Supporting Information

Charge Carrier Dynamics and Morphological studies in Efficient Defect

Free-Polythiophene:Fullerene blend Organic Solar cells
Naresh Chandrasekaranabc, Eliot Gannce, Nakul Jainb, Anshu kumard, Sreelekha P.Gopinathand, Anil
Kumard, Christopher R. McNeillc* and Dinesh Kabrab*

Mr. N. Chandrasekaran
IITB-Monash Research Academy, IIT Bombay, Mumbai 400076, India.

Mr. N. Chandrasekaran, Mr. N. Jain, Prof. D. Kabra

Department of Physics, Indian Institute of Technology Bombay, Powai, Mumbai, 400076,
India.
dkabra@iitb.ac.in

Mr. N. Chandrasekaran, Dr. E. Gann, Prof. C. R. McNeill

Department of Materials Science and Engineering, Monash University, Wellington Road,
Clayton, VIC 3800 Australia.
christopher.mcneill@monash.edu

Mr. A. Kumar, Mrs S. P. Gopinathan, Prof. A. Kumar

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076,
India.

Dr. E. Gann.
Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168 Australia.

Keywords: Defect free P3HT, charge carrier dynamics, morphology, organic solar cells.
 The results of DF:P3HT:PCBM solar cells fabricated in the optimum condition of RR-
P3HT:PCBM cells and the other way round are shown in the picture below. The solar cell
parameters are listed in the table S1. The best performing RR-P3HT:PCBM (3.51% PCE) and
the DF-P3HT:PCBM solar cells fabricated in the same condition shows similar performance.

14
a) RR-P3HT:PCBM 70 RR-P3HT:PCBM
12 DF-P3HT:PCBM b) DF-P3HT:PCBM
60
10
J (mA/cm2)

50

EQE (%)
8
40
6
30
4
20
2
10
0
0
-2
-0.2 0.0 0.2 0.4 0.6 300 400 500 600 700 800
Bias (V) Wavelength (nm)

Figure S1: Figure S1: Dark (hollow) and lighted (solid) J-V characteristic under AM 1.5G b)
External quantum efficiency (EQE) spectrum of inverted RR-P3HT:PCBM (square) and DF-
P3HT:PCBM solar cells (circle). The thickness of RR-P3HT:PCBM and DF-P3HT:PCBM
Films are 230nm and 130nm respectively.

Table S1: Summary of the mean of 16 devices and best device parameters of
ITO/PEIE/P3HT:PCBM/MoO3/Ag solar cells.
 0.8
RR-P3HT:PCBM(high performance)
RR-P3HT:PCBM
1.0 RR-P3HT:PCBM(high performance)
RR-P3HT:PCBM
DF-P3HT:PCBM(high performance) DF-P3HT:PCBM(high performance)

0.6 DF-P3HT:PCBM
0.8
DF-P3HT:PCBM

Norm OD
0.6
OD

0.4
0.4
0.2
0.2

0.0 0.0
400 500 600 700 800 400 500 600 700
Wavelength (nm) Wavelength (nm)

Figure S2: Absorption spectrum of RR-P3HT:PCBM and DF-P3HT:PCBM films with

different thickness which were used in the device fabrication. The devices which gave the
best performance are mentioned in the legend. One can also observe from the normalized plot
the increase in the absorption at 558nm and 607nm in DF-P3HT:PCBM films.

Figure S3: Fraction of light absorbed in the different layers of the device simulated by the
transfer matrix method. The shape of the light absorbed by the active layer resembles much
similar to the device IQE spectrum shown in figure 2b main text.
Figure S4: a) Raw data of transient photovoltage measurement at different background sun intensity;
b) Mono exponential fit of the transient voltage decay used to extract the decay time of the
charge carriers; c) Transient photocurrent curves obtained from the transient photocurrent
measurement at different background intensities.
Figure S5: S5:Electron only P3HT:PCBM devices with the structure ITO/PEIE/Active
layer/Ca/Al. The plots also shows the fit using Mott-gurney equation to extract the
parameters A, Vo

Table S2: The parameters extracted by the fit using Mott-gurney equation for electron only
devices.
Figure S6:Hole only P3HT:PCBM devices with the structure ITO/MoOx/Active layer/Au.
The plots also shows the fit using mott-gurney equation to extract the parameters A, Vo. The
extracted parameters are shown in the table 2 main text.

Figure S7: AFM images of neat RR-P3HT films (a) and (b); neat DF-P3HT films (c) and (d)
over ITO/PEIE substrates.
Defect Free (100% regioregular) P3HT polymer was procured from Sycon Polymers India Pvt Ltd and
was characterized using 1H NMR as detailed below:

Figure: 1H NMR analysis of defect free P3HT in CDCl3 (symbol # designates 13C satellite signals); (a)
and (b) are expanded spectra in aromatic and aliphatic regions respectively where (C) shows full
spectrum. Analysis was done based on i) Kohn, P.; Huettner, S.; Komber, H.; Senkovskyy, V.;
Tkachov, R.; Kiriy, A.; Friend, R. H.; Steiner, U.; Huck, W. T. S.; Sommer, J.-U.; Sommer, M. J. Am.
Chem. Soc. 2012, 134, 4790 and ii) Senkovskyy, V.; Sommer, M.; Tkachov, R.; Komber, H.; Huck, W.
T. S.; Kiriy, A. Macromolecules 2010, 43, 10157.

The defect free nature of the P3HT was confirmed based on following analysis:

a) The absence of two singlet of equal intensity at 6.86 and 6.93 confirm the absence of TT
defect at the chain end group carrying bromine;
b) The absence of signal at 7.0 ppm confirms the absence of TT defect within the chain;
c) The presence of two doublets at 7.16 and 6.93 ppm further confirm the defect free nature of
the P3HT