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White-light bias external quantum efficiency measurements of standard and inverted P3HT:
PCBM photovoltaic cells
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2012 J. Phys. D: Appl. Phys. 45 415101
(http://iopscience.iop.org/0022-3727/45/41/415101)
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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 45 (2012) 415101 (10pp) doi:10.1088/0022-3727/45/41/415101
White-light bias external quantum
efciency measurements of standard and
inverted P3HT: PCBM photovoltaic cells
Thomas J K Brenner
1
, Yana Vaynzof, Zhe Li, Dinesh Kabra,
Richard H Friend and Christopher R McNeill
2
Cavendish Laboratory, Department of Physics, University of Cambridge J J Thomson Ave, Cambridge,
CB3 0HE, UK
E-mail: christopher.mcneill@monash.edu
Received 21 June 2012, in nal form 23 August 2012
Published 27 September 2012
Online at stacks.iop.org/JPhysD/45/415101
Abstract
We have investigated the behaviour of inverted poly(3-hexylthiophene) : [6,6]-phenyl-
C
61
-butyric acid methyl ester (P3HT: PCBM) solar cells with different active layer thickness
upon changing light intensity. Using white-light bias external quantum efciency (EQE)
measurements and photocurrent transient measurements we explain the different thickness
dependence of device performance of inverted (ITO/ZnO/P3HT: PCBM/WO
3
/Ag) and
standard (ITO/PEDOT: PSS/P3HT: PCBM/Ca/Al) cells. Whereas for inverted devices where
high EQEs of up to 68% are measured under low light intensities (3.5 mWcm
2
), a dramatic
reduction in EQE is observed with increasing white-light bias (up to 141.5 mWcm
2
)
accompanied by a severe distortion of the EQE spectrum. For the inverted device this spectral
distortion is characterized by a dip in the EQE spectrum for wavelengths corresponding to
maximum light absorption and becomes more prominent with increasing active layer
thickness. For regular P3HT: PCBM devices, in contrast, a less dramatic reduction in EQE
with increasing light intensity and only a mild change in EQE spectral shape are observed.
The change in EQE spectral shape is also different for standard devices with a relative
reduction in EQE for spectral regions where light is absorbed less strongly. This asymmetry in
device behaviour is attributed to unbalanced charge transport with the lower mobility carrier
having to travel further on average in the inverted device structure. Thus at high light
intensities charge recombination is more pronounced at the front half of the device (close to
the transparent electrode) for inverted cells where most of the light is absorbed, and more
pronounced at the back half of the device for standard cells. Our results therefore indicate that
bulk charge transport mobilities rather than vertical composition gradients are the dominant
factor in determining the performance of standard and inverted P3HT: PCBM cells.
(Some gures may appear in colour only in the online journal)
1. Introduction
Solar cells based on organic molecules have shown
considerable progress over the last twenty years [1, 2]
with lab-based cell efciencies now exceeding 9% on a
laboratory scale [3]. Larger modules on exible plastic
1
Present address: Max Planck Institute for the Science of Light, Guenther-
Scharowsky-Str. 1/Bldg.24, 91058 Erlangen, Germany.
2
Present address: Department of Materials Engineering, Monash University
Wellington Rd, Clayton, VIC 3800, Australia.
substrates can be fabricated and are already becoming
commercially available for portable applications. The
photoactive layer in these devices usually consists of a
conjugated polymer acting as an electron donor mixed
with a fullerene derivative acting as electron acceptor
[4]. Generally, these solar cells consist of a transparent
hole-collecting anode, typically indium-tin oxide (ITO) coated
with poly(3,4-ethylenedioxythiophene) : polystyrene sulfonic
acid (PEDOT: PSS), and an electron-collecting low-work
0022-3727/12/415101+10$33.00 1 2012 IOP Publishing Ltd Printed in the UK & the USA
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
(a)
(b)
P3HT:PCBM
ZnO
ITO
Glass
WO
Ag/Al
3
Ca/Al
P3HT:PCBM
PEDOT:PSS
ITO
Glass
Figure 1. Schematic of the regular device geometry (a) and the
inverted device geometry (b). In the inverted case, electrons are
collected at the transparent ZnO/ITO contact (the cathode) and holes
are collected at the WO
3
/Ag electrode (the anode).
function metal cathode with the photoactive layer sandwiched
in between, see gure 1(a).
The inverted device geometry where cathode and anode
are reversed (see gure 1(b)) has attracted considerable interest
in recent years [2]. This alternate architecture allows for
efcient tuning of electrical and optical elds and the use of
thick active layers [57], but also facilitates the realization
of semitransparent devices that are essential for tandem and
multijunction solar cells [810]. The inverted device geometry
is also thought to be better suited to the vertical-phase
segregation that occurs in P3HT: PCBM blends, where a
P3HT-rich capping layer is observed to form on top of the lm
potentially affecting electron collection at the top electrode [2].
Additionally, due to the avoidance of a low-work function
metal top contact, inverted devices are more environmentally
stable against moisture and oxygen than regular devices
[11]. Using transition metal oxides as the electron and hole-
collecting contacts, external quantum efciencies (EQEs) of
over 70%reachingthose of conventional device structures have
been reported [2] for blends of P3HT and PCBM. Optimized
efciencies of >4% have been achieved with the inverted
architecture [1214] matching that typically achieved with the
standard device architecture [15].
Despite the fact that there has been signicant work
devoted to optimizing the combination of materials to improve
inverted cells [2, 16], less is known about the device physics of
this geometry. In this paper we investigate the light intensity
dependence of the photocurrent spectra of both inverted and
regular devices of poly(3-hexylthiophene) (P3HT) and [6,6]-
phenyl-C
61
-butyric acid methyl ester (PCBM) in combination
with transient photocurrent measurements. Measuring the
EQE spectrum as a function of background illumination can
provide additional insight into the nature of recombination
in organic solar cells [6, 17]. In contrast to the expectation
that the inverted device structure is better suited to charge
collection from morphological considerations, we present
evidence for enhanced charge recombination in inverted cells
due to unmatched bulk charge carrier mobilities, with hole
mobility limiting device performance.
2. Experimental details
2.1. Device fabrication and characterization
Inverted cells were fabricated on glass substrates covered with
an ITO stripe. These ITO-glass substrates were cleaned in an
ultrasonic bath in methanol, acetone and 2-propanol for 15 min
each and zinc oxide (ZnO) was deposited by spray pyrolysis at
370

Cfromzinc acetate dihydrate in ethanol to achieve a total

thickness of about 50 nm. On top of the ZnO the active layer,
a 1 : 1 blend of poly(3-hexylthiophene) (P3HT) (Rieke Metals,
M
w
= 50 00060 000 g mol
1
, RR 9293%) and [6,6]-
phenyl-C
61
-butyric acid methyl ester (PCBM) (Nano-C) with
concentrations between 36 and 64 mg ml
1
in dichlorobenzene
was spin coated and annealed at 140

C for 10 min to achieve

active layer thicknesses of 90, 200 and 420 nm. Inverted
devices were completed by thermal evaporation (<10
6
mbar)
of 10 nm WO
3
, 20 nm Ag and 80 nm Al serving as the top
electrode as shown in gure 1(b). ZnO was deposited in air,
active layer deposition and evaporation were carried out in a
glovebox with water and oxygen levels of <1 ppm.
To fabricate standard geometry devices (gure 1(a)), a
PEDOT: PSS layer of 40 nm thickness was deposited by spin-
coating and annealing at 230

C for 30 min under owing

nitrogen. Active layer deposition on top of PEDOT: PSS
and annealing was done as described for inverted devices
with active layer thicknesses of 130, 250 and 400 nm.
Standard devices were completed by evaporation of Ca/Al
(10 nm/80 nm) and were encapsulated with epoxy resin and
glass to prevent degradation.
2.2. EQE and solar simulator measurements
EQE spectra were recorded as a function of wavelength by
passing light from a tungsten lament lamp (Newport 250 W
QTH) through a monochromator (Oriel Cornerstone 130) with
a spot size smaller than the pixel size. The light intensity
was below 1 mWcm
2
and the short-circuit current was
recorded using a Keithley 2635 source measure unit. Intensity-
dependent EQE was measured using a white-light background
illumination source (ring of 6 white Lumiled LUXEON V
LXHL-NWE7 LEDs), see gure 2 for a schematic. To
distinguish between the monochromatic probe beam and the
white background illumination, the monochromatic light was
chopped using a Thorlabs MC 2000 mechanical chopper with
the modulated current recorded using a Femto LIA-MVD-
200 lock-in amplier in concert with a Stanford Research SR
570 current preamplier to subtract the constant background.
White-light intensity was varied between 3.5 mWcm
2
and
141.5 mWcm
2
through adjustment of the LED current.
The intensity of the chopped incident monochromatic light
was continuously monitored using a beam splitter, reference
photodiode and a separate lock-in amplier. When measured
2
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
Lamp
Monochromator
Aperture
Filter
Wheel
Chopper Control
Chopper
Beamsplitter
Lens
Lens
Reference
Photodiode
Ring of 6
White-light
LEDs
Lock-in
Amplifier
#1
Lock-in
Amplifier
#2
Detection
electronics
Device
Under
Test
Lens
Figure 2. Schematic of the white-light bias EQE setup for recording intensity-dependent EQE spectra.
in this way, the EQE can be seen as differential EQE
expressed as
EQE =
1240J
I
,
where is the wavelength of the monochromatic light
and J the increase in photocurrent measured due to the
additional monochromatic illumination I. Currentvoltage
characteristics under 120 mWcm
2
AM 1.5 G illumination
were measured with a Keithley 2635 source measure unit with
illumination provided by an ABET Sun 2000 Class A solar
simulator. Further experimental details can be found in our
previous paper [17] and we note that our approach is similar
to that recently employed by Koster et al [18].
2.3. Transient measurements
Transient photocurrent measurements [19] were performed
using square pulses of light generated with a Hewlett Packard
8116A pulse generator driving a green LED (Kingbright,
L-7104VGC-H, peak emission wavelength of 525 nm, 35 nm
half-width). Rise/fall time of the pulses was measured to be
less than 50 ns. Photocurrent was recorded using an Agilent
DSO 6032A digital oscilloscope (50 input impedance).
Intensity was varied using a neutral density lter wheel
calibrated with a silicon photodiode.
2.4. Optical simulation
Optical simulation of device stacks was carried out using the
transfer matrix approach [20]. A Matlab script developed by
BurkhardandHoke was employedusingoptical constants from
the literature [21]. For the case of WO
3
the optical constants of
MoO
3
were used instead as the optical constants of WO
3
were
not available. Substitution of MoO
3
with WO
3
is not likely to
affect the results since the WO
3
layer is only 10 nm thick and
both MoO
3
and WO
3
are transparent over the spectral region
of interest.
Figure 3. Currentvoltage characteristics under 120 mWcm
2
simulated sunlight (AM 1.5 G) for regular (a) and inverted
(b) P3HT:PCBM devices with different active layer thickness.
3. Results and discussion
3.1. Currentvoltage characteristics
Figure 3 presents the currentvoltage characteristics of
standardandinverteddevices under 120 mWcm
2
AM1.5 G
simulated sunlight, comparing the operation of devices with
thin (90 or 130 nm), medium (200 or 250 nm) and thick
(400 or 420 nm) active layer thickness. For the regular device
3
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
Table 1. Summary of the properties of both regular and inverted devices.
Device Active layer EQE @ 520 nm EQE @ 520 nm with J
sc
(AM 1.5 G) V
oc
FF PCE
structure thickness (nm) without bias (%) 142 mWcm
2
bias (%) (mAcm
2
) (V) (%) (%)
Inverted 90 60 42 9.0 0.52 45 1.7
Inverted 200 64 15 8.6 0.47 41 1.6
Inverted 420 27 10 3.0 0.41 37 0.6
Regular 130 57 53 9.4 0.56 52 2.2
Regular 250 65 55 10.9 0.56 49 2.5
Regular 400 64 42 11.5 0.56 48 2.6
Figure 4. Regular (a), (c), (e) and normalized (b) ,(d), (f ) white-light bias EQE spectra of P3HT: PCBM devices in standard device
geometry with an active layer thickness of 130 nm (a), (b), 250 nm (c), (d) and 400 nm (e), (f ).
structure, gure 3(a), an increase in J
sc
from 9.4 mAcm
2
for the 130 nm thick device to J
sc
= 11.5 mAcm
2
for the
400 nm thick device is observed. The open-circuit voltage
remains constant at V
oc
= 0.56 V while the overall power
conversion efciency (PCE) increases from 2.2% (130 nm) to
2.6% (400 nm). Such an increase in device efciency with
active layer thickness is consistent with previous thickness
dependent measurements such as those of Moul e et al [22].
In the case of the inverted device structure, gure 3(b), a drop
in J
sc
, V
oc
and PCE is observed with increasing active layer
thickness. Whereas J
sc
is reduced from 9.0 mAcm
2
for the
90 nmthick device to 3.0 mAcm
2
for the 420 nmthick device,
V
oc
drops from 0.52 V to 0.41 V with increasing active layer
thickness. PCE accordingly drops from 1.7% (90 nm) to 0.6%
(420 nm). Device parameters are also summarized in table 1.
3.2. White-light bias EQE measurements
Figure 4 presents the EQE spectra of regular P3HT: PCBM
devices as a function of white-light bias intensity. For the thin
device, gure 4(a), a moderate drop in EQEwith light intensity
from 57% without white-light bias (<1 mWcm
2
) to 53%
with 142 mWcm
2
background illumination is observed, with
the shape of the spectrum remaining essentially unchanged,
see normalized spectra in gure 4(b). For the 250 nm thick
medium device, gure 4(c), without bias a broadening of the
EQE spectrum compared to the thin device is observed, due
to the increased absorption in the photoactive layer [22]. With
increasing white-light bias, a drop in EQE from 65% (without
bias) to 55% (at 142 mWcm
2
white-light bias) is observed.
Upon normalization at = 600 nm, gure 4(d), a small
narrowing of the spectral response with increased white-light
4
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
Figure 5. Regular (a), (c), (e) and normalized (b),(d),(f ) white-light bias EQE spectra of P3HT: PCBM devices in inverted device
geometry with an active layer thickness of 90 nm (a), (b), 200 nm (c), (d) and 420 nm (e), (f ).
illumination can be seen. More pronounced changes in the
magnitude and shape of EQE spectrum are observed for the
thick device, gure 4(e). Peak EQE drops from 64% to
42% when the white-light bias is increased to 142 mWcm
2
.
Examining the normalized curves of gure 4(f ), the spectral
region from 450 to 550 nm sees a strong relative increase
with increased background light intensity, with the spectrum
acquired with high white-light bias intensity resembling that
of a device with a signicantly thinner active layer.
Figure 5 presents the white-light bias dependent EQE
data of inverted P3HT: PCBM devices. For the thin inverted
device, gure 5(a), the EQE spectrum of the device with
an active layer thickness of 90 nm closely resembles the
absorption spectrum. However a pronounced drop in EQE
with increased background light intensity is observed, with
EQEdropping from60%(without bias) to 42%(142 mWcm
2
white-light bias). This drop in EQE for the thin device is
more dramatic than observed for the thin standard device
that actually has a slightly higher active layer thickness.
Upon normalization, gure 5(b), a small relative enhancement
in EQE towards the blue end (400 nm to 475 nm) with
increasing bias can be seen. For the inverted device with a
medium active layer thickness of 200 nm, spectral changes
with increasing background illumination become prominent,
gure 5(c). Not only does the peak EQE drop from 64%
without white-light bias to 15% at 100 mWcm
2
, but this
drop is also accompanied by a signicant distortion of the
spectral shape visible both in the raw EQE data, gure 5(c),
and in the normalized data, gure 5(d). Without bias, the
EQEspectrumfollows the absorption spectrumof the blend but
becomes increasingly attened as the background illumination
is increased to 142 mWcm
2
. For the thick inverted device,
gures 5(e) and (f ) the EQE spectrum becomes even more
distorted; the spectrum without background illumination no
longer resembling the absorption spectrum. The EQE spectra
of the thick inverted device show antibatic features with low
EQE at wavelengths corresponding to high optical absorption
(500 nm). Examining the normalized curves, gure 5(f ),
the antibatic shape becomes more prominent with increasing
white-light bias intensity. There is also a signicant decrease in
absolute EQE for the thick device with increasing background
illumination with the EQE measured at = 550 nm dropping
from 27% to 14% with increased bias.
Qualitatively, the observed changes in the EQE spectral
shape can be explained by considering vertical gradients
in photocurrent generation efciency and/or recombination
[6, 23]. For thick lms, photons with wavelength close to
the peak absorption wavelength of P3HT (500 nm) will
mostly be absorbed within the rst 100 nmfromthe transparent
electrode. Photons with wavelengths away fromthe absorption
5
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
maximum such as 400 and 600 nm on the other hand
are more uniformly absorbed by the lm. This observation
largely explains the broadening of the standard device EQE
spectrumwith increasing lmthickness as thicker active layers
are required to absorb photons with wavelength far from the
absorption maximum. The distorted antibatic or M-shape of
the thick inverted device can be explained by poor photocurrent
generation in the region close to the transparent electrode
where most of the light with wavelength 500 nmis absorbed.
The peaks at 400 and 600 nm indicate that photocurrent
generation is more efcient at the back half of the device where
few 500 nm photons reach but many 400 and 600 nm photons
are still absorbed. An increase in the antibatic character of the
EQE spectrum with increasing white-light bias indicates that
the region close to the transparent anode becomes increasingly
less efcient at producing photocurrent compared to the back
half of the device. Conversely, for the thick standard device
structure the fact that the peak EQE at 500 nm becomes
more prominent with increasing background illumination can
be explained by the region close to the transparent electrode
becoming more efcient at producing photocurrent relative to
the back half of the device.
To conrm the nature of light absorption in the standard
and inverted devices we have performed optical simulations
via the transfer matrix method [21]. Figure 6 presents the
spatial distribution of the optical electric eld intensity for
wavelengths of 400, 500 and 600 nm for the 400 nm thick
standard device and the 420 nm thick inverted device. As
anticipated, the optical eld of 500 nm excitation is efciently
attenuated by the active layer in both devices. In contrast, the
optical eld of 400 and 600 nm light is only weakly attenuated
with a much higher relative intensity in the back half of the
device than 500 nm excitation.
The reason why the front half or back half of the
device is more efcient at producing photocurrent can be
understood by considering the charge-density prole in the
device and the associated internal electric eld. We have
previously used optical and device simulations to explain
the behaviour of standard and inverted all-polymer solar
cells based on blends of P3HT with the acceptor polymer
F8TBT [6]. In this system there is an imbalance in charge
mobility with the electron mobility being signicantly lower
than the hole mobility due to electron trapping [24]. In
contrast to the observations here, thick standard P3HT: F8TBT
devices exhibit decreasing device efciency with increasing
active layer thickness with the evolution of a pronounced
antibatic EQEspectrum, while inverted P3HT: F8TBTdevices
exhibit increasing device efciency with increasing active
layer thickness with a narrowing of the EQE spectrum about
500 nm. Due to the lower electron mobility compared to hole
mobility, in standard P3HT: F8TBT devices charge builds up
close to the transparent electrode causes a decrease in the
local electric eld strength and increased recombination. For
inverted P3HT: F8TBT devices in contrast where electrons
on average have to travel less distance to exit the device,
charge builds up in the rear of the device with an increase
in the electric eld strength near the transparent cathode.
Thus 500 nm thick inverted all-polymer devices are able to
0 100 200 300 400 500 600 700
0.0
0.2
0.4
0.6
0.8
N
o
r
m
a
l
i
s
e
d

E
l
e
c
t
r
i
c
F
i
e
l
d

I
n
t
e
n
s
i
t
y

|
E
|
2



ITO PEDOT P3HT:PCBM Ca Al
400 nm
500 nm
600 nm
(a)
(b)
Position in Device (nm)
0 100 200 300 400 500 600 700
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
N
o
r
m
a
l
i
s
e
d

E
l
e
c
t
r
i
c
F
i
e
l
d

I
n
t
e
n
s
i
t
y

|
E
|
2
Position in Device (nm)
400 nm
500 nm
600 nm
ITO ZnO P3HT:PCBM
M
o
O
3
Al
A
g
Figure 6. Spatial distribution of the optical electric eld intensity
for wavelengths of 400, 500 and 600 nm excitation simulated via the
transfer matrix method. (a) displays the case for the 400 nm thick
standard device while (b) displays the case for the 420 nm thick
inverted device.
exhibit high EQEs due to a high internal electric eld being
maintained close to the transparent electrode where most of the
photons are absorbed. The observation of the opposite effect
here, with thick inverted P3HT: PCBM devices exhibiting an
antibatic EQE spectral shape while standard devices maintain
a symbatic EQE spectral shape, is also consistent with
imbalanced charge transport but in this case with a higher
electron mobility compared to hole mobility [2527]. The
dominant recombination mechanisms for the P3HT: F8TBT
and P3HT: PCBM devices are likely to be different, however.
While enhanced geminate recombination due to decreased
electric elds were used to explain the decreasing performance
of standard P3HT: F8TBT devices with increasing active
layer thickness, geminate recombination is not as dominant
a recombination mechanism in P3HT: PCBM cells. Instead,
bimolecular recombination can be used to explain regions of
higher recombination particularly those far from the electrode
of the slowest carrier species [23].
3.3. Transient photocurrent measurements
In order to investigate charge transport in the actual
P3HT: PCBM devices studied here we have performed
6
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
Figure 7. Unnormalized (a), (c), (e) and normalized (b), (d), (f ) photocurrent transients of a regular P3HT: PCBM solar cell; data for a
130 nm thick active layer (a), (b), for a 250 nm (c), (d) and for a 400 nm (e), (f ) thick lm are displayed.
transient photocurrent measurements. These measurements
are performed by pulsing devices with 200 s square light
pulses from a 525 nm high-brightness LED and recording the
photocurrent response of the device on an oscilloscope. The
response is recorded at short circuit with devices connected
directly to the oscilloscope using a 50 input impedance.
By studying the turn-on and turn-off dynamics of the device
as a function of pulse light intensity, information regarding
charge transport dynamics and charge trapping can be obtained
[19]. Furthermore, charge transport can be investigated in
actual solar cell architectures without the need for creating
thick lms (as for time-of-ight measurements) or fabricating
separate devices with different electrodes. Figure 7 presents
the short-circuit photocurrent transients of the three standard
P3HT: PCBM devices studied. For all devices fast turn-on
and turn-off dynamics are observed, regardless of active layer
thickness. Little difference in the shape of the normalized
curves are observed, consistent with an absence of deep charge
trapping [19]. An increase in rise time is observed with
increasing device thickness, with the 400 nm thick device
exhibiting a rise time of 6 s compared to 3 s for the thin
device. In the absence of charge trapping the device rise time
is a reection of the transport dynamics of free charges [28],
and hence the slower rise time of the thick device is consistent
with the longer extraction time of the thick device as a result
of the increased active layer thickness and decreased internal
electric eld.
The short-circuit photocurrent dynamics of the inverted
P3HT: PCBM devices are shown in gure 8. Compared to
the devices in standard geometry, signicant changes in the
photocurrent dynamics are observed with increasing pulse
intensity, highlighted in the insets to the normalized graphs,
gures 8(b), (d) and (e). In general a quickening of the turn-
on dynamics is observed with increasing light intensity that
could be explained either by density dependent mobility [29]
or charge trapping [19]. In particular, the rise time of the
thin inverted device decreases from 7 s to 3 s while the
rise time of the thick inverted device decreases from 16.5 to
7 s as the pulse intensity is varied from 1.7 to 32 mWcm
2
.
The turn-off dynamics, however, do not exhibit a pronounced
pulse intensity dependence that would accompany charge
trapping [19]. Thus the charge transport dynamics of the
inverted devices are consistent with an absence of charge
trapping, but with a more pronounced density dependence of
charge transport compared to the standard device geometry.
Although in principle electron and hole transport in the active
layer in both inverted and standard devices should be similar
(morphology notwithstanding), due to the geometry of the
devices the turn-on and turn-off dynamics of inverted devices
will be more sensitive to hole dynamics, while the turn-
on and turn-off dynamics of the standard devices will be
7
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
Figure 8. Unnormalized (a), (c), (e) and normalized (b), (d), (f ) photocurrent transients of an inverted P3HT: PCBM solar cell; data for a
90 nm thick active layer (a), (b), for a 200 nm (c), (d) and for a 420 nm (e), (f ) thick lm are displayed. The insets show the rise and fall
dynamics in more detail.
more sensitive to electron dynamics. Thus the intensity-
dependent transient photocurrent dynamics of the inverted
devices are likely to reect a stronger density dependent
hole mobility compared to electron mobility, consistent with
previous observations by Shuttle et al [29]. Thus these
transient photocurrent observations indicate that that charge
collection is more efcient in the standard device geometry
rather than the inverted device geometry, consistent with
superior electron transport [23]. This conclusion is supported
by many other studies that have directly measured electron
and hole mobilities in P3HT: PCBM blends where the hole
mobility is consistently observed to be lower than the electron
mobility [2527].
The slower charge collection dynamics of the inverted
cells compared to the standard cells indicate that the distorted
EQE spectra of the inverted cells can indeed be explained
by a build-up of space-charge in the device due the lower
hole mobility. Tumbleston et al have come to a similar
conclusion regarding the inferior charge collection properties
of inverted P3HT: PCBM devices by modelling the current
voltage curves of standard and inverted devices extracting the
carrier transport length of electrons and holes [23]. Under
solar illumination they estimated the carrier transport length
for electrons to be 340 nm compared to only 90 nm for holes.
Thus in thick inverted devices hole transport severely limits
device operation with signicant recombination occurring near
the transparent electrode where holes are furthest from their
collection electrode [30]. This enhanced recombination close
to the transparent electrode explains the antibatic features
observed in the EQE spectra of inverted devices.
Interestingly, it has been suggested that the inverted
geometry should result in better charge collection due to the
vertical composition proles observed in P3HT: PCBM lms
[2]. Measurements by Vaynzof et al [7] and Parnell et al [31]
and others [2, 32] indicate a tendency for PCBMto segregate to
the substrate/lm interface and P3HT to the air/lm interface.
Thus an inverted cell where the P3HT-rich layer is at the hole-
collecting electrode and the PCBM-rich layer is at the electron-
collecting electrode should provide an advantage. A recent
report by Wang et al however found that devices prepared
where the active P3HT: PCBMhadbeenipped hadthe same
characteristics as conventionally prepared devices, suggesting
that interfacial segregation does not signicantly inuence
device performance. While it is expected that interfacial
segregation should play a role in inuence charge collection,
as revealed by Monte Carlo simulations [33], our observations
agree with those of Tumbleston et al that differences in bulk
charge transport mobility are more important in determining
the thickness-dependent performance of inverted and standard
P3HT: PCBM devices with interfacial segregation playing a
more minor role.
8
J. Phys. D: Appl. Phys. 45 (2012) 415101 T J K Brenner et al
4. Conclusions
White-light bias EQE and transient photocurrent measure-
ments have been used to compare the operation of standard
and inverted devices based on P3HT: PCBM blends. The
EQE spectra of inverted P3HT: PCBM devices were found
to exhibit antibatic features that become more prominent with
increasing white-light bias and active layer thickness. The
EQE spectra of standard devices in contrast were found to be
less sensitive to light intensity and more closely matched to
the absorption spectrum of the blend. Transient photocurrent
measurements on standard and inverted devices found slower
charge carrier dynamics in inverted cells consistent with in-
ferior hole collection compared to electron collection. These
data are consistent with hole transport limiting the performance
of thick inverted P3HT: PCBM solar cells leading to signi-
cant recombination close to the transparent electrode. Thus
differences in the bulk charge transport mobility of electrons
and holes in P3HT: PCBM blends plays a more dominant role
in determining the performance of standard and inverted cells
rather than vertical composition gradients.
Acknowledgments
This work was supported by the Engineering and Physical
Sciences Research Council (TJKB and CRM, EP/E051804/1,
EP/G031088/1, ZL and CRM). ZL also acknowledges the
Cambridge Overseas Trust and the Mott Physics of the
Environment Award for nancial support.
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