Complex

Complex Impedance
Impedance Spectroscopy
Spectroscopy

S. S. Bhoga
Department of Physics
RTM Nagpur University, Nagpur
What is Complex Impedance Spectroscopy ?

Involves measurement of
Real and imaginary parts of impedance/
admittance
Over wide frequency range (10-3 to 1014 Hz)
Convey information
Microscopic ion dynamics
Ionic bulk conductivity
Electrode polarisation
Activation enthalpy for ion migration
Micro-heterogeneities
Dielectric constant
Electric polarization
Etc.
What is Complex Impedance Spectroscopy ?

() is Fourier transform of autocorrelation function

of current density, i

V 
 ( )    i (0).i (t )  exp(  j t )dt ,
3k  T 0
V - volume of the sample
1 N qi - Charge on mobile specie
here i (t )   qi vi (t ),
V 1 vi - Velocities
 - Angular frequency

It resolves elementary hopping processes

It is a very powerful microscope in time.
Why Complex Impedance Spectroscopy ?

Mass transport in solids is vital for many technological

applications
Mobility of ions under influences
Chemical gradient - Diffusion
Electric potential gradient - Conductivity

Disadvantage of dc conductivity
No instrument is

S/cm)
Polarization of ions introduces  Bulk
 capable to
error determine
ac Conductivity electronic
Avoids polarization
Time (Min)
Single frequency
Fig:- Variation of dc conductivity with
First hand information (screening time
test)

 is time/frequency dependent
Why Complex Impedance Spectroscopy ?

polarization
Electrode

Dielectric
 S/cm)

losses
Bulk

Bulk conductivity – dc
Log f (Hz)
Fig:- Variation of ac conductivity

Only due to ion migration

with frequency

Dielectric

polarization
losses

Electrode
Excludes electrode polarization

Z” Ohm)
RBulk
Dielectric loss Z’ (Ohm)
Fig:- Cole-Cole plot
(impedance)

Grain-boundary contribution

polarization
Electrode
Y” S)
GBulk Y’ (S)

Fig:- Cole-Cole plot

(Admittance)
Why Complex Impedance Spectroscopy ?

Provides straight-forward determination of electrolyte

resistance irrespective of degree of electrode
polarisation.

Does not necessarily require use of reversible

electrodes or complicated cell geometry

Determine dielectric properties of material

Ease of studying electrode polarisation

Mathematical Formulation and
Electrical Equivalent Models
System
Systemcharacterization
characterization

Experiment
Experiment Theory
Theory

Mathematical
Mathematicalmodel
modeland
and
Analyses
Analyses

Plausible
PlausiblePhysical
Physicalmodel
model Equivalent
Equivalentcircuit
circuit
CIS – Basics/Electrical Equivalence

Sine waves are use

V(t) = Vm exp(jt ) Input

Output

I(t) = Im exp(jt )

Input and output waveforms are same

Z in time domain obeys Ohms law

Z () = |Z| exp (-j)
 CIS – Basics/Electrical Equivalence

Real and Imaginary parts

0 (R/2, R/2)

G R
Z  2  ,

Z”
r G  B 2 1  ( RC ) 2
(0,0) Z’ (R,0)
B R 2 C
Z  2 
i G  B 2 1  (RC ) 2 Electrical Equivalent Complex impedance response

Eliminate  and rearrange

(Zr -R/2)2 + Zi2 = (R/2)2 .

Eq. of circle with radius R/2

 CIS – Basics/Electrical Equivalence

Real and Imaginary parts 0 (R/2, [R cos(ap/2)]/[2(1+sin(ap/2]

R{1  ( )1 sin( / 2)}

Zr 
2 (1   )
1  2( 0 )1 sin( / 2)  ( 0 )

Z”
CPE
1
R{( 0 ) cos( / 2)} (0,0) Z’
Zi 
2 (1   )
1  2( 0 )1 sin( / 2)  ( 0 ) Electrical Equivalent Complex impedance response

Eliminate n and rearrange Depressed by angle 

Centre (R/2,[R tan{/2}]/2)
(Zr -R/2 )2 + ( Zi -{[R tan (/2)]1/2 })2 = r 2
Top - (R/2, [R cos(/2)]/[2(1+
sin . (/2])
where, r 2 = (R/2)2 + {(R/2)2 + tan(/ 2)}2
Radius r
 CIS – Basics/Electrical Equivalence
Solid ion conductor

Each physical processes

Metal electrodes
give separate semicircle
provided their values of
 are widely different
Z”

R1 Z’ R1 + R2

Bulk Grain-boundaries Metal electrode As first approximation,

each semicircles may be
R3
R1 R2
Zw considered as response
of R-C combination.
C1 C2 Cdl
Electrical Equivalence - Complications
C1
C2

R1
(a’)

Obtaining equivalent circuit to

R1C1=1
simulate phenomenon of
Z”=(jC2)-1

electrode
Z”

Z”

Z’ R1 Z’
(a) (b) Highly convoluted combination
of line and semicircle
Z”

Z”

Z’ Z’

(c) (d)
 Experimental - Measurement

Impedance data during T1

ts1 te1 ts  Start time
cooling cycle ts2 te2 te  End time
T2 ts3 te3
Cooling 2oC per min T3 ts4 te4

Temperature
T4 Dwell time, 30 min.
ts5 te5
Dwell time 30 min T5
T6
Measurement at end of
dwell time 40 100 160 220 280
Time
 Experimental – Set up

HP4192A
meters
Mass flow Display
Key pad
parameters
Low High
O2 2gas
CO2/SO gasgas
Ar cylinder
cylinder

HP 16048 test leads

ntium processor

G
P

B
I
compatible PC

Sample 1
Keithley 7001
Sample 2
Sample 3
Sample 4 R.F. Switch
Sample 5
Sample 6
Temperature
Furnace Programmer

Six samples Gas partial pressure Frequency

5 to 13mm dia 100ppm to 10% 5 to 13x106 Hz

Temperature - R.T. to 700oC

 Experimental – Set up

Frequency
10x10-6 to 1x106 Hz

meters
Mass flow Solartron 1287
Temperature
R.T. to 700oC
O2 2gas
CO2/SO gasgas
Ar cylinder
cylinder Solartron 1255B
FRA
G
P

Scribner Z-plot and Z-view

I

(Pentium processor
IBM compatible PC

Sample Temperature
Holder programmer

Furnace
 Data Fitting/Circuit Simulation

2
Fitted (CNLSF) data to
Z (0)  Z ()
Z    Z (  ) 
0

0 2 4 6 8 10 12 
 
1   j  
”(k 

 
20
Sum of squares is minimized by
10
unity weighting

 
0

S i   R i    I i 
0 10 20 30 40 50 60 2 2 1/ 2
Z’ (k)
 Data Fitting/Circuit Simulation
Parallel to interface
Cg
||
R
C
C
R C
||
R
|| || ||
R R
4
C
i
C
2 i
C
0
Ci

0 2 4 6 8 10 12 i I i R
R R R
”(k 

Bulk (interior) C
20
R
Grain Perpendicular
10
(a) (b) to interface
||
C
0
0 10 20 30 40 50 60

Z’ (k)
CPE C

R
|| CPE
Ci
CPE R

Ri

(c)
 Conduction Mechanism

1.4

1.3 Intragrain
1.2
Intergrain
 Ea 
f p  fo exp  1.1

 kT  1

0.9

Ea (eV)
La

Intragrain conduction
1.3 0 Dy
Y

modifies on doping
1.2

1.1

But not grain-boundary 1

0.9
0 5 10 15

Vacancy %