Impedance Spectroscopy

and
Material Science

Dr. Muhammad Idrees

Department of Physics, CIIT,
Lahore, Pakistan

Importance
Electronic,
Ionic , Mixed
Conductor
and
Even
Insulators
Alloys, Ceramics, Polymeric,
Superconductors
Dynamic behavior of bound
and mobile charges
Isolate Electrical Response of
Different Phases
Grain
boundaries can be
Characterized and Interpreted

Principle
Sinwave input

Sinwave output

Linear System

V( i) = Vo sin t

Excite a system
with AC voltage

V() Vo exp(it )

I( i) = Iosin (t

System responds with an AC

current

I ( ) Io exp i (t )

The ratio output / input signal determines the

Impedance for the corresponding
frequency:
Z( ) Zo exp(
i )
The impedance also includes the
Phase Shift

Z (i ) R iX

resistive part

capacitative part

Other Formalisms of the

Impedance Data
Complex permittivity

* = / + j //

Complex admittance

Y* = Y/ + j Y//

Complex Modulus

M* = M/ + j M//

Data Presentation and Interpretation

Bode and Plane
Plots
Bode Plots
1. At low frequencies the applied signal
behaves like a dc signal (Phase shift is
zero) and the corresponding quantity is
equivalent to dc counterpart .
2. At low frequencies the, the larger
polarization is due to presence of
response from all type of polarizations
3. As the frequency increases the phase
shift increases and the carriers lag
behind the applied frequency and the
polarization seizes..
4. The fr indicated by dotted lines is the
frequency beyond which the carriers or
dipoles are not mobile enough to follow
the applied ac signal

Plane Plots
1. Real
quantity
is
plotted
against
imaginary part as a parametric function
of frequency.
2. Higher intercept (low frequency) at real
axis is the total impedance of the
system and is equal to the dc
resistance
3. As the frequency increases, the phase
shift ( or ) increases and the

R
impedance is given
Z * by the phasor
Z jZ
1 jRC
diagram..

R
Z/
2
1

RC
)

RC
2
1

RC
)

Z // R

Systems with Multiple Relaxations

Larger the product RC, larger

will be fr

Relaxation frequency of
different phases is different

carriers

at

Difference in fr depends upon the relative

resistances and capacitances.
Grain boundaries are generally more
resistive and capacitive, Hence, the
carriers
relax
at
relatively
lower
frequencies
In some cases the electrode polarization
effect is also present and it usually
appears at very low frequencies

Other Formalisms of the

Impedance Data
Complex permittivity

* = / + j //

Complex admittance

Y* = Y/ + j Y//

Complex Modulus

M* = M/ + j M//

Advantages of Other Formulism

For Example

C
M
Cg

C
Cg

(Rg C g ) 2

2
1 (Rg C g ) C gb

M* = jwCoZ* = M/ + j
M//

(RgbC gb ) 2

2
1 (RgbC gb )

Rg C g
RgbC gb
C

2
2
1

R
C
)
C
1

R
C
)

g g
gb
gb gb

Disorder in a System

Data Modeling

The brick layer model

S.M. Haile, D.L. West, J. Campbell, Journal of Materials Research 13 (1998) 1

NorFERM-2008, Gol

10000

8000
6000
4000
2000

LaFe0.9Ni0.1O3

0
0

10

10

10

10

10

10

10

10

Frequency (Hz)

-10000

202K
218K
226K
234k
246K

-8000

-6000

If fr/T > 0

-4000

-2000

Ionic or electronic conductivity?

10

10

10

10

10

10

1E-3

gb
1E-4

1E-5
-1

(s )

= 2fr

10

Frequency (Hz)

(activation energy for migration)

= oexp(Er/kT)

10

//

fr/T > 0 in oxide (localized)

12000

Z ( )

Localized or delocalized nature of

the electrical charge carriers
fr/T < 0 (metals and Si, Ge)

218K
226K
238K
250K
268K
288K

14000

Z ( )

Applications
Electrical Investigations

16000

1E-6

1E-7

1E-8
0.0032

0.0036

0.0040

0.0044
-1

-1

T (K )

0.0048

0.0052

Microstructure and Defect Chemistry at G.Bs

Electron Phonon Interactions
Polaron Formations

Impedance spectroscopy continued..

LaFeO3
Two types of thermal
activations
In case of the elemental semiconductors
On the other hand, in oxide
semiconductors where charge carriers are
localized
SPH
= (o/T) exp(-Ec/kBT)
Ec = WH+Wb/2
= oexp(WH/kBT)
T xQuant
tan(max
) ndEexpW(-W
/2k
T)
E (g)
(g)b
WB
c

ity

(gb)

Wb/2

Wb/2

(gb)

(g)

(gb)

Resistan

0.475

0.541

----

----

----

----

ce
Tan()

0.477

0.553

0.448

0.514

0.029

0.039

Modulus

----

----

0.438

0.554

----

----

Idrees et.
(M ) al.
//

Acta Materialia 59 (2011) 1338.

14

On Adding Ni in LaFeO3
LaFe0.9Ni0.1O3

LaFe0.7Ni0.3O3

LaFe0.5Ni0.5O3

Relaxation frequency increases in

accord to the increase in the Fe4+
content or band L
Activation energy for carrier hopping
also decreases with doping Ni in
accordance to the increase in band L

15

Now we make a qualitative analysis of the

localized and itinerant behavior
Jonscher Power Law

(d(/ac)/d > 0)

Peminov et. al.

16

Impedance spectroscopy continued..

Origin of colossal dielectric

response in LaFeO3
hd = (2/ZNd(Vb-Va))1/2
Ce 1/hd

dgb nt/nf
Cgb = gb Agb/dgb

M. Idrees et. al.

Acta Materialia 59 (2011) 1338.

17

Thanks