Nano Energy (2015) 12, 457–467

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

Critical role of domain crystallinity, domain

purity and domain interface sharpness
for reduced bimolecular recombination
in polymer solar cells
Swaminathan Venkatesana, Jihua Chenb, Evan C. Ngoa,
Ashish Dubeya, Devendra Khatiwadaa, Cheng Zhangc,
Qiquan Qiaoa,n

a
Center for Advanced Photovoltaics, Department of Electrical Engineering and Computer Science,
South Dakota State University, Brookings, SD, USA
b
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
c
Department of Chemistry and Biochemistry, South Dakota State University, Brookings, SD, USA

Received 2 October 2014; received in revised form 12 December 2014; accepted 22 December 2014
Available online 31 December 2014

KEYWORDS Abstract
Polymer solar cells; Inverted bulk heterojunction solar cells were fabricated using poly(3-hexylthiophene) (P3HT)
Bimolecular recombi- blended with two different fullerene derivatives namely phenyl-C61-butyric acid methyl ester
nation; (PC60BM) and indene-C60 bis-adduct (IC60BA). The effects of annealing temperatures on the
Domain crystallinity; morphology, optical and structural properties were studied and correlated to differences in
Domain purity;
photovoltaic device performance. It was observed that annealing temperature significantly
Domain interface
improved the performance of P3HT:IC60BA solar cells while P3HT:PC60BM cells showed relatively
sharpness
less improvement. The performance improvement is attributed to the extent of fullerene
mixing with polymer domains. Energy filtered transmission electron microscopy (EFTEM) and
x-ray diffraction (XRD) results showed that ICBA mixes with disordered P3HT much more readily
than PC60BM which leads to lower short circuit current density and fill factor for P3HT:IC60BA
cells annealed below 120 1C. Annealing above 120 1C improves the crystallinity of P3HT in case
of P3HT:IC60BA whereas in P3HT:PC60BM films, annealing above 80 1C leads to negligible change
in crystallinity. Crystallization of P3HT also leads to higher domain purity as seen EFTEM.
Further it is seen that cells processed with additive nitrobenzene (NB) showed enhanced short
circuit current density and power conversion efficiency regardless of the fullerene derivative
used. Addition of NB led to nanoscale phase separation between purer polymer and fullerene

n
Corresponding author.
E-mail address: qiquan.qiao@sdstate.edu (Q. Qiao).

http://dx.doi.org/10.1016/j.nanoen.2014.12.027
2211-2855/& 2015 Elsevier Ltd. All rights reserved.
458 S. Venkatesan et al.

domains. Kelvin probe force microscopy (KPFM) images showed that enhanced domain purity in
additive casted films led to a sharper interface between polymer and fullerene. Enhanced
domain purity and interfacial sharpness led to lower bimolecular recombination and higher
mobility and charge carrier lifetime in NB modified devices.
& 2015 Elsevier Ltd. All rights reserved.

Introduction boiling point solvents are preferred to increase throughput and

thickness uniformity for roll to roll printing implementation
Due to increased demand for clean energy and depletion of [27]. Further it has been shown that mixing behavior of
fossil fuels, alternative energy sources such as solar and wind fullerene with P3HT is dependent upon the fullerene derivative
are of interest currently. Organic semiconductors have gained used [28]. There exists a need for understanding the correlation
significant amount of interest for photovoltaic applications in between processing conditions and resulting morphology and
the last several decades due to their lower cost [1] and between complex nanoscale morphological features and charge
processability from solution for lightweight and flexible devices transport/recombination to achieve faster commercialization of
[2]. Polymer–fullerene bulk heterojunction (BHJ) solar cells low cost plastic solar cells.
have shown photovoltaic efficiencies up to 11% [3,4]. Nano- In this study we found that mixing behavior of P3HT and
morphology plays a crucial role in BHJ solar cells as it dictates fullerene is dependent upon the fullerene derivative used.
both charge generation and transport [5–7]. Nanomorphological ICBA was found to mix with P3HT more readily and the blend
features such as donor/acceptor crystallinity [8], vertical/ films require higher thermal energy to segregate into pure
lateral phase separation [9,10], domain purity [11], orientation polymer and fullerene phases. Inclusion of additives that are
[12] and domain interfaces [13] can be tailored by optimizing poor solvents for P3HT and good solvent for fullerene leads to
the processing conditions to enhance device conversion effi- formation of ideal morphology consisting of interconnected
ciencies. Processing parameters such as solvent selection pure polymer domains that have sharper interfaces for
[8,14,15], annealing temperature [16], donor–acceptor mixing exciton dissociation and lower bimolecular recombination.
ratio [17,18], and coating techniques can be fine-tuned to
attain high photovoltaic performance.
Molecular miscibility between polymer and fullerene is Results and analysis
critical to acquire homogenous phase separation between
polymer and fullerene components leading to efficient exciton The chemical structures of the donor and acceptor materials
dissociation [19]. However higher miscibility can lead to highly used are shown in Figure 1a. The experimental procedures for
intermixed domains preventing ordering of polymer chains. film deposition, device fabrication and characterization are
These highly intermixed amorphous domains have shown to given in detail in Supporting Information. To evaluate the effect
possess poor charge transport [20]. It is desired to have pure of annealing on the optical properties and structural properties
polymer domains having sharp interface between polymer and of P3HT:PC60BM and P3HT:IC60BA blend films, UV–Visible absorp-
fullerene phase (less intermixing at domain boundaries) to tion and XRD diffraction spectra were taken as shown in
improve charge transport and suppress trap assisted losses [21]. Figure 1b and Figure 1c respectively. In both cases films without
Several studies have focused on the mixing of donor polymers thermal annealing (as deposited) showed a single peak at
and fullerene blend films and have shown that domain purity 476 nm. For P3HT:PC60BM films annealing at and above 80 1C,
and crystallinity [5,22,23] play an important role in enhancing the peak red shifted to 504 nm and also showed formation of
device performance, but the physics behind efficient charge vibronic shoulders around 545 nm and 595 nm. These vibronic
transport correlated to nanoscale morphology is still elusive. shoulders formation at 545 nm and 595 nm is related to
Further, the processing parameter required to achieve ideal intrachain and interchain packing of P3HT respectively [29–31].
morphology is dependent upon the material selection and When the P3HT:PC60BM films were subjected to thermal
needs to be studied. Such an insight will be beneficial to attain annealing these shoulders start to form suggesting interchain
high power conversion efficiency at large scale. and intrachain stacking. In particular the intensity of the
P3HT:PCBM solar cells have been widely studied [24] in the shoulder at 595 nm (0–0 transition) was low in the as deposited
past decade and efficiencies of 4–5% have been regularly films indicating poor packing between chains. When the films
achieved. Device efficiencies were further improved to 5–7% were annealed these shoulders become more pronounced which
[25,26] by using a bis-adduct fullerene derivative namely indicated that the P3HT chains assemble to form ordered chains
indene-C60 bisadduct (IC60BA) resulting in higher open circuit as supported by the XRD spectra. However in P3HT:IC60BA films,
the vibronic shoulder at 595 nm had low intensities even when
voltage due to the higher LUMO level in ICBA. One of the most
annealed below 120 1C. The absorption peaks of P3HT:IC60BA
prominent approaches to improve efficiency in P3HT based
films also stayed at 468 nm and did not show any red shift
blends has been slow drying of cast films. Slow drying leads to which represents less crystalline and defective P3HT when
structural ordering of P3HT and diffusion of fullerene to achieve blended with IC60BA up to 120 1C. Annealing at and above
nanoscale phase separation between crystalline P3HT and full- 120 1C led to red shift of the peak to 486 nm and annealing
erene domains. This approach has demonstrated efficient solar beyond 150 1C, the vibronic shoulder at 595 nm became more
cells, however, is not practical for roll to roll processing. Lower pronounced leading to the conclusion that higher temperatures
Critical role of domain crystallinity, domain purity and domain interface sharpness 459

were required for P3HT chains to pack in P3HT:IC60BA films. This crystallite size of P3HT phase. Annealing the films led to
could also be easily observed from the color of the film. The as narrowing of (1 0 0) peak which indicated increased crystallite
deposited films had an orange color for both. P3HT:PC60BM films size of P3HT phase. In P3HT:PC60BM negligible change is seen in
turned purple when annealed at 80 1C and above. However the the XRD peaks when films were annealed above 80 1C. However
orange color was still visible in P3HT:IC60BA films when annealing in the case of P3HT:IC60BA broad peaks are observed for as
temperatures were below 120 1C which indicated that ICBA deposited and 80 1C annealed films. With increasing annealing
prevented P3HT chains to order at lower annealing tempera- temperatures above 100 1C the peaks get narrower up to 150 1C
tures. Figure 1c and 1d show the XRD spectra of P3HT:PC60BM after which negligible changes were seen as shown in the inset.
and P3HT:IC60BA films, respectively. A peak at 5.41 was observed The trend in peak narrowing in P3HT:IC0BA is similar to that
for all films corresponding to (1 0 0) diffraction of P3HT [32]. observed in the vibronic shoulder formation seen in optical
2θ=5.41 relates to d-spacing of 1.61 nm which corresponds to absorption spectra. Hence higher annealing temperatures were
distance between hexyl side chains of P3HT. A small second required for P3HT to aggregate into larger crystallites in P3HT:
order (2 0 0) diffraction peak was also observed at 10.51 in IC60BA blend films.
annealed films. The as deposited P3HT:PC60BM and P3HT:IC60BA To observe the changes in the nanoscale purity of P3HT
show broad peaks indicating higher disorder and smaller and PC60BM/IC60BA domains, energy filtered transmission

Figure 1 (a) Chemical structure of P3HT, PC60BM and IC60BA. UV–visible absorption spectra of (b) P3HT:PC60BM and (c) P3HT:IC60BA
films with different annealing temperatures. X-ray diffraction spectra of (d) P3HT:PC60BM and (e) P3HT:IC60BA films with different
annealing temperatures. Inset shows the region from 41 to 6.51.
460 S. Venkatesan et al.

electron microscopy (EFTEM) was performed to obtain donor smaller crystallites of P3HT and further impedes crystallization
and acceptor maps. The donor and acceptor maps were of P3HT phase to a higher extent than PC60BM. Such a different
overlaid to find the donor purity in as deposited and behavior could be attributed to several different reasons such as
thermally annealed P3HT:PC60BM and P3HT:IC60BA films as higher solubility, molecular structure, size of the molecule,
shown in Figure 2. The orange color in EFTEM composite diffusion coefficient in solid state or intermolecular attraction
maps corresponds to donor purity (sulfur) and green color between IC60BA and P3HT. Our results with P3HT:PC70BM shows
shows the acceptor purity. Gray areas in the map are due to the same trend as P3HT:PC60BM even though PC70BM has higher
thickness variations in the films. In the as deposited films of solubility than PC60BM [36]. Hence we believe that higher
P3HT:PC60BM and P3HT:IC60BA films small P3HT domains intermixing between P3HT and IC60BA is not due to its higher
(5–10 nm width) distributed homogenously throughout the solubility and real reason could be due to the physical proper-
films were observed. P3HT:PC60BM films when annealed at ties of IC60BA molecule and is not clear yet. The rigid molecular
120 1C show larger P3HT domains aggregating together. structure of IC60BA due to two symmetrical indene groups could
When annealed at 150 1C purer donor domains come be one of the major reason that could impede diffusion at lower
together to form an interconnecting network. The donor temperatures; however such a claim requires further
purity was qualitatively analyzed by the enhanced contrast experimental proof.
in the image. However in the case of as deposited and The current voltage characteristics of P3HT:PC60BM and
120 1C annealed P3HT:IC60BA films negligible change in P3HT:IC60BA solar cells with different active layer thermal
donor purity or domain size was observed. When annealed annealing temperatures are shown in Figure 3a and b
at 150 1C formation of interconnected domains was respectively. As observed thermal annealing was essential
observed. Due to thickness variations in the blend films to enhance the Jsc and fill factor for both P3HT:PC60BM and
quantitative analysis was not feasible. From XRD results in P3HT:IC60BA solar cells. The photovoltaic parameters are
Figure 1, it was shown that annealing above 80 1C led to the tabulated in Table 1. The best efficiencies (η) obtained for
improvement in crystallization of P3HT domains in P3HT: P3HT:PC60BM and P3HT:IC60BA are 3.08% and 4.19% respec-
PC60BM blend films. On the contrary, higher annealing tively when the active layer was thermally annealed at
temperatures (4120 1C) were required in P3HT:IC60BA films 180 1C. Higher Vocs ( 0.25 V) were observed for P3HT:
to enhance crystallization of P3HT phase. Correlating the IC60BA solar cells attributed to the higher LUMO level of
XRD and EFTEM results it can be concluded that crystallization IC60BA (3.74 eV) compared to that of PC60BM (3.91 eV)
of P3HT is the driving force to obtain higher purity polymer [25,26,37]. The dependence of Voc, Jsc, FF and efficiency
domains in the blend films consistent with the observation of with annealing temperature is shown in Figure 4. There is a
other reports [33–35]. Hence IC60BA mixes with disordered or small reduction (0.07–0.09 V) in open circuit voltage with

Figure 2 Energy filtered transmission electron microscopy (EFTEM) donor and acceptor composite maps of P3HT:PCBM and P3HT:
ICBA thin films with different annealing temperatures.
Critical role of domain crystallinity, domain purity and domain interface sharpness 461

Figure 3 Current–voltage characteristics of (a) P3HT:PC60BM and (b) P3HT:IC60BA with different annealing temperatures.

Table 1 Photovoltaic parameters of P3HT:PC60BM and P3HT:IC60BA solar cells.

Annealing temperature P3HT:PC60BM P3HT:IC60BA

(1C) Voc Jsc FF η Voc Jsc FF η

(V) (mA/cm2) (%) (V) (mA/cm2) (%)

As deposited 0.69 4.16 0.36 1.03 0.90 1.15 0.29 0.30

80 0.64 6.62 0.50 2.14 0.88 1.66 0.31 0.46
120 0.61 6.56 0.58 2.33 0.85 6.22 0.45 2.40
150 0.61 7.03 0.65 2.77 0.85 7.18 0.58 3.57
180 0.63 7.64 0.64 3.08 0.85 8.04 0.61 4.19
200 0.61 7.55 0.63 2.90 0.83 7.68 0.60 3.84

thermal annealing for both cases attributed to HOMO level increase is attributed to swelling of the films due to packing of
shift formed as a result of improved P3HT crystallization polymer chains to form larger fiber-like morphology. This can be
[38,39]. In the case of P3HT:IC60BA the Jsc and FF showed seen clearly in phase images of P3HT:PC60BM films when
higher dependence with annealing temperature. Jsc increa- annealed. For P3HT:IC60BA samples the aggregated phases are
sed from 1.66 mA/cm2 to 6.22 mA/cm2 when annealing observed in both topography and phase images of as deposited
temperature is increased from 80 1C to 120 1C and further and 80 1C annealed films. The aggregated phase is the largest in
increased with higher annealing temperatures till 180 1C. the as deposited films and gets smaller for 80 1C films. The RMS
However for P3HT:PC60BM bulk heterojunction solar cells Jsc roughness increases from 0.53 nm for as deposited films to
increased from 4.16 mA/cm2 in as deposited active layers to 0.608 films. For 150 1C annealed films the RMS roughness was
6.62 mA/cm2 in 80 1C annealed films. No significant change found to be 1.28 nm and showed fiber-like morphology. From
in Jsc were observed higher annealing temperatures. Better XRD and optical absorption results, it was shown that P3HT was
performance in P3HT:PCBM cells is attributed to increase in more disordered and possessed smaller crystallites in P3HT:
fill factor increases with thermal annealing up to 180 1C and PC60BM and P3HT:IC60BA films when no thermal annealing was
negligible decrease was observed when annealed at 200 1C. applied. From EFTEM it was observed that in films without
Photovoltaic efficiency trend with annealing temperature thermal annealing P3HT and fullerenes mix very well which led
shows similar behavior as Jsc with annealing temperature. to low domain purity. It was also observed that low annealing
Hence higher (150–200 1C) annealing temperature was req- temperatures (Z80 1C) were required for P3HT:PC60BM films
uired to obtain comparable short circuit current density and however relatively higher temperatures (Z120 1C) were
photovoltaic efficiencies in P3HT:IC60BA solar cells. required in the case of P3HT:IC60BA films to enhance crystal-
Figure 5 shows the topography and phase images of the as lization of P3HT. Based on this, the morphology evolution can
deposited, 80 1C and 150 1C annealed P3HT:PC60BM and P3HT: be explained by taking into account the following three
IC60BA blend films. For the as deposited P3HT:PC60BM films fiber different phases namely (a) intermixed disordered polymer
type morphology was seen in surface topography images and fullerene phase, (b) crystalline polymer pure phase and
whereas phase images show both fiber type and agglomerated (c) fullerene nanocrystals or clusters. As deposited P3HT:PC60BM
phases marked by dashed red circles in phase images. When and P3HT:IC60BA films have higher intermixed polymer and
P3HT:PC60BM films were annealed the root mean square (RMS) fullerene phases that were observed in phase images as
roughness values increase from 0.77 nm for the as deposited agglomerated regions marked by the dashed red circles. Upon
films to 0.81 nm for 80 1C annealed films. The RMS roughness thermal annealing of P3HT:PC60BM films at 80 1C P3HT crystal-
for 150 1C annealed P3HT:PC60BM films is 1.001 nm. Roughness lized in fibrillar form and these agglomerated phase
462 S. Venkatesan et al.

Figure 4 Effect of thermal annealing temperature on (a) Voc, (b) Jsc, (c) FF and (d) efficiency on P3HT:PCBM and P3HT:ICBA
solar cells.

disappeared. Upon further annealing at 150 1C PC60BM phase respectively. The photovoltaic parameters are tabulated in
possibly diffused to form clusters [7] as seen in the regions Table 2. The dark curves are shown in supporting informa-
marked by yellow dashed circles. For P3HT:IC60BA films the tion and it is observed that NB modified devices possessed
agglomerated phases regions were observed in both as depos- lower saturation current density as well as lower ideality
ited and 80 1C annealed films attributed to higher degree of factor than annealed and as deposited devices. Ideality
intermixing between disordered phase of P3HT and IC60BA. factor has been linked to energy disorder in bulk hetero-
Annealing at 150 1C led to enhancement in P3HT domain size to junction solar cells [40], hence addition of NB could lower
form interconnected fibers due to possible growth of IC60BA the energy disorder in the active layers.
phase form clusters, 150 1C annealed P3HT:IC60BA showed To investigate the reasoning behind effect of NB on enhanced
similar morphology as of 150 1C annealed P3HT:PC60BM films. photovoltaic performance, the morphology was characterized
Formation of fullerene clusters improved charge transport by EFTEM and Kelvin probe force microscopy (KPFM) and
pathways and hence the fill factor as observed in the photo- compared with as deposited and annealed samples as shown
voltaic performance. in Figure 7. EFTEM images showed highly intermixed domains in
Further role of solvent additive namely nitrobenzene (NB) as deposited samples and upon thermal annealing the domain
on the photovoltaic performance of P3HT:PC60BM and P3HT: purity increased. Addition of NB additives enhanced the P3HT
IC60BA cells were studied and compared with best annealed domain purity with larger interconnected domains as observed
devices as shown in Figure 6. 4 and 2 vol% NB was added to from the higher sulfur contrast in EFTEM images. KPFM images
P3HT:PC60BM and P3HT:IC60BA blend solutions respectively of as deposited showed large aggregates (100–150 nm dia-
before spin coating the active layers. 180 1C was chosen as meter) of higher surface potential and fiber-like morphology
the annealing temperature for comparison and termed as ( 20 nm mean diameter) as matrix. The RMS surface potential
‘Annealed’ in all the future sections. It is obvious that NB variation of as deposited films was 17.3 mV. In annealed film
additive improved the Jsc of solar cells with minor changes distinct fiber like domains (15 nm mean diameter) were
in Voc and FF in both P3HT:PC60BM and P3HT:IC60BA cells observed with smaller aggregates (40–55 nm diameter). The
when compared to annealed devices. The power conversion RMS surface potential variation for annealed films increased to
efficiencies were enhanced to 4.32% and 5.77% with the 27.5 mV. In the case of NB casted films predominantly fiber type
addition of NB in P3HT:PC60BM and P3HT:IC60BA solar cells of morphology was observed having average diameter of 20 nm
Critical role of domain crystallinity, domain purity and domain interface sharpness 463

Figure 5 AFM topography and phase images of P3HT:PC60BM and P3HT:IC60BA films. Regions marked in red circles are indication of
formation of intermixed phase. Regions marked in yellow circles are indication of formation of fullerene clusters.

Figure 6 Current–voltage characteristics of thermally annealed and solvent additive modified P3HT:PC60BM and (b) P3HT:IC60BA
solar cells.
464 S. Venkatesan et al.

Table 2 Photovoltaic parameters of thermally annealed and NB modified P3HT:PC60BM and P3HT:IC60BA solar cells.

Voc (V) Jsc (mA/cm2) Fill factor Efficiency (%) Enhancement (%)

P3HT:PCBM – annealed 0.63 7.64 0.64 3.08 –

P3HT:PCBM – 4% NB 0.61 10.83 0.65 4.32 40.26
P3HT:ICBA – Annealed 0.85 8.04 0.61 4.19 –
P3HT:ICBA – 2% NB 0.83 10.99 0.63 5.77 37.71

Figure 7 (a) EFTEM donor and acceptor composite maps of P3HT:PC60BM films, (b) Kelvin probe force microscopy images of P3HT:
PC60BM thin films, (c) pixel distribution of surface potential from KPFM images of P3HT:PC60BM thin films. Values in parenthesis show
the full width half maximum (FWHM) of Gaussian fits, and (d) line profiles of surface potential variation in P3HT:PC60BM thin films.

and RMS variation of 41.4 mV. The length scales observed for of 40 mV. For annealed and NB modified films, a broader
features in annealed and NB films were consistent with the distribution is observed having FWHM of 64 mV and 74 mV
length scales of pure P3HT domains observed in EFTEM images. respectively were observed. Line profile variation of surface
To further analyze the KPFM images of the films, surface potential showed that as deposited films had the least variation
potential distribution and line profiles were plotted as shown over length. Annealed films showed higher variation and NB
in Figures 7c and 7d. For the as deposited films, a narrow modified films showed the highest variation in surface poten-
distribution is observed having full width half maximum (FWHM) tial. From EFTEM and KPFM images it can be concluded that NB
Critical role of domain crystallinity, domain purity and domain interface sharpness 465

additive enhanced the domain purity that led to enhanced carrier lifetime decreases with increasing Voc attributed to
interfacial potential variation due to less intermixing at domain higher bimolecular recombination in the cells at higher light
interfaces. No change in crystallite size was observed in XRD intensity. For the as deposited cells the charge carrier
spectra of NB modified films (Supporting Information Figure 3). lifetime decreased to a much higher extent at higher Vocs
However optical absorption showed pronounced vibronic than annealed and NB modified devices. At 1 sun condition
shoulders and red shift for films cast with NB additive. This when the cell reaches the optimum Voc the measured
discrepancy could be due to packing orientation of P3HT chains lifetimes for as deposited, annealed and NB modified cells
which might not be sensitive to Cu Kα X-rays. Further insight is are 1.57 ms, 3.87 ms and 5.17 ms respectively. Charge carrier
needed on the structural arrangement caused by NB addition lifetimes were plotted as a function of charge carrier
and will be carried out in future. Nevertheless, nitrobenzene density as shown in Figure 8b. As deposited cells showed
(NB) effectively controlled the morphology of polymer–fullerene the lowest charge carrier density ( 1016 cm 3) among all
blends as it selectively solubilized the fullerene and induced cells which decreased rapidly with increasing charge carrier
self-ordering of purer polymer phase. Due to this selective density. For annealed devices, the charge carrier density
solubility, blend films cast with NB additive possessed homo- increased by almost two orders of magnitude compared to
geneous interpenetrating network of nanoscale phase separated as deposited cells. NB modified devices showed higher
domains. Thermal annealing also induced crystallization of charge carrier density with the lowest decline in lifetime.
polymer but due to local inhomogeneity in domain purity [41] The slope of the linear region in charge carrier density vs
and lack of free energy for diffusion of polymer or fullerene, lifetime plots was measured to evaluate the bimolecular
homogenous phase separation between them was not achieved. recombination order. The bimolecular recombination order
To evaluate the charge density and lifetime, transient obtained for as deposited, annealed and NB modified
photocurrent (TPC) and photovoltage (TPV) spectroscopy devices are 8.02, 4.9 and 1.8 respectively. Higher interfacial
were done on as deposited, annealed and NB modified solar potential variation in NB modified devices led to efficient
cells. From TPV measurements, the charge carrier lifetimes exciton dissociation and suppressed interfacial bimolecular
were measured with increasing light intensities which led to recombination [23,42]. Charge carrier mobility was evalu-
different Voc in the cells as shown in Figure 8a. Charge ated using photo-charge carrier extraction by linearly

Figure 8 Charge carrier lifetime as a function of (a) open circuit voltage and (b) charge carrier density. The values in the legend of
(a) and (b) show the charge carrier lifetime at 1 sun Voc and bimolecular recombination order respectively. (c) Photo-CELIV spectra
of P3HT:PC60BM solar cells at 10 ms delay time between light pulse and voltage ramp, and (d) extracted charge carrier density (next)
from photo-CELIV curves with varying delay times.
466 S. Venkatesan et al.

increasing voltage (Photo-CELIV) technique. The Photo- Acknowledgment

CELIV at 10 ms delay time for as deposited, annealed and
NB modified solar cells are shown in Figure 8c. The Photo- We acknowledge the support from NASA EPSCoR (NNX13AD31A),
CELIV current signal approached maximum earlier (lower NSF CAREER (ECCS-0950731), and NSF MRI (grant no. 1229577).
tmax) in NB modified cells than annealed devices. The as TEM experiments were conducted at the Center for Nanophase
deposited samples had the highest tmax of 5.35 ms among all Materials Sciences, which was sponsored at Oak Ridge National
solar cells. tmax for annealed and NB cells were 4.7 ms and Laboratory by the Division of Scientific User Facilities, Office of
3.4 ms respectively. Since the same voltage ramp was used Basic Energy Sciences, U.S. Department of Energy.
for all cells lower tmax is related to lower bias voltage (field)
required to extract the maximum charge carriers from the
device. NB modified solar cells showed the highest mobility Appendix A. Supporting information
of 4.81  10 5 cm2/V s and also resulted in the highest
extracted charge carriers (next) of 4.35  1016 cm 3. Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/
j.nanoen.2014.12.027.

Conclusions
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Critical role of domain crystallinity, domain purity and domain interface sharpness 467

[21] B.P. Lyons, N. Clarke, C. Groves, Energy Environ. Sci. 5 (2012) Devendra Khatiwada received his Master’s
7657–7663. degree in Physics from Prithvi Narayan Cam-
[22] B.A. Collins, J.R. Tumbleston, H. Ade, J. Phys. Chem. Lett. 2 pus, Tribhuvan University, Nepal in 2009. He is
(2011) 3135–3145. currently pursuing his Master’s degree in
[23] B.A. Collins, Z. Li, J.R. Tumbleston, E. Gann, C.R. McNeill, Electrical Engineering from South Dakota
H. Ade, Adv. Energy Mater. 3 (2013) 65–74. State University under the supervision of Dr.
[24] M.T. Dang, L. Hirsch, G. Wantz, Adv. Mater. 23 (2011) Qiquan Qiao. His research work includes
3597–3602. morphology study of Polymer Bulkheterojunc-
[25] G. Zhao, Y. He, Y. Li, Adv. Mater. 22 (2010) 4355–4358. tion solar cell. Presently he is actively
[26] Y.-J. Cheng, C.-H. Hsieh, Y. He, C.-S. Hsu, Y. Li, J. Am. Chem. involved in fabrication and characterization
Soc. 132 (2010) 17381–17383. of Perovskite solar cell.
[27] I. Burgues-Ceballos, M. Stella, P. Lacharmoise, E. Martinez-
Ferrero, J. Mater. Chem. A 2 (42) (2014) 17711–17722. Jihua Chen is a staff scientist at the Center
[28] H. Chen, J. Peet, Y.-C. Hsiao, B. Hu, M. Dadmun, Chem. Mater. for Nanophase Materials Sciences (CNMS) of
26 (2014) 3993–4003. Oak Ridge National Laboratory. He received
[29] J. Jo, S.-S. Kim, S.-I. Na, B.-K. Yu, D.-Y. Kim, Adv. Funct. his Ph.D. degree in Macromolecular Science
Mater. 19 (2009) 866–874. and Engineering in 2006 from the University
[30] F.-C. Chen, C.-J. Ko, J.-L. Wu, W.-C. Chen, Sol. Energy Mater. of Michigan, Ann Arbor. Up to date, he has 80
Sol. Cells 94 (2010) 2426–2430. scientific publications in peer-reviewed jour-
[31] J. Liu, S. Shao, H. Wang, K. Zhao, L. Xue, X. Gao, Z. Xie, nals in the field of novel organic semiconduc-
Y. Han, Org. Electron. 11 (2010) 775–783. tors, polymers, and hybrid nanomaterials.
[32] W. Ma, C. Yang, X. Gong, K. Lee, A.J. Heeger, Adv. Funct.
Mater. 15 (2005) 1617–1622.
[33] M.A. Brady, G.M. Su, M.L. Chabinyc, Soft Matter 7 (2011) Cheng Zhang, an assistant professor, Depart-
11065–11077. ment of Chemistry and Biochemistry, South
[34] N.D. Treat, M.A. Brady, G. Smith, M.F. Toney, E.J. Kramer, Dakota State University. Dr. Zhang received his
C.J. Hawker, M.L. Chabinyc, Adv. Energy Mater. 1 (2011) Ph.D. degree in chemistry in 1999 from Uni-
82–89. versity of Southern California (USC), Los
[35] D.R. Kozub, K. Vakhshouri, L.M. Orme, C. Wang, A. Hexemer, Angeles, California, and his B.S. degree in
E.D. Gomez, Macromolecules 44 (2011) 5722–5726. physical chemistry in 1987 from Department
[36] D.T. Duong, B. Walker, J. Lin, C. Kim, J. Love, of Chemistry, Wu Han University, China.
B. Purushothaman, J.E. Anthony, T.-Q. Nguyen, J. Polym. Before joining SDSU, he was an associate
Sci. Part B: Polym. Phys. 50 (2012) 1405–1413. professor of chemistry at Norfolk State Uni-
[37] Y. He, H.-Y. Chen, J. Hou, Y. Li, J. Am. Chem. Soc. 132 (2010) versity (NSU), Norfolk, Virginia and a research associate professor at
1377–1382. the Center for Materials Research, NSU. From 2000 to 2004, he was the
[38] K.S. Nalwa, R.C. Mahadevapuram, S. Chaudhary, Appl. Phys. Director and Chief Scientist of Material R&D Division, Pacific Wave
Lett. 98 (2011) 093306-01–093306-03. Industries, El Segundo, California. He is mainly interested in material
[39] K. Vandewal, W.D. Oosterbaan, S. Bertho, V. Vrindts, design, synthesis, and device fabrication for various optoelectronic and
A. Gadisa, L. Lutsen, D. Vanderzande, J.V. Manca, Appl. Phys. electro-optic applications, including solar cells, high-speed electro-
Lett. 95 (2009) 113301-01–113301-03. optic modulation and optical signal processing.
[40] G. Garcia-Belmonte, Solid-State Electron. 79 (2013) 201–205.
[41] A.J. Moulé, K. Meerholz, Adv. Mater. 20 (2008) 240–245.
Dr. Qiquan Qiao is an associate professor in
[42] M.-S. Su, C.-Y. Kuo, M.-C. Yuan, U.S. Jeng, C.-J. Su, K.-H. Wei,
the Department of Electrical Engineering
Adv. Mater. 23 (2011) 3315–3319.
and Computer Science at South Dakota
State University (SDSU), where he estab-
Ashish Dubey is a graduate student in lished the Organic Electronics Laboratory.
Electrical Engineering at South Dakota State Current research focuses on polymer photo-
University, US. He received his master voltaics and dye-sensitized solar cell mate-
degree in Nanotechnology from Amity Uni- rials and devices. He received 2014 F O
versity, India. Currently he is carrying out Butler Award for Excellence in research,
his doctoral thesis work in Dr. Qiquan Qiao 2012 College of Engineering Young Investi-
group. His research work includes, perovs- gator Award, 2010 US NSF CAREER Award, and 2009 Bergmann
kite based solar cells, organic–inorganic Memorial Award from the US–Israel Bi-national Science Foundation
semiconductor hybrid solar cells, structural (BSF).
and morphological studies of donor–accep-
tor blend films, and their optical and electrical characterization.