Polythiophene Photo- and Impedance Spectroscopy

Intensity Modulated Photo- and
Impedance Spectroscopy at
Polythiophenes on TiO2 and Pt in the
Reduced State
W. Plieth1, C.A. Schiller2*, U. Rammelt1, N. Hebestreit1

1
Dresden University of Technology, Institute of Physical Chemistry and
Electrochemistry,
Mommsenstr. 13, D-010602 Dresden, Germany
2
ZAHNER-Messtechnik, Thüringer Str. 12, D-96317 Kronach, Germany
cas@zahner.de
Outline
Aims of this work:
 Understanding organic polymer semiconductors with
the help of their photo-electrochemical properties.
 Refinement of the intensity modulated photo-
spectroscopy IMPS: controlled intensity modulated
photo-spectroscopy ‚CIMPS‘.
Modeling experimental IMPS results by merging the
results of dynamic photo-potential, photo-current and
EIS measurements.
Plieth, Schiller, Rammelt, Hebestreit: Intensity Modulated Photo- and Impedance Spectroscopy on Polythiophenes ...
Overview of the Systems Under Test
and the Experimental Techniques Used
Systems  Ti- Pt- Ti- Photo-
TiO2- PTP TiO2 Diode-
Methods PTP Network
CIMPS
Potential   
CIMPS
Current    
Photo-
Pulse-   
response
EIS    
Preparation of Electrodes
• TiO2
Electrolysis of 0.5 M K2SO4 / 10 V, ca. 10 min.
(thickness: 25 nm)
• PTP / Pt
Electropolymerisation of 0.1 M 2,2‘ bithiophene / TBAPF6
(‘CV-scan‘ : 0 - 1.3 V vs SCE, scanrate = 20mV/s, 15 min.
thickness 200 nm)
• PTP / TiO2
- Pretreatment of TiO2-electrode with adhesion promotor TUTS
(11-(3-thienyl)undecyltrichlorsilane), ca. 30 min.
- Oxidation of Thiophene with FeCl3 in CHCl3, ca. 90 min.,
(thickness: 50-100 nm)
Comparison Between EIS and IMPS
EIS IMPS
I I
P
C U Z* U C H*
U*
Z*()=
I* I* A m 2
HIP() = P* , H IP =1
W
1) U* = U0.e jt
U* 2
2) I* = I0.e ( jt+ ) HUP() = P* , H UP = 1 V m
W
Principle of EIS: Principle of IMPS:

Modulation of the current I or the Modulation of the light, illuminating an
voltage U at an electrochemical cell C. electrochemical cell C. The quotient of one
The quotient of the dynamic magnitudes electric magnitude (current or voltage) with
leads to the Impedance Z* (or the dynamic light intensity P* leads to the
Admittance Y*=1/Z*). IMPS spectrum H*.
IMPS vs. Controlled Intensity
Modulated Photo Spectroscopy
IMPS CIMPS
FRA: Frequency Response Analyzer *)
: Content of the ZAHNER CIMPS Equipment
PG/IM6-FRA: Electrochemical Workstation IM6 *)
EPOT: Slave-Potentiostat / Power OPA *)

I
PSA IM6-FRA
PD/PSA: UV-VIS Photodetector / Sense Amplifier *)
BUVZ/GRL: UV-VIS Multi-LED-Emitter *)

H*
I PD EPOT
FRA
PG
U C H* U C
LED UVBL or GRL Ref
Usual IMPS set-up: Principle of CIMPS:

The function generator output of an FRA The LED light source is supplied by a
supplies an LED light source with modulated power-OPA, regulating the LED current in a
current. Mostly the cell current is correlated way, that the measured intensity tracks the
with the LED current to calculate the photo- set value at the cell‘s site. The cell voltage or
electrochemical transfer function H*. current is correlated with the measured
intensity to calculate H*.
Ti-PTP: CIMPS Current at 535nm.
150
6Hz 2
3n
|photocurrent| / AW -1m2
100
imaginary part / nAW -1m2

1n 50 0
phase 0
0
300p -2
-50
535pcur+007
100p 535pcur-150
535pcur-250 -100 4KHz 535pcur+007 -4
535pcur-350 535pcur-150
535pcur-250
-150 535pcur-350
30p
10m 1 100 10K -1 0 1 2 3 4 5 6 7

real part / nAW -1m2
frequency / Hz
Dynamic photo-current measurements at the binary system Ti-TiO2-PTP

under different cathodic polarization, starting at the OCP vs. Ag-AgCl.
Intensity: 10W/m2 at 535nm.
Left: Modulus/phase diagram. Right: Complex plane diagram.
Ti-PTP: CIMPS Potential from 535nm to
370nm.
100
0
phase/0
0
1m
imaginary part / mVW -1m2

|photovoltage| / VW -1m2
-100
 VW -1m2 -1
100
0
-2
-100
535ocpa
10 535ocpa 472ocpa
472ocpa 429ocpa 0 100 200
429ocpa 370ocpa -3
370ocpa
1m 10m 100m 1 3 10 100 1K 0 0.5 1 1.5 2 2.5 3 3.5

real part / mVW -1m2
frequency / Hz
Dynamic photo-potential measurements of the binary system Ti-TiO2-PTP

under light of different wavelengths at the OCP.
Intensity: 10W/m2.
Left: Modulus/phase diagram. Right: Complex plane diagrams.
Ti-PTP: EIS Measurements.
90
1M
75
100K
60
|impedance| / 
|phase| /
10K
45
0
535eis-150 30
1K
535eis-250
370eisocpb 535eis-350
429eisocpa
535eis-150 15
100
0
100m 10 1K 100K 100m 10 1K 100K
frequency / Hz
EIS measurements of the binary system Ti-TiO2-PTP

under light of different wave lengths at the OCP (left)
and under green light with different cathodic polarization (right).
The intensity was 10W/m2 except in the case of the 429 nm
illumination (2.5 W/m2).
Pt-PTP CIMPS Current
330
200
535pcur+281
150 535pcur+100 100
280
535pcur-100
imaginary part / nAW -1m2

|photocurrent| / nAW -1m2
100
230
50
phase 0
180
50
130 0
-80
20
-50
15
-30
10m 100m 1 3 10 100 1K -200 -150 -100 -50

frequency / Hz real part / nAW -1m2
Dynamic photo-current measurements of the system Pt-PTP

under light of 535nm wavelength at different cathodic polarization.
Intensity: 10W/m2.
Left: Modulus/phase diagram. Right: Complex plane diagram.
Schematic Section, Band Structure, and
Equivalent Circuit of a Semiconductor Electrode
SB: Schottky barrier junction
DL: Electrode double layer
CB: Conductance band
VB: Valence band
Ti TiO2 SB DL Electrolyte EF: Fermi level in equilibrium

Csb, Rsb, Isb: Impedance elements
and current source in the photo-
CB
active junction area
EF
Cox, Rox: Impedance elements of
the semiconductor bulk
VB
Cdl, Rct, Wct, Rel: Impedance
Csb elements of the electrode-
Cox Cdl electrolyte system (Randles
Rsb
circuit)
Rox Rct W ct
Rmet Isb Rel
W
Ti-TiO2-CIMPS Current Measurements and Model Fit
90
370pcur+100
8
370pcur+200
370pcur+300 75
10 370pcur+400 Cox Csb
370pcur+500 6
|photocurrent| / nAW -1m2
Cdl
photocurrent '' / nAW -1m2

370pcur+600 Rsb
60 Rox W ct
370pcur+700 Isb Rct Rel
7
|phase| /
W
4
Oxide Schottky- Double
45 barrier layer
5 2
0
30
0
3 15
-2
2.5
0
1m 10m 100m 1 3 10 30 100 2 4 6 8 10 12 14
frequency / Hz photocurrent ' / nAW -1m2
Dynamic photo-current measurements of the system Ti-TiO2

under light of 370nm wavelength at different anodic polarization.
Intensity: 10W/m2. The measurement series was fitted with the model
displayed in the inlay of the complex plane diagram (right).
Pt-PTP-CIMPS Current Measurements and Model Fit
535pcur+100
200 535pcur-100 100
Semicond. Schottky- Porous
535pcur+000 40 polymer barrier polymer-electrolyte
|photocurrrent| / nAW -1m2
bulk system
photocurrrent ''/nAW -1m2

Cad Rad
Csb Cdl
Cpoly
150 Rpoly Rct
20
phase/o
Isb Rsb Rel
50
100
0
-20
80
1m 3m 10m 100m 1 3 10 30 100 80 100 120 140 160 180 200 220
frequency / Hz photocurrrent '/ nAW -1m2
Dynamic photo-current measurements of the system Pt-PTP

under light of 535nm wavelength at different cathodic polarization.
Intensity: 10W/m2. The measurement series was fitted with the model
displayed in the inlay of the complex plane diagram (right).
Conclusions
Semiconductor-electrodes like conducting polymers can be modeled
with the same strategy as their two-pole impedance: for that,
current sources, representing the photoactive process, have to be
introduced.
Photocurrent and photovoltage reflect different parts of the total
electrode network.
An equivalent circuit model, common to potentiostatic and
galvanostatic produced CIMPS and EIS spectra under identical
current load conditions promise to prove a proper modeling.
Measurements at the OCP under illumination as well as
measurements with resistance load complicate the analysis
Future aims: repeating the measurements under orthogonal
conditions.

Polythiophene Photo- and Impedance Spectroscopy

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Intensity Modulated Photo- and

W. Plieth1, C.A. Schiller2*, U. Rammelt1, N. Hebestreit1

Principle of EIS: Principle of IMPS:

EPOT: Slave-Potentiostat / Power OPA *)

BUVZ/GRL: UV-VIS Multi-LED-Emitter *)

Usual IMPS set-up: Principle of CIMPS:

imaginary part / nAW -1m2

10m 1 100 10K -1 0 1 2 3 4 5 6 7

Dynamic photo-current measurements at the binary system Ti-TiO2-PTP

imaginary part / mVW -1m2

1m 10m 100m 1 3 10 100 1K 0 0.5 1 1.5 2 2.5 3 3.5

Dynamic photo-potential measurements of the binary system Ti-TiO2-PTP

EIS measurements of the binary system Ti-TiO2-PTP

imaginary part / nAW -1m2

10m 100m 1 3 10 100 1K -200 -150 -100 -50

Dynamic photo-current measurements of the system Pt-PTP

Ti TiO2 SB DL Electrolyte EF: Fermi level in equilibrium

photocurrent '' / nAW -1m2

Dynamic photo-current measurements of the system Ti-TiO2

photocurrrent ''/nAW -1m2

Dynamic photo-current measurements of the system Pt-PTP

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