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Engineering vertical morphology with nanoparticulate organic photovoltaic

devices Ben Vaughan a , Andrew Stapleton b , Elisa Sesa c , Natalie P. Holmes a ,
Xiaojing Zhou a , Paul C. Dastoor a , Warwick J. Belcher a , * a Centre for Organic
Electronics, University of Newcastle, Callaghan, NSW, 2308, Australia b Australia
Future Industries Institute, The University of South Australia, Mawson Lakes, SA ,
5095, Australia c Department of Physics, Tadulako University, Kampus Bumi
Tadulako, Tondo, Palu 94118, Indonesia a r t i c l e i n fo Article history: Received
22 December 2015 Received in revised form 11 February 2016 Accepted 14
February 2016 Available online 7 March 2016 Keywords: Nanoparticle Graded
Morphology Organic photovoltaic abstract Seque ntial deposi tion of monol ayer
s, compose d of nanop articles with varied donor-acceptor conc en- tration ratios,
has allowed t he fabri cation of orga nic photovoltai c ( OPV) active layer s with
engine ered vertical morph ology.
The perfo rmance of polymer-po lymer poly(9,9-dioctyl ? uorene-co-bis- N ,N

-phenyl- 1,4- phenylenediamine ):poly[(9,9-di- n-octyl ? uorenyl-2,7-diyl)-alt-
(benzo[2 ,1,3]thi adiazol -4,8-diyl)] (PFB:F 8BT) and polymer-full erene poly(3-
hexylthiophen e):phe nyl C61 butyric acid methyl ester (P3HT:PCBM) nanopa
rticul ate (NP ), graded nanopa rticulate (GNP ) and bulk heterojunction (BHJ)
OPV devic es have been studied .
For both ma terial systems the highes t device V OC is obser ved for the graded
struct ure. Furthermore, therma l treatments can be used to alleviate parasitic
series resistance in the GNP devic es, thus improving devic e J SC an d ef ? ciency.
Overall, this work shows that the nanopa rticle approach provid es a new exp
eriment al le ver for morph ology control in OPV devices. © 2016 Elsevie r B.V.
All rights reserved. 1. Introduction The fabrication of an optimal donor-acceptor

OPV device sets a fascinating challenge for the researcher. Fundamentally
contradic- tory requirements for active layer morphology must be balanced to
allow for ef ?cient charge separation between the materials, whilst still
maintaining charge transport pathways which minimise bimolecular
recombination [1] .
Exacerbating this task is the limited number of experimental levers available to

the researcher to in- ? uence active layer morphology [2]. In general, the
experimental parameters which can be utilised to optimise device morphology
and performance are limited to temperature, solvent and material choice (Fig. 1 ).
Consequently, researchers have attempted, with varying degrees of success,

methods to affect active layer morphology such as: thermal and solvent
annealing [3,4], the addition of additives [5] and the application of new materials
such as block-co-polymers [6]. Indeed, one of the main reasons for the continued
interest in the ubiquitous P3HT:PCBM material system [7], despite extensive
research and development into alternative materials, is that signi? cant
optimisation of the active layer morphology can achieved by simple ?ne-tuning
of the temperature and solvent parameters [8].
Whilst active layer nanomorphology and material domain size have been
recognised as key factors in optimising device performance for some time [4], it
is only relatively recently that vertical strati ? cation and phase segregation in
devices has been considered and examined [9]. Previous work has shown that
vertical phase segregation is an important optimisation parameter in OPV fabri-
cation [17].
In particular, having incorrect phases at the electrode interfaces reduces device

performance through increased recombination, whereas when the
concentration gradient is aligned correctly improved performance is observed
[18]. As such, given the carrier selectivity of the electrodes, having vertically
graded donor and acceptor concentrations in OPV active layers is potentially an
elegant way both to reduce recombination and increase device charge collection
[10].
Consequently, recent years have seen a steady increase in the number of
publications reporting attempts to induce and characterise graded active layers in
OPV devices using the aforementioned experimental levers [11 e16 ]. However,
the methodologies available to systematically control vertical phase segregation
are limited. The use of graded heterostructures is well established in small- *
Corresponding author. E-mail address: warwick.belcher@newcastle.edu.au (W.J.
Belcher).
Contents lists available at ScienceDirect Org anic Electr onics j o u r n a l h o m e

p a g e : www.elsevier.com / l o c a t e / o r g e l
http://dx.doi.org/10.1016/j.orgel.2016.02.022 1566-1199/ © 2016 Elsevier B.V. All
rights reserved. Organic Electronics 32 (2016) 250e 257 molecule OPV systems
fabricated via vapour phase deposition where the composition of each layer can
be readily controlled [19].
Enhanced concentration gradients are known to lead to both increased Voc and
Jsc, which can attributed to reduced recombination (associated with reduced
charge build-up within the device) and an increased charge collection ef? ciency
due to the composition gradient driving charges to the appropriate electrodes,
respectively [20e22].
However, to date, proven examples of graded heterostructures in all-solution

processed devices have been rare due to the limited experimental levers available
for controlling layer composition [23]. Consequently, the fabrication approaches
have been limited to manipulating the surface energy of the component
polymers/molecules relative to the electrode interfaces via thermal treatment
[24,25] , direct manipulation of surface energy [16], electric ? elds [26] or the use
of additives [27].
The application of nanoparticulate materials to OPV active layers provides a

unique opportunity to control directly the vertical morphology at length scales
appropriate for ef ?cient charge separation within the active layer. We have
previously shown that, by thermally modifying the nanoparticulate active layer
surface, sequential deposition of nanoparticle monolayers can be used to
systematically increase active layer thickness [28].
In this report, we demonstrate fabrication of vertically graded active layers of

P8BT:PFB polymer:polymer and P3HT:PCBM polymer:fullerene blends via the
sequential deposition of nanoparticle monolayers. Moreover, we show that
engineering these vertical donor-acceptor concentration gradients across the
device provides a level of control of device parameters hitherto only achieved in
vapour deposited OPVs. 2. Experimental 2.1. Materials All of the water required
for experiments was treated via a reverse osmosis system.
When ultra clean water was required, the reverse osmosis water was further
treated with a Milli-Q ® plus system in which the conductivity of the water was
kept below 10 m S cm 1 . All of the chloroform used was distilled, in house, prior
to use. Pre-patterned indium tin oxide (ITO) substrates were purchased from
Kintec Company, Hong Kong.
Sodium dodecyl sulphate (SDS) used during the miniemulsion process was pur-
chased from BDH Lab and Sigma-Aldrich at a purity of 90 e99% and used as
received. The aqueous suspension of PEDOT:PSS PEDOT:PSS used during this
investigation was obtained from H.C Stark, U.S and used as received. The
semiconducting polymers used were obtained from a range of suppliers; F8BT
and PFB were obtained from American Dye Source, Canada, with molecular
weights of 15,0 0 0e 20 0,0 0 0 g/mol for F8BT and 15,0 0 0 e75,0 0 0 g/mol for
PFB quoted by the manufacturer and as measured by GPC against polystyrene
standards.
P3HT and PCBM were supplied by Reike, Canada and Solenne B.V, Netherlands,
respectively. 2.2. Nanoparticle synthesis Fabrication of the aqueous polymer
dispersions of all material weight ratios required were performed as described
previously. The semiconducting materials (a total of 30 mg) were initially
dissolved in chloroform (0.8 g) and introduced to an aqueous SDS solution (52
mM in 2.8 mL).
The mixture was stirred at 120 0 RPM for 1 h to form a macroemulsion. The
emulsion was then sonicated using a Branson 450 analogue soni ? er operating at
60% of maximum amplitude for 2 min. After sonication, the miniemulsion
samples were heated at 60 C and stirred at 120 0 RPM for a minimum of 3 h in
order to evaporate the chloroform from the suspension.
Upon evaporation of the chloroform an aqueous suspension of polymer

nanoparticles remained. The resulting particle suspensions were then dialysed to
remove excess surfactant until the surface tension of the ?ltrate reached 38 ± 2
mN/m. 2.3. Nanoparticle characterisation A NanoSeries ZetaSizer Nano-ZS
(Malvern Instruments, UK) equipped with a helium-neon laser source (wavelength
633 nm; power 4.0
mW) was used for measuring the hydrodynamic diameter of the
semiconducting polymer colloids produced. Each sample Fig. 1. The parameter
space available for active layer morphology optimisation in OPV. Fig. 2. Scanning
electron microscopy image of P3HT:PCBM 1:1 nanopartic ulate single and double
layer structures.
The inset shows a magni ?ed image of the monolayer region emphas izing the
hexagonal close-packing of the particles . B. Vaughan et al. / Organic Electronics
32 (2016) 250e257 251 was measured and the z-average diameter recorded. A
Varian Cary 60 0 0i UV-Vis-NIR spectrophotometer was used to obtain UV-Vis
spectra of nanoparticle ? lms.
The samples were spin cast onto quartz substrates and measured over the 20
0e11 0 0 n m wavelength range. An experimental optical thickness was calcu-
lated for each nanoparticle monolayer deposition of the device active layers.
Using the measured thickness and absorption of the ? rst deposited layer as a
reference point, an optical thickness for each subsequent layer was calculated by
considering the composition of the deposited nanoparticles and the increase in
absorption at 377 nm (a PFB dominated absorption) or 513 nm (a P3HT
dominated absorption) for the respective material systems.
The results of these calculations are compared to measured and theo- retical
layer thicknesses in the active layers and this data is presented in Fig. 4 . 2.4.
Device fabrication and testing PEDOT:PSS (Baytron P) ?lms were spin-coated (50
0 0 rpm) on pre-cleaned patterned ITO glass slides and annealed at 140 C for 30
min to eliminate water in the ? lms.
PFB:F8BT or P3HT:PCBM nanoparticle layers were deposited by spin coating 35 m

L of dispersion (20 0 0 rpm for 1 min) in air to form a hexagonally close- packed
nanoparticle monolayer. Following the deposition of each layer, the ? lm was
dried at 70 C for 15 min. After depositing the ? nal layer, the ? lms were dried at
140 C for 15 min and then transferred into a vacuum chamber for cathode
evaporation.
Aluminium (Al) electrodes were evaporated on the active layers in vacuum (2 10

6 Torr) to a thickness of ~10 0 nm. Devices were annealed at 140 C on a hot
plate for an optimised 4 min (or 2 min for the PFB:F8BT GNP devices) under a
nitrogen atmosphere. Photocurrent density-voltage (J-V) measurements were
conducted using a Newport Class A solar simulator with an AM 1.5 spectrum ?
lter.
The light intensity was measured to be 10 0 m W c m 2 by a silicon reference
solar cell (FHG-ISE) and the J-V data were recorded with a Keithley 240 0 source
meter. The device area was 5 mm 2 and the average device characteristics were
calculated for devices processed on different substrates. External quantum ef?
ciency measurements were recorded when the devices were exposed to light
from a tungsten halogen lamp passed through an Oriel Cornerstone 130
monochromator, using an Ithaco Dynatrac 395 analogue lock-in ampli? er and
Thorlabs PDA55 silicon diode to collect the reference signal, and a Stanford
Research Systems SR830 DSP digitising lock-in ampli? er to measure device
current.
For the purposes of comparison bulk heterojunction devices for both material
systems were prepared and characterised as described previously [28,29]. 3.
Results and discussion In order to make graded devices, F8BT:PFB and
P3HT:PCBM nanoparticles were prepared with ? ve donor:acceptor weight ratios
varying systematically from 1:0 to 0:1. Table 1 shows the weight ratios of the
samples prepared, along with their z-average particle size and PDI as measured
by DL S.
The shape of the particle size distribution was a log-normal (skewed to higher
particle sizes) with an upper diameter cut-off around 150 nm and 10 0 nm for the
PFB:F8BT and P3HT:PCBM nanoparticles respectively. The polymer:polymer
F8BT:PFB nanoparticles show an approximately 30% variation in size across the
weight ratios prepared and low dispersity of particle size within each particle
batch.
By contrast, the polymer:fullerene nanoparticles display a much greater variation

in particle size (~30 0%) across the weight ratio range, with particle size
decreasing signi? cantly as they become more molecular in nature (i.e. as the
fullerene content increases). As shown in Fig. 2 , the nanoparticulate active layers
deposit in a hexagonal close packed (HCP) structure when the size distribution of
the nanoparticles used is low.
Indeed, the sequential deposition of nanoparticulate layers results in an HCP

structure for both single and double layers. Fig. 3 shows schematics of the
architectures for the graded nanoparticulate OPV devices fabricated in this study.
In each case a monolayer of pure hole transport polymer (PFB or P3HT) was ? rst
deposited onto the PEDOT:PSS layer, followed by subsequent monolayers of
particles containing successively higher weight fractions of the acceptor material
(F8BT or PCBM), and ? nally the active layer was capped by a monolayer of pure
acceptor material nanoparticles.
This stepwise fabrication method ensures the direct formation of a

nanoparticulate active layer which is graded from Table 1 F8BT:PFB and
P3HT:PCBM nanoparticle diameter and polydispersity (PDI) as a function of
weight ratios of the semiconducting materials. Nanoparticle sample Z-average
diameter (nm) PDI Nanoparticle sample Z-average diameter (nm) PDI F8BT 67.10
0.188 P3HT 65.2 0.281 2:1 F8BT:PFB 56.65 0.136 2:1 P3HT:PCBM 37.8 0.199 1:1
F8BT:PFB 50.48 0.128 1:1 P3HT:PCBM 30.5 0.296 1:2 F8BT:PFB 56.65 0.138 1:2
P3HT:PCBM 34.0 0.244 PFB 49.68 0.083 PCBM 22.6 0.241 Fig.
3. Device architecture for a) F8BT:PFB and b) P3HT:PCBM nanopartic ulate GNP

OPV devices prepared in this study. NP devices were prepared in a similar way
using 1:1 nanoparticles. B. Vaughan et al. / Organic Electronics 32 (2016) 250
e257252 pure donor material at the anode to pure acceptor material at the
cathode.
The composition of the active layer at any vertical point is solely determined by
the nanoparticle composition at that point. Furthermore, we have shown
previously that the nanoparticle structure is consistently core-shell for the range
of donor-acceptor ratios explored here. Changing the donor-acceptor ratio of
overall particle blend results in corresponding change in shell donor- acceptor
composition.
This internal particle morphology plays a role in determining device performance,

which is dominated by the donor-acceptor ratio in the shell [30] . Fig. 4 a and b
show the evolution of the UV-vis spectra for the active layers of the 5-layer
graded devices as they are deposited layer by layer for the F8BT:PFB (Fig. 4a) and
P3HT:PCBM (Fig. 4b) nanoparticulate systems.
These spectra con? rm that the ? rst layer deposited is pure donor material (PFB
or P3HT, peaks at ~ 380 and ~510 nm, respectively) with systematically more of
the acceptor material (F8BT or PCBM, peak s at ~ 470 and < 40 0 nm,
respectively) being added with each layer until a 1:1 material ratio is reached for
the overall active layer.
In order to establish that the active layer was indeed built up of sequential
monolayer depositions over the 5 layers, a model for active layer thickness was
developed and compared to the experimental results. The model for layer
thickness was calculated from the measured radii of the deposited nanoparticles
(from Table 1 ) by assuming a hexagonal close packed structure of spheres. This
data is shown in solid red circles in Fig. 4c and d for F8BT:PFB and Fig. 4.
UV-vis spectra for the stepwise formation of the 5-layer graded nanoparticulate
active layers for the: a) F8BT:PFB and b) P3HT:PCBM systems. In Figure 4a the
spectra correspond to a monolayer of pure PFB nanoparticles (green dots),
followed by the add ition of: a second monolayer of 1:2 F8BT:PFB nanoparticles
(olive short dashes), a third monolayer of 1:1 F8BT:PFB nanoparticles (light green
medium dashes), a fourth monolayer of 2:1 F8BT:PFB nanoparticles (light brown
long dashes), anda ?nal monolayer of pure F8BT nanopartic les (solid orange
line). Also shown is the ? nal post annealed 5 layer structure (orange double line).
In Figure 4b the spectra co rrespond to a monolayer of pure P3HT nanoparticles

(purple dots), followed by the addition of: a second monolayer of 2:1 P3HT:PCBM
nanoparticles (violet short dashes), a third monolayer of 1:1 P3HT:PCBM nano-
particles (pink medium dashes), a fourth monolayer of 1:2 P3HT:PCBM
nanoparticles (light pink long dashes), and a ?nal monolayer of pure PCBM
nanoparticles (solid orange line). Also shown is the ?nal 5 layer active layer post
annealing (orange double line).
Figure 4c and d show the modelled graded active layer thickness as a function of
the number of deposited layers (closed red circles) and the calculated optical
thickness derived from the UV-vis sp ectra as a functio n of the number of
deposited layers (open black circles) for the F8BT:PFB and P3HT:PCBM systems,
respectively. The error bars are derived from the standard deviation of the initially
deposited nanopartic le diameter. Dashed lines are included as a guide to the
eye.
(For interpretation of the references to colour in this ?gure legend, the reader is
referred to the web version of this article.) Table 2 Device characteristics for
F8BT:PFB nanoparticle (NP), graded nanoparticle (GNP) and bulk heterojunction
(BHJ) OPV devices. The data presented is the best device and the average of 6
devices (in brackets). The errors presented are the standard deviation of the data.
F8BT:PFB 1:1 devices Thickness (nm) J sc (mA cm 2 ) V oc (V) FF h (%) BHJ 311 (±
37) 0.851 (0.738 ± 0.077) 1.18 (1.16 ± 0.04) 0.272 (0.273 ± 0.002) 0.273 (0.234 ±
0.024) 5 layer NP 257 (± 28) 1.81 (1.53 ± 0.21) 0.770 (0.829 ± 0.062) 0.281 (0.254
± 0.020) 0.387 (0.320 ± 0.039) 5 layer GNP 246 (± 27) 1.31 (1.19 ± 0.09) 1.32 (1.30
± 0.05) 0.278 (0.276 ± 0.006) 0.385 (0.340 ± 0.032) B. Vaughan et al. / Organic
Electronics 32 (2016) 250e257 253 P3HT:PCBM nanoparticulate systems,
respectively.
For comparison, an experimental optical thickness for the each ?lm was also
calculated. By using the measured thickness and absorption of the ? rst deposited
layer as a reference point, an optical thickness for each subsequent layer was
calculated by considering the composition of the deposited nanoparticles and
the increase in absorption at 377 nm (a PFB dominated absorption) or 513 nm (a
P3HT dominated absorption) for the respective material systems. This data is
shown in Fig. 4 c and d as the open black circles.
The error bars shown are derived from the standard deviation of the particle size
of the initially deposited nanoparticle layer. The data presented in Fig. 4c and d
shows that the observed UV-vis spectra are well explained in terms of sequential
deposition of spherical nanoparticle monolayers, with the minor differences
observed likely being the result of deviations from hexagonal close packing as a
result of variation in particle size.
This result is in contrast to the recent report of Pedersen et al. who observed that
their spherical particles in dispersion collapsed into oblate nanoparticles upon ?
lm deposition [31]. We speculate that difference in the two ? lm structures is
driven by the differences in nanoparticle synthesis, in particular, the lower
evaporation temperature used for solvent removal.
In order to compare the photovoltaic properties of these graded active layers

with more traditional active layer structures, standard 1:1 acceptor:donor BHJ and
nanoparticulate devices using the same device architecture were prepared, in
addition to the graded nanoparticulate devices, for both material systems. In the
case of the P3HT:PCBM system, standard nanoparticulate devices with 2, 3 and 5
nanoparticle active layers were prepared in order to directly compare to the
corresponding graded devices.
Table 2 shows the device characteristics for the F8BT:PFB nanoparticle and BHJ
OPV devices and Table 3 shows the device characteristics for the P3HT:PCBM
nanoparticle and BHJ OPV devices. While the use of an Al cathode is known to
result in lower ef- ? ciency NP devices [32], the presence of a Ca interfacial layer
has been shown to substantially change the vertical phase segregation of
P3HT:PCBM active layers in devices with both BHJ and NP active layers [33] .
Furthermore, the Ca/Al cathode, whilst more optimal in terms of device ef?
ciency, is extremely hydrolytically sensitive and prone to act as a site for device
degradation [34,35] . Since the NP and GNP devices are fabricated from aqueous
material suspensions, the use of Ca was avoided in order to simplify the
architecture and remove effects which might arise from the hydrolysis of the
cathode interface, as well as electrode driven phase segregation. Fig.
5 shows J-V and EQE plots for the best devices in Table 2 and reveals some
general trends in the behaviour of the NP and GNP devices. Firstly, the GNP
devices all exhibit a signi? cantly higher V oc than the corresponding NP devices
across both polymer:polymer and polymer:fullerene active layers. Secondly, J sc is
lower for all GNP devices than the corresponding NP devices across both ma-
terial systems.
Finally, for a given active layer material system, there is no signi? cant difference
between the normalised EQEs of the NP and GNP devices, indicating that the
relative charge contribution from the donor and acceptor species does not
change. Fig. 6 shows the effect of changing the number of NP layers in both NP
and GNP devices upon the device parameters.
For the NP devices, we observe that both V OC and J SC increase systematically

with the number of layers; consistent with a systematic increase in active layer
thickness. By contrast, for the GNP system both the active layer thickness and
compositional gradient are affected by the number of layers. Whereas the V OC
of the GNP system increases systematically with the number of layers, we observe
maxima in the J SC and FF for the three layer device.
These maxima correspond to the most ef ?cient device for the P3HT:PCBM
material system. The observation that the GNP devices have a systematically
higher Voc than their non-graded counterparts clearly indicates that electron-
hole recombination is reduced in the graded device [36,37].
Furthermore, Voc increases with the number of graded layers in the GNP devices;
consistent with reduced recombination as the compositional gradient across the
device changes. However, the increase in V OC is not simply correlated with a
greater J SC (for example, due to greater exciton harvesting in the thicker
devices) since the 5 layer GNP device exhibits the lowest J SC .
In OPV devices, the current ? ux is a function of both the elec- trical potential
gradient V U ðx Þ, and electron concentration gradient, Vn ðx Þ, across the device
[38] such that (for electrons): J n ð xÞ¼ n ð xÞ m n VU ð xÞþ kT V nð x Þ (1)
Where n (x ) is the electron concentration as function of distance, x, in the device
and m n is the electron mobility.
Under illumination, the chemical potential gradient is a function of the

concentration gradient [39]: Vm hn ð x Þ ¼ ð kT = nð x ÞÞV nð x Þ (2) In general,
the photo-voltage of a solar cell is a function of both the built-in ? eld and the
photo-induced chemical potential differences across the cell, which in turn are
in ?uenced by the concentration gradient across the device.
Thus, in the absence of any other effects (such as non-ohmic contacts at the
active layer/electrode interfaces) both J SC and V OC should increase with
increased concentration gradient [39] . Early attempts to create graded CuPc/C
60 Table 3 Device characteristics for P3HT:PCBM nanoparticle (NP), graded
nanoparticle (GNP) and bulk heterojunction (BHJ) OPV devices. The data
presented i s the best device and the average of 6 devices (in brackets). The
errors presented are the standard deviation of the data.
P3HT:PCBM 1:1 devices Thickness (nm) J sc ( m A cm 2 ) V oc (V) FF h (%) BHJ 90

( ±10) 9.00 ± 0.61 0.575 ± 008 0.452 ± 0.028 2.34 ± 0.32 2 layer NP 103 ( ±31)
2.65 (2.06 ± 0.39) 0.248 (0.222 ± 0.018) 0.376 (0.359 ± 0.023) 0.198 (0.133 ±
0.043) 3 layer NP 132 ( ±38) 2.68 (2.60 ± 0.34) 0.395 (0.320 ± 0.056) 0.287 (0.273
± 0.009) 0.244 (0.185 ± 0.052) 5 layer NP 189 ( ±49) 3.90 (3.62 ± 0.27) 0.421
(0.419 ± 0.012) 0.347 (0.342 ± 0.007) 0.457 (0.362 ± 0.271) 2 layer GNP 107 ( ±29)
1.75 (1.62 ± 0.18) 0.405 (0.332 ± 0.103) 0.287 (0.282 ± 0.007) 0.163 (0.130 ±
0.047) 3 layer GNP 156 ( ±55) 2.31 (2.27 ± 0.06) 0.580 (0.566 ± 0.012) 0.380 (0.346
± 0.023) 0.406 (0.356 ± 0.030) 5 layer GNP 192 ( ±49) 0.99 (1.13 ± 0.07) 0.615
(0.612 ± 0.007) 0.308 (0.290 ± 0.011) 0.150 (0.147 ± 0.010) B. Vaughan et al.
/ Organic Electronics 32 (2016) 250 e257254 OPV devices indicated that pure
donor or acceptor layers at the respective electrodes were required for high ef?
ciency devices [20] . Subsequently, Chen et al. showed that, for CuPc/C 60
devices, both J SC and V OC increased when the concentration gradient of the
donor and acceptor across the device was increased [39] .
Moreover, Pandey et al. showed that optimally graded CuPc/C 60 devices exhibit
the lowest dark currents, and hence lowest electron-hole recombination [22] ,
further highlighting that fabricating OPV devices with concentration gradients
creates chemical potential gradients that drive charge carriers apart; reducing
recombination and thus enhancing device performance.
By contrast, composition gradients in ZnPc/C 60 devices only lead to
improvements in V OC , due to other effects (such as parasitic resistance)
dominating J SC [21] . Returning then to the nanoparticulate device data, the
observation that the V OC of the GNP devices is systematically higher than that of
the corresponding NP devices is entirely consistent with reduced electron-hole
recombination due to an increased concentration gradient (and hence V mð xÞ).
Furthermore, the fact that this increased V OC is observed for both polymer-
polymer and polymer-fullerene nanoparticulate devices, and that these differ-
ences are much larger than those reported for any previous solution processed
graded OPV devices, demonstrates that the nanoparticulate approach produces
devices with tunable chemical potential gradients.
Moreover, whereas V OC is directly related to J n (x) via the Schockley equation

[40] ,J SC is a function of both J n (x) and any current loss mechanisms (e.g. non-
radiative electrode recombination) that occur under short-circuit conditions
[41]. As discussed earlier, the increase in V OC and J SC in going from the 2 to 5
layer NP devices is driven by increased exciton harvesting with Fig. 5.
Current density as a function of voltage for the best: a) F8BT:PFB, b) two layer
P3HT:PCBM, c) three layer P3HT:PCBM and d) ?ve layer P3HT:PCBM devices. Also
shown are the normalised EQE plots for the best: e) F8BT:PFB and f) P3HT:PCBM
device. In all cases the black line, the blue dotted line and the red dashed line
correspond to the data for the BHJ, NP and GNP devices, respectively.
(For interpretation of the references to colour in this ?gure legend, the reader is
referred to the web version of this article.) B. Vaughan et al. / Organic Electronics
32 (2016) 250e257 255 increasing device thickness. By contrast, the
compositional gradient of the GNP devices actually decreases in going from 2 to
5 layers and yet V OC rises; indicating that it is the increased concentration of
charges ( n( x)), rather than the decreased concentration gradient ðV mð xÞÞ that
is dominating J n ( x) and hence V OC .
Thus, for both NP and GNP devices, going from 2 to 5 layers leads to higher V OC
due to increased charge generation. The fact that we do not observe a
corresponding increase in J SC for the 5 layer GNP device indicates that there
are other losses which now dominate charge extraction in this device.
Given that FF follows a similar trend to J SC with increasing number of layers in

the GNP devices, it seems reasonable to conclude that the current losses are
attributable to parasitic series resistance in the devices, as observed by Tress et al.
for graded ZnPc/C 60 devices [21] . Despite the increased Vm ðxÞ ,J SC for the
GNP devices is lower than that of the corresponding NP devices and as such
there is room for further improvement in device performance. As discussed
earlier, the reduced J SC arises from other limiting effects in the device
architecture.
We have previously reported the improvement in performance of NP OPV

devices upon thermal treatment; arising primarily from improved
interconnectivity between NP particles [30]. Thus, it seems reasonable to
speculate that the limitation in the GNP devices presented here is most likely due
to a non-optimal inter-particle morphology and connectivity leading to reduced
exciton harvesting. Table 4 and Fig.
7 show the device characteristics and J-V curves for the hero three layer GNP
devices annealed for different times and reveal that there is a systematic increase
in FF and J SC with annealing time while V OC remains constant. Previ- ous work
has shown that optimising the annealing time results in NP devices with
minimised series resistance (R S ); correlating with maximum J SC due to
improved inter-particle connectivity and reduced surface SDS concentration [42] .
This observation and the results presented here indicate that thermal treatments
allow the GNP morphology to improve (thus reducing current losses from
parasitic series resistance) whilst retaining the high V OC associated with the
graded architecture. It is anticipated that further optimisation of these thermal
treatments will result in further improvements in device performance. 4.
Conclusions The performance of OPV devices is a complex balance of charge

density and charge concentration gradient. In general, it is chal- lenging to
control the charge concentration gradient in solution processed BHJ devices
since the vertical compositional distribution Fig. 6. Performance characteristics for
the P3HT:PCBM NP (solid blue bars) and GNP (open red circles) devices.
The error bars are calculated from the standard deviation of the data. (For
interpretation of the references to colour in this ?gure legend, the reader is
referred to the web version of this article.) Fig. 7. Current density (open circles),
open circuit voltage (closed circles), ?ll factor (open squares) and ef ?ciency (open
triangles) for the hero P3HT:PCBM 3 layer GNP device as a function of annealing
time at 140 C. Dashed red lines have been added as a guide to the eye.
(For interpretation of the references to colour in this ? gure legend, the reader is
referred to the web version of this article.) Table 4 Device characteristics for three
layer P3HT:PCBM GNP devices annealed for different durations. Annealing time
(min) J SC (mA cm 2 ) V OC (V) FF h (%) R S ( U ) 0 1.84 0.646 0.352 0.335 3106 4
2.31 0.580 0.380 0.406 1911 9 2.35 0.577 0.397 0.432 1651 13 2.62 0.572 0.415
0.498 1484 B. Vaughan et al. / Organic Electronics 32 (2016) 250 e257256 in these
devices is governed by the complex thermodynamics of ? lm formation.
By contrast, here we have shown that the use of nanoparticulate active layers
allows for the controlled fabrication of graded active layer structures. In
particular, it is possible to improve the V OC of NP devices by controlling the
concentration gradient, as previously achieved in vapour deposited devices.
Moreover, judi- cious use of thermal treatment allows for a systematic increase in
J SC whilst maintaining a higher V OC than in the ungraded devices.
Acknowledgements The University of Newcastle (AS and BV) and the Australian
Renewable Energy Agency (NP) are gratefully acknowledged for PhD
scholarships. The Indonesian Directorate General of Higher Education (DIK TI) is
acknowledged for PhD scholarship funding (ES). This work was performed in part
at the Materials node of the Australian National Fabrication Facility, a company
established under the National Collaborative Research Infrastructure Strategy to
provide nano and micro-fabrication facilities for Australia's researchers.
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