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C 2003 Kluwer Academic Publishers. Manufactured in The Netherlands.
Submitted March 11, 2003; Revised August 1, 2003; Accepted October 13, 2003
Abstract. Modelling of impedance spectroscopy (IS) data of electroceramics depends critically on the correct
choice of equivalent electrical circuit so that the extracted parameters have physical significance. The strategy
proposed to choose the correct circuit involves analysis of IS data in several of the four complex formalisms:
impedance, electric modulus, admittance and permittivity together with consideration of the frequency and temper-
ature dependence of data and the magnitude and temperature dependence of extracted resistance and capacitance
values. This is demonstrated using IS data from oxide-ion conducting La0.80 Sr0.20 Ga0.83 Mg0.17 O2.82 ceramics over
the range 182 to 280◦ C. Low temperature data are fitted first, to allow a full characterisation of the bulk response;
some of the bulk parameters may then be fixed to enable fitting of the higher temperature data which increasingly
feature lower frequency phenomena such as grain boundary impedances. The most appropriate circuit in this case
is found to consist of a parallel combination of a resistor, capacitor and constant phase element (CPE) for the bulk
response in series with a resistor and capacitor in parallel for a constriction resistance. The origin of the constric-
tion resistance may be associated with the presence of plate-like LaSrGaO4 secondary phase within the grains
and/or with the presence of pores at the grain boundaries. The importance of choosing (a) the correct equivalent
circuit and (b) approximately correct input values for the various circuit parameters to be fitted and refined are
demonstrated.
From Eq. (5), is to analyse first the lowest temperature data in which
the bulk response of the sample is dominant and for
M ∗ = M + j M = jωCo Z ∗ = jωCo (Z − j Z ) which the circuit in Fig. 2 is usually appropriate. This
region of the ac spectrum, when log Y is plotted against
= ωCo Z + jωCo Z . log ω, should contain a low frequency plateau which
may, or may not overlap with dispersions at lower fre-
Hence, M = ωCo Z and M = ωCo Z . Detailed quencies associated with the onset of grain boundary or
consideration of the equations for M and Z shows other thin layer phenomena, together with the high fre-
that for a circuit consisting of a single parallel RC ele- quency dispersion characterised by a power law, with
ment, Z and M have the same functional form, giving a gradient equal to n. Only at the lowest temperatures,
rise to a Debye peak when plotted against frequency, is the power law dispersion adequately displayed since
but have different weighting factors in that the Z peak it is a high frequency effect that moves to increasingly
is scaled according to R whereas the M peak is scaled higher frequencies with increasing temperature. In our
according to C −1 . Hence, Z ∗ and M ∗ complex plane experience, all ionic conductors and electronic semi-
plots (or Z and M spectra) highlight different aspects conductors show this bulk power law dispersion, which
of the same data. Since Z ∗ plots are dominated by Rgb is an example of Jonscher’s ‘Universal Law of Dielec-
if Rgb Rb , they provide useful information about the tric Response’ [4] and therefore, to recognise and char-
grain boundaries but little or no information on the bulk acterise this region of the ac spectrum provides a good
response. Any equivalent circuit analysis based only on starting point in data analysis. If suitable low tempera-
conventional Z ∗ plots, therefore, does not necessarily ture data are not available and instead, only the onset of
provide adequate weighting to the bulk response of the power law dispersion is seen, overlapping with the
such ceramics. In contrast, M ∗ plots are dominated by bulk conductivity plateau, then it is very easy to obtain
the bulk response since Cb Cgb but provide little or erroneous values of n and A by fitting over a limited
no information about the grain boundaries. Thus, by data set. In such cases, n may be fixed at a typical value
using a combination of formalisms, different aspects of 0.6.
of the same data are highlighted [3]. Once the data in the region of the bulk response
This brings us to the critical step in data interpre- have been fitted, higher temperature data may be con-
tation and analysis. Often, no prior information about sidered by fixing, if necessary, the value for n of the
the expected equivalent circuit and/or magnitudes of bulk response (n usually shows little temperature de-
resistance and/or capacitance for a sample is available. pendence). It should then be possible, progressively, to
The approach that we adopt in such cases is to first, find the best circuit to model the grain boundary and
visually inspect the data in at least two of the four for- other, lower frequency components.
malisms, usually Z ∗ and M ∗ , and determine the number The temperature dependence of R and/or C val-
of RC circuit combinations that are likely to be needed ues extracted from the data analysis using various
to model and fit the data. For most samples, a series equivalent circuits may also be useful in discriminat-
combination of parallel RC elements is usually appro- ing between circuits. Thermally-activated resistances
priate, which is why Z ∗ and M ∗ formalisms are used associated with electronic and ionic conduction are
since each parallel RC element gives rise to its own commonly governed by the Arrhenius law. A plot of
Z , M peaks. A range of equivalent circuits with, or log(R −1 ) against reciprocal temperature should be lin-
without CPEs in addition to, or in place of the R and ear unless curvature associated with phenomena such
C components are then fitted to the data. The quality as extrinsic-intrinsic crossover, phase transitions, es-
of the fits over the entire frequency range, for all four pecially order-disorder transitions, and defect dissoci-
formalisms is assessed. ation occurs. In the absence of such effects, any depar-
In the early stages of data analysis, especially if ture from linear, Arrhenius-type behaviour for Rb and
the equivalent circuits contain a large number of fit- Rgb and/or unexpected high or low activation energies
ting parameters and all are allowed to vary simultane- may be evidence for an incorrect equivalent circuit.
ously, it may be difficult to obtain a fully satisfactory With the exception of ferroelectric materials, capaci-
fit. An important strategy is then to focus on a range tance values usually have little or no temperature de-
of temperatures over which one particular feature of pendence. For ferroelectric materials in the temperature
the impedance response is dominant. Our preference range above the Curie temperature, Tc , the capacitance
A Strategy for Analysis and Modelling of Impedance Spectroscopy Data of Electroceramics 169
data should follow Curie-Weiss behaviour, with a lin- with various equivalent electrical circuits using ZView
ear dependence of C −1 on temperature, and this is a equivalent circuit fitting software [5]. At frequencies
useful diagnostic. Anomalous values or temperature above 1 MHz, the impedance data were unreliable due
dependence of capacitance may indicate an incorrect to inductive effects and were excluded.
equivalent circuit.
In our experience, when considering each of the
points above, it is usually possible to find one equiv- 3. Equivalent Circuit Analysis
alent circuit that accurately fits IS data over a wide
ω, T range in all four formalisms and which gives a IS data were analysed assuming a brickwork model for
physically reasonable set of R, C values. In particu- the ceramic microstructure; four equivalent circuits, A,
lar, it is often possible to discriminate between equiva- B, C and D, shown in Fig. 3, were used to try and at-
lent circuits which appear to give acceptable fits to Z ∗ tain the best fit to the experimental data. Circuits A–C
plots. Here we illustrate this approach to analyse data assume the ceramic response to be modelled on a bulk
for oxide-ion conducting La0.80 Sr0.20 Ga0.83 Mg0.17 O2.82 component only, whereas circuit D, assumes a series
ceramics over the temperature range ∼182 to 280◦ C. combination of two components which would repre-
sent bulk and grain boundary regions. The lower fre-
quency limit for modelling the data was chosen from
2. Experimental Z ∗ and/or ε spectroscopic plots so as to exclude, as
far as possible, data associated with the electrode pro-
La0.80 Sr0.20 Ga0.83 Mg0.17 O2.82 (LSGM) ceramics were cesses (see Fig. 4). This was necessary as it was not
synthesised by a solid state route. Stoichiometric possible to obtain sufficient data from the available
amounts of La2 O3 (99.99% pure), Ga2 O3 (99.995%),
MgO (reagent grade) and SrCO3 (99.9%+) powders
were milled together in water with zirconia beads. The
La2 O3 and MgO powders were dried at 1000◦ C prior
to weighing. After drying, the mixture was calcined
at 1250◦ C for 6 hours, milled and dried. Pellets were
pressed uniaxially at about 50 MPa and sintered at
1470◦ C for 6 hours. Phase purity was checked by X-ray
diffraction (XRD) using a Guinier-Hägg camera with
Cu Kα1 radiation of wavelength 1.5405 Å, and by Scan-
ning Electron Microscopy (SEM) using a JEOL JSM
6400 scanning electron microscope with a 20 kV accel-
erating voltage. Ceramic density as a percentage of the
theoretical X-ray density was calculated using LSGM
lattice parameters and the mass and dimensions of the
ceramics.
Sputtered gold electrodes were deposited on ce-
ramic samples for 8 minutes at 20 mA current under
argon using an Emscope SC500 gold sputter-coater.
Samples were connected to a measuring jig and placed
in a non-inductively wound furnace where the tempera-
ture was controlled to ±2◦ C over the temperature range
150 to 300◦ C. IS was performed at ∼10◦ C intervals
using a Hewlett Packard 4192A impedance analyser at
frequencies ranging from 5 Hz to ∼13 MHz. IS data
were corrected for the geometric factor of the sam-
ple (thickness/electrode area), the stray capacitance of
the measuring jig and the resistance and inductance Fig. 3. Equivalent electrical circuits A, B, C and D used to model
of the measuring leads. Corrected data were modelled IS data from an LSGM ceramic.
170 Abram, Sinclair and West
5. Discussion
Circuit D gives the best fit to the data in all four for-
Fig. 7. log-log spectroscopic plots of the real and imaginary parts malisms over the measured temperature range. The
of Z ∗ (a), M ∗ (b), Y ∗ (c) and ε ∗ (d) measured at 232◦ C. ε plateau magnitude of CD1 , ∼3 pF, is a typical bulk capacitance
regions are indicated by short arrows. and an n value of 0.59 and A value of ∼10−10 S sn for
A Strategy for Analysis and Modelling of Impedance Spectroscopy Data of Electroceramics 173
Fig. 9. log-log spectroscopic plots of the real and imaginary parts of Fig. 10. log-log spectroscopic plots of the real and imaginary parts of
Z ∗ (a), M ∗ (b), Y ∗ (c) and ε∗ (d) measured at 190◦ C (open symbols) Z ∗ (a), M ∗ (b), Y ∗ (c) and ε∗ (d) measured at 190◦ C (open symbols)
and the best-fit simulation (crosses) for circuit C. and the best-fit simulation (crosses) for circuit D.
174 Abram, Sinclair and West
−1 −1
Fig. 11. Arrhenius plot of fitted values of RD1 and RD2 from circuit
D for the temperature range 182 to 280◦ C.
Fig. 14. Z ∗ plot of data measured at 280◦ C (open symbols) and the
−1 −1
best-fit simulation (crosses) for circuit B with the n value for CPEB Fig. 15. Arrhenius plots of RD1 and RD2 from solutions 1, 2, 3 and
allowed to refine. 4 for circuit D.
176 Abram, Sinclair and West
working model with which to analyse the impedance and their satisfactory inclusion in data analysis helps
data. It may be that, in practice, a two or three di- greatly in discriminating between competing model
mensional model provides a more accurate description circuits.
of the impedance response, as discussed by Fleig and
Maier [12–14], but there is no experimental justifica-
Acknowledgments
tion for the use of such a more complex model in this
case.
We thank the EPSRC for funding.
6. Conclusions References
The electrical behaviour of oxide-ion conducting 1. J.T.S. Irvine, D.C. Sinclair, and A.R. West, Advanced Materials,
La0.80 Sr0.20 Ga0.83 Mg0.17 O2.82 ceramics was modelled 2, 132 (1990).
2. D.P. Almond and A.R. West, Solid State Ionics, 9/10, 277 (1983).
successfully using an equivalent electrical circuit con-
3. D.C. Sinclair and A.R. West, Journal of Applied Physics, 66(8),
sisting of a parallel combination of a resistor, capac- 3850 (1989).
itor and CPE to model the bulk response, connected 4. A.K. Jonscher, Nature, 267, 673 (1977).
in series with a parallel combination of a resistor and 5. ZView Version 2.1b, Derek Johnson, Scribner Associates, Inc.
capacitor to model the response of a constriction resis- 6. K. Huang, R.S. Tichy, and J.B. Goodenough, Journal of the
American Ceramic Society, 81(10), 2576 (1998).
tance. To identify and deconvolute these two responses
7. A.R. West, D.C. Sinclair, and N. Hirose, Journal of Electroce-
it was necessary to analyse IS data using log-log spec- ramics, 1(1), 65 (1997).
troscopic plots of the real and imaginary parts of all 8. R.J. Grant, I.M. Hodge, M.D. Ingram, and A.R. West, Nature,
four complex formalisms over a temperature range be- 266(5597), 42 (1977).
tween 182 and 280◦ C. Alternative equivalent circuits 9. K. Huang, R.S. Tichy, and J.B. Goodenough, Journal of the
American Ceramic Society, 81(10), 2565 (1998).
were eliminated by critically assessing the quality of
10. E.J. Abram, D.C. Sinclair, and A.R. West, Journal of Electroce-
fit to the measured data over a range of frequency and ramics, 7, 179 (2001).
temperature. 11. D.C. Sinclair and A.R. West, Physical Review B, 39, 13486
It is probably true to say that the reasons why (1989).
impedance data often show departures from Debye- 12. J. Fleig and J. Maier, Journal of the Electrochemical Society,
145(6), 2081 (1998).
like ideality are not well-understood. At the simplest
13. J. Fleig and J. Maier, Journal of the European Ceramic Society,
level, n and A may be regarded as adjustable fitting pa- 19, 693 (1999).
rameters. Nevertheless, n and A are parameters whose 14. J. Fleig and J. Maier, Journal of the American Ceramic Society,
temperature (in)dependence is usually well-behaved 82(12), 3485 (1999).