leads 共RsLs兲. Below 150 ° C, Cole-Cole plots, as shown
RsLs represents the contribution of measuring leads and elec-
trodes, which is responsible for the high frequency non-zero in Fig. 3, also showed a large semicircle arc at lower fre-
intercept in Zⴱ plots and upturn in M ⬙ data. The values of C1 quencies, with a poorly resolved smaller second arc at high
and C2 were extracted from the arc intercepts on the M ⬘ axis frequencies. The Z⬙ and M ⬙ versus frequency plots in Fig.
below 150 ° C as shown. C1 and f max data were then used to 5共a兲 showed the presence of at least two peaks: one in Z⬙
calculate R1 values using Eq. 共2兲, with f max ⬍ 100 Hz and a associated resistance 共R2兲 greater
than 41 M⍀ cm and one peak in M ⬙ with f max, R1, and
␻␶ = 2␲ f maxRC = 1, 共2兲 capacitance 共C1兲 values, of 5 kHz, 1.61 M⍀ cm, and
19.84 pF cm−1, respectively, at 27 ° C. From the magnitude
where f max is the frequency of maxima of semicircles and ␶ of C1 this is attributed to the bulk response.13 The capaci-
is the relaxation time. Below 150 ° C, it was not possible to tance C2 was estimated to be ⬃60 pF cm−1 calculated from
calculate R2 in the same manner as f max for the semicircular the smaller circle in Fig. 4共b兲 at room temperature; R2C2 is
arc corresponding to R2C2 was below the measurable fre- therefore attributed to the grain boundary response.
quency limit of the equipment used. Above 150 ° C we ob- Above 150 ° C, Cole-Cole plots showed a single arc as
serve only one semicircular arc on the lower frequency side shown in Fig. 3. The Z⬙ and M ⬙ plots in Fig. 5共b兲 showed a
which indicates that the dominant contribution to the imped- peak in Z⬙ as well as in M ⬙ at 0.5 kHz at 150 ° C which shifts
ance stems from R2C2. toward higher frequencies with increasing temperature and a

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054103-4 Srivastava, Garg, and Morrison J. Appl. Phys. 105, 054103 共2009兲

TABLE I. Various calculated parameters for BFO thin films at various temperatures.

Temperature f max C1 R1 C2 R2 ␶b Tgb

共°C兲 共kHz兲 共pF cm−1兲 共M⍀ cm兲 共pF cm−1兲 共M⍀ cm兲 共␮s兲 共␮s兲

27 5 ⬃19.84 1.61 ⬃60 ¯ 31.9 ¯

75 11 ⬃19.84 0.73 ⬃60 ¯ 14.5 ¯
100 25 ⬃19.84 0.32 ⬃60 ¯ 6.3 ¯
125 55 ⬃19.84 0.15 ⬃60 ¯ 2.9 ¯
150 0.3 ¯ ¯ 116.0 4.58 ¯ 531.0
175 1.8 ¯ ¯ 102.0 0.87 ¯ 88.5
200 5.3 ¯ ¯ 94.7 0.32 ¯ 30.0
250 63 ¯ ¯ 41.0 0.06 ¯ 2.5

high frequency 共⬎107 Hz兲 incline in M ⬙. The Z⬙ peak at

150 ° C has associated R2 共=Rgb兲 and C2 共=Cgb兲 values of
4.58 M⍀ cm and 116 pF cm−1, respectively, which de-
crease to 0.06 M⍀ cm and 41 pF cm−1 at 250 ° C; this is
attributed to a semiconducting grain boundary component.
The C2 values were again calculated using Eq. 共2兲 and are
collated in Table I along with those for R2, R1, and C1. The
high frequency incline in M ⬙ is attributed to resonance of the
measuring leads. From the room temperature measurements,
we calculated value of real part of dielectric constant ␧⬘ from
the bulk response which was estimated to be ⬃225⫾ 15
which is in reasonable agreement with the values reported
for epitaxial BFO thin films.10
The relaxation times for both bulk and grain boundary
responses, ␶b and ␶gb, were calculated using respective R and
C values and the values are listed in Table I. It is clear that as
the maxima are shifted toward higher frequencies, the relax-
ation times decrease with increasing temperature. This cor-
roborates the observations made from Fig. 2 and is an indi-
cation of decreasing resistance of the samples as discussed
later.
To study the relaxation phenomena 共i.e., contribution of
bulk, grain boundary, and electrode interface effects兲 in the
material, we calculated the real and imaginary parts of di-
electric constant of BFO as

− Z⬙ Z⬘
␧⬘ = , ␧⬙ = . 共3兲
␻Co共Z⬘2 + Z⬙2兲 ␻Co共Z⬘2 + Z⬙2兲
Real and imaginary dielectric constants 共␧⬘ and ␧⬙兲 were
plotted against the frequency for all temperatures and are
shown in Fig. 6. The data in Fig. 6共a兲 show a strong disper-
sion in the real dielectric constant at low frequencies. The
plots of imaginary part of dielectric constant ␧⬙ versus fre-
quency are shown in Fig. 6共b兲 for temperatures from 27 to
125 ° C and Fig. 6共c兲 for temperatures from 150 to 250 ° C.
While a peak was observed in ␧⬙ versus frequency plots at
and below 125 ° C, 关Fig. 6共b兲兴, above 150 ° C, no peak in ␧⬙
is observed in the measurable frequency range. In Fig. 6共c兲,
the slope of the straight line of log-log plot at lower fre-
quency side equals ⫺1 which is the natural result of the
frequency independent conduction.14
This is also reflected in Fig. 7共a兲 which shows the ac
conductivity plots as a function of frequency at different
FIG. 6. 共Color online兲 Plots of the 共a兲 real dielectric constant 共␧⬘兲 vs fre-
temperatures. The curves tend to flatten with increasing tem- quency at all temperature; 共b兲 and 共c兲 complex dielectric constant 共␧⬙兲 with
perature, especially in the low frequency regions, suggesting frequency at different temperatures.

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054103-5 Srivastava, Garg, and Morrison J. Appl. Phys. 105, 054103 共2009兲

cies from the slopes of lines in Fig. 7共b兲 共ln ␴ac versus
1000/ T兲. The Arrhenius plots of the bulk 共␴b ⬵ 1 / Rb兲 and
grain boundary 共␴gb ⬵ 1 / Rgb兲 contributions are shown in the
inset in Fig. 7共b兲. The apparent values of activation energies
for bulk conduction 共Eb兲 and grain boundary conduction
共Egb兲 are 0.28 and 0.81 eV, respectively. The nature of these
plots simply suggests that frequency independent regions are
indicative of the grain boundary and bulk relaxation pro-
cesses, rather than a change in the conduction mechanism.
Previous studies made by Jonscher15 and Iguchi et al.16
suggested that the spectral intensity of the dielectric relax-
ation was activated thermally by virtue of hopping process of
charge carriers and small polarons in multigrain thin films.
However, in the present case it is likely that the high fre-
quency dispersion could well be due to the relaxation of
resistance 共Rs兲 than a separate conduction mechanism.
The calculated activation energy 共Ea兲 of 0.81 eV which
was obtained from the data on the higher temperature side is
comparable to activation energy of 0.84 eV for diffusion of
oxygen ions in titanate based bulk materials BaTiO3 and
Pb共Zr, Ti兲O3.17,18 Similar to many other perovskite-type ox-
ide polycrystalline thin films, oxygen vacancies in the
present BFO films are believed to create charge carriers via a
defect compensation mechanism and thus play an important
role in resistance and dielectric degradation.17
As seen in Fig. 6, there was a strong low frequency
dielectric dispersion in the high temperature region 共at and
above 150 ° C兲 where the frequency dependence of ac con-
ductivity reduced gradually. Hence the dc conduction mecha-
nism is not that of a simple metal-semiconductor-metal struc-
ture because this should not contribute to any polarization
FIG. 7. 共Color online兲 共a兲 ac conductivity plots for BFO films as a function and thus to the dielectric constant. There are a number of
of frequency at different temperatures. 共b兲 Plots of ac conductivity of vs possibilities for the origin of this polarization process at the
1000/ T共K兲 for BFO films at different frequencies. Dotted line in 共b兲 repre- electrode: the first can be accumulation of carriers either due
sents total conductivity which is roughly equal to dc conductivity above
to acceptor states trapping electrons at a depletion layer or a
150 ° C.
diffusion limited transfer process through the metal electrode
for ionic species such as oxide ions; the second may be re-
dc conduction behavior. The figure shows that, below lated to the catalytic activity of Pt for reaction with oxygen;
150 ° C, the data exhibit steplike behavior characteristic of a such an electrochemical reaction would again result in a po-
multiple relaxation process. The frequency independent pla- larization process. In the low temperature region 共below
teau in the 10–100 kHz range indicates relaxation of the bulk 125 ° C兲, the conduction behavior of Pt/BFO/Pt junction may
conduction ␴b = 1 / R1, while at lower frequency there is a be ascribed to the trap controlled space charge. In the present
strong frequency dependence associated with the dispersion samples, space charge could have been created by migration
toward relaxation of the grain boundary and total dc conduc- of oxygen vacancies toward various trap sites such as
tion ␴total = ␴dc = 1 / 共R1 + R2兲 ⬵ 1 / R2 as R2 Ⰷ R1. On the other interfaces/electrodes. The conduction mechanism appears
hand, at and above 150 ° C, the frequency independent be- more complicated than well known ionic hopping model,
havior of dc conduction becomes dominant. The dispersion because the data at temperatures above 125 ° C did not col-
seen at the highest frequency is related to the dispersion be- lapse on the single master curve as observed previously, e.g.,
tween relaxation of R1 and Rs. The full expression for the in BaFe0.5Nb0.5O3.19
total conductivity is actually ␴total = ␴dc = 1 / 共Rs + R1 + R2兲 and
the “bulk” relaxation is ␴b = 1 / 共Rs + R1兲, but the contribution
of Rs has been ignored for simplicity as Rs ≪ R1 , R2. IV. CONCLUSIONS
Figure 7共b兲 shows the Arrhenius plots of ac conductivity Detailed temperature dependent impedance studies were
at different frequencies. The dependence of the ac conduc- conducted on the chemical solution deposition derived BFO
tivity on temperature is explained by the Arrhenius equation thin films grown on Pt/Si substrates. Combination of imped-
␴ac = ␴o exp共− Ea/kT兲, 共4兲 ance and electric modulus showed the presence of grain
boundary relaxation in the lower frequency regime and tem-
where ␴o is a constant and Ea is the electrical activation peratures ⱖ150 ° C and bulk relaxation at higher frequencies
energy of conduction. Ea was calculated at different frequen- and temperature below 150 ° C. The real part of the dielectric

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054103-6 Srivastava, Garg, and Morrison J. Appl. Phys. 105, 054103 共2009兲

constant extracted from the bulk response was estimated to 共2006兲.

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This work was financially supported by the Department 13
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