Quantitative evaluation of inhomogeneous device operation in thin film solar cells by

luminescence imaging
,
Marco Seeland, Christian Kästner, and Harald Hoppe

Citation: Appl. Phys. Lett. 107, 073302 (2015); doi: 10.1063/1.4929343

View online: http://dx.doi.org/10.1063/1.4929343
View Table of Contents: http://aip.scitation.org/toc/apl/107/7
Published by the American Institute of Physics
 APPLIED PHYSICS LETTERS 107, 073302 (2015)

Quantitative evaluation of inhomogeneous device operation in thin film solar

cells by luminescence imaging
Marco Seeland,1,2 Christian Ka
€stner,1,3 and Harald Hoppe1,4,5,a)
1
Institute of Physics, Technische Universit€
at Ilmenau, Langewiesener Str. 22, 98693 Ilmenau, Germany
2
Institute of Computer and Systems Engineering, Helmholtzplatz 5, 98693 Ilmenau, Germany
3
Institute of Thermodynamics and Fluid Mechanics, Helmholtzring 1, 98693 Ilmenau, Germany
4
Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena,
Philosophenweg 7a, 07743 Jena, Germany
5
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena,
Humboldtstrasse 10, 07743 Jena, Germany
(Received 5 July 2015; accepted 10 August 2015; published online 20 August 2015)
We present a method for quantitative evaluation of electroluminescence images from thin film
solar cells. The method called “quantitative electroluminescence imaging” (QuELI) is based on
decoupling local equivalent circuit parameters and allows calculation of the local current-density
as well as the local series resistance and saturation current-density. By application of this method
to electroluminescence images obtained from polymer-fullerene based solar cells, we show that
QuELI allows efficient separation between: (a) properties of the electrodes and their associated
interfaces by the local series resistance and (b) properties of the active layer by the saturation
current-density. We furthermore reveal large scale lateral phase separation via the strong variation
in the saturation current-density, which delivers information on the energetic difference of thermal
C 2015 AIP Publishing LLC.
activation of charge carriers across the effective active band gap. V
[http://dx.doi.org/10.1063/1.4929343]

Apart from other methods, such as Lock-In Thermography1 phase separation occurring within the photoactive layers of
and Light-Beam Induced Currents,2 luminescence imaging these devices.
has evolved to a versatile characterization method for study- The emission of luminescence is caused by radiative
ing the spatially resolved behavior of polymer solar cells. decay of excess charge carriers in an “excited semiconductor”.
Especially in degradation studies, the use of luminescence The description of this emission is given by W€urfel’s general-
imaging is beneficial because it is non-invasive and offers ization of Planck’s law accounting for non-equilibrium condi-
short measurement times.3 Depending on the excitation tions by introduction of a chemical potential of radiation.12 A
mechanism, i.e., either electrical or optical excitation, it non-zero chemical potential is equal to the separation of the
allows characterization of the electrical contacts and the quasi-Fermi-levels of the excess charge carriers and thus to
active layer separately.4 However, except for the correction the voltage V applied to the junction in the case of electrolu-
of the active area,4–6 the data analysis so far is mainly quali- minescence (EL). The spectral photon flux U of the EL
tative, i.e., interpretation of the measured luminescence depending on both the photon Energy E and the local voltage
image by comparison with other techniques.6–8 A quantita- can thus be calculated as
tive analysis was realized for extraction of the local current-
voltage characteristics of the active layer as well as for 2pE2 aðEÞ
UðE; V Þ ¼ ; (1)
determination of the involved resistances in an equivalent 3 2
h c exp½ðE=q  V Þ=Vth   1
circuit network model.9 However, this analysis was restricted
to laterally homogeneous solar cells. Here, we present a with the absorption coefficient a and the thermal voltage
quantitative analysis of electroluminescence images of later- Vth ¼ kB T=q. For E/q – V  Vth, i.e., for voltages that are
ally inhomogeneous polymer solar cells that can be generally small compared to the emitted photon energies, Eq. (1) can
applied to solar cells of any kind. By decoupling the local be approximated to
physical parameters from each other, this analysis yields cal-  
culation of the local current flow through the active layer, as V
UðE; V Þ ¼ aðEÞUbb ðEÞexp ; (2)
well as the local series resistance and saturation current- Vth
density. Upon application to polymer solar cells based on
anthracene containing PPE-PPV copolymer (poly(p-phenyl- where Ubb ðEÞ is the blackbody spectrum. If no spectral filters
ene-ethynylene)-alt-poly(p-phenylene-vinylene))10,11,13-PCBM are used, the laterally resolved luminescence signal Ui
(phenyl-C61-butyric-acid-methyl-ester) blends, the local sat- detected by the spectrally integrating CCD camera is the
uration current-density correlated well with the strong lateral spectrally integrated photon flux multiplied with the trans-
mission of the optics and the quantum efficiency of the de-
tector and can be simplified to
 
a)
Author to whom correspondence should be addressed. Electronic mail: Vi
Ui ðV Þ ¼ Ci exp ; (3)
harald.hoppe@tu-ilmenau.de and harald.hoppe@uni-jena.de Vth

0003-6951/2015/107(7)/073302/5/$30.00 107, 073302-1 C 2015 AIP Publishing LLC

V
073302-2 €stner, and Hoppe
Seeland, Ka Appl. Phys. Lett. 107, 073302 (2015)

where the index i denotes local values. According to Eqs. (2) The local series resistance Rs,i is then calculated from
and (3), lateral variations in the detected EL intensity origi- the change in the two EL images
nate either from lateral variations in the absorption coeffi-
cient or in the local voltage Vi. Variations in the absorption DVext DðlnJi Þ
Rs;i ¼  Vth : (8)
can be induced by, e.g., optical losses or local material prop- DJi DJi
erties and enter the prefactor Ci in Eq. (3), whereas changes
in the local voltage are due to series resistance effects and Once Rs,i is obtained, the local saturation current-density can
enter exponentially in Eq. (3). As the EL intensity is propor- be calculated from Eq. (7).
tional to the injection current-density, the prefactor C is also The local current-density Ji is calculated by relating the
proportional to the saturation current-density Js from the local EL intensity Ui to the total current Iext measured at the
Shockley equation terminals of the solar cell
   
V Ui Iext
J ðV Þ ¼ Js exp 1 : (4) Ji ¼  : (9)
Vth X
N Apx
Ui
i¼1
The saturation current-density itself originates from the ther-
mal generation of charge carriers at the donor/acceptor (D/ In Eq. (9), Apx is the pixel area and N the total number of
A) interface or in the bulk of the phase separated materials pixels.
and is thus equal to the Boltzmann factor with the activation This quantitative evaluation of electroluminescence
energy DE and the material dependent prefactor Js,013 images (QuELI) was applied to EL images of polymer solar
  cells based on an anthracene-containing PPE-PPV alternat-
DE
Js ¼ Js;0 exp  : (5) ing copolymer (AnE-PV) blended with PCBM.11,14 The
2nkB T
synthesis, material, and photovoltaic properties of this
The factor 2 in Eq. (5) is arising from the thermal generation material along with the preparation protocols were detailed
of both an electron and a hole that can contribute to the dark previously.10,11 As large interfacial energies cause a repul-
current. The activation energy DE depends on the energy dif- sion of AnE-PVab from PCBM, the material system tends
ference between the HOMO (highest occupied molecular or- to phase separate on a large scale11,14,16 which makes it a
bital) and the LUMO (lowest unoccupied molecular orbital) perfect candidate for the method presented here.
Figure 1 shows the JV-curves of the measured solar cell
(
heterojunction interface : EHOMO;D  ELUMO;A under 1 sun illumination using a class A solar simulator and
DE ¼ ; in the dark. The measurement was performed using a
pristine material phases : EHOMO;D  ELUMO;D
Keithley K2400 source-measurement-unit in voltage sweep
(6) mode. Electroluminescence imaging (ELI) was performed
with a cooled silicon charge-coupled-device camera with
and is different for the D/A-interface and a single material
enhanced NIR sensitivity as described before.3 The first EL
phase. As the activation energy for the single material
image was taken at an injection current equal to the short-
phases is larger compared to the heterojunction interface
circuit current under 1 sun illumination, where the dark for-
activation energy, less charge carriers are thermally gener- ward current was dominated by the exponential diode char-
ated in the single material phase. This causes a reduced sat- acteristics. For the second EL image, we used a higher
uration current-density for the phase separated regions on injection current amounting to five times the short-circuit
the sample. The lateral phase separation can thus be
deduced from the lateral distribution of the saturation cur-
rent-density.
For separation between the different influences on the
EL intensity discussed in Eq. (3), we use an appropriate
equivalent circuit model and two EL images taken at differ-
ent externally applied voltages. Every pixel of the solar cell
in the images is then represented by an equivalent circuit
including an ideal diode with one serial resistor and all pix-
els connected in parallel. The local series resistance Rs,i
represents a quasi-external series resistance as it connects
every pixel to the external contacts. According to this
equivalent circuit model, the local current-density Ji can be
written as
 
Vext  Ji Rs;i
Ji ¼ Js;i exp ; (7)
Vth

where Vext is the voltage applied at the terminals of the solar FIG. 1. JV-curves of the investigated AnE-PV:PCBM solar cell under simu-
cell. lated solar illumination (black line) and in the dark (dotted red line).
073302-3 €stner, and Hoppe
Seeland, Ka
current where the global current is already limited by the se-
ries resistance of the solar cell. All ELI measurements were
background corrected by subtraction of corresponding cam-
era readout without electrical excitation.
The resulting EL image taken at Jext ¼ Jsc and the images
calculated by the QuELI are shown in Figures 2(a)–2(c).
Whereas the bare EL intensity in Figure 2(a) exhibits many
inhomogeneities of unknown origin (compare with Eq. (3)),
QuELI allows decoupling the different contrast mechanisms
on the ELI data. The local current-densities were obtained by
comparing the integral local EL intensities to the total current
flow through the device according to Eq. (9). As shown in
Figures 2(b) and 2(c), the series resistance and the saturation
current-density can be effectively decoupled. The dark areas
visible in the unaltered electroluminescence image of the cell,
i.e., the rim near the edges and the large dark spot centered on
the cell area, correspond to an increased series resistance in
the range of 50 Xcm2 and are presumably caused by a local
injection barrier at the aluminum cathode introduced by deg-
radation of the device due to long shelf storage of 10 months.
The device area that is not affected by degradation exhibits
typical series resistances of about 5 to 15 Xcm2. The
FIG. 2. EL image (a) of the polymer solar cell and calculated parameter
images: (b) series resistance and (c) saturation current-density. The relative
donor emission image (d) was obtained by spectral selection of the electrolu-
minescence signal.
Appl. Phys. Lett. 107, 073302 (2015)
FIG. 3. EL spectrum (solid line) of the AnE-PV-based polymer solar cell
used in this study. The emission between 600 nm and 800 nm origins from
bimolecular recombination in the donor phase whereas the emission in the
NIR origins from recombination of a charge-transfer exciton at the donor/
acceptor interface. Both emissions were separated in the luminescence imag-
ing experiment by using a longpass filter whose transmission is included in
the graph as dashed line.
saturation current-density image in Figure 2(c) yields a well
resolved contrast on the whole cell area, only the noise is
increased in the high series resistance areas as the electrolumi-
nescence intensity is considerably reduced. In Figure 2(c),
regions with high saturation current-densities on the order of
1011 mAcm2 are clearly visible and separated from each
other by trenches with reduced saturation current-densities in
the order of 1016 mAcm2.
We attribute this contrast in saturation current-density to
the microscale phase separation of donor and acceptor com-
ponents. For verification of the phase separation indicated by
the saturation current-density images according to Eq. (6),
additional ELI measurements with spectral selection of sin-
gle material and D/A-interface emission were performed by
using a longpass filter with a cut-off wavelength of 840 nm.
The EL spectrum in Figure 3, recorded with an Avantes
AvaSpec ULS-2048 fiber spectrometer, indicates two radia-
tive recombination mechanisms: whereas recombination in
the pristine donor material (D* ! GS in Figure 4) leads to
EL emission ranging from 600 nm to 800 nm, the recombina-
tion of a charge transfer exciton (CTE) at the D/A-interface
FIG. 4. Energy diagram displaying the excited states D* and (AD*) relative
to the ground state: Whereas large HOMO-LUMO differences DE in the
pristine donor phase correspond to reduced Js and EL emission ranging from
600 to 800 nm, the decreased DE0 at the heterojunction interface corresponds
to large Js and red-shifted EL emission from 850 nm to 1100 nm. The energy
dE defining the red-shift is the electron transfer energy and can be calculated
by the ratio of Js.
073302-4 €stner, and Hoppe
Seeland, Ka
is red-shifted and ranges from 850 nm to 1100 nm ((AD)* in
Figure 4). Radiative recombination within the fullerene
phase, typically peaking around 730 nm, was not observed.
Using the longpass filter, only the EL emission originating
from radiative recombination of the CTE at the D/A inter-
face was detected. The EL emission of the donor phase,
shown in Figure 2(d), was determined by the relative differ-
ence of the unfiltered and the spectrally selected ELI meas-
urements. Here, a large difference accounts for a relative
increase of the emission from the donor phase. Comparison
of the saturation current-density image with the evaluated
emission originating from the pristine donor phase, i.e.,
Figures 2(c) and 2(d), indeed shows that the low saturation
current-density regions exhibited a large change in the emis-
sion spectrum, as the radiative recombination within the do-
nor phase was more intense. Thus, it can be deduced that in
these regions, a microscale phase separation has occurred,
resulting in the decrease of saturation current-density accord-
ing to Eq. (5).
According to the calculated saturation current-density
(Figure 2(c)) and the relative donor phase emission image
obtained by spectral selection of the EL signal (Figure 2(d)), it
can be deduced that regions with reduced saturation current-
densities correlate to large scale phase separation yielding pris-
tine donor phases, whereas the mixed phase shows relatively
large saturation current-densities. Previous reports have
pointed out that AnE-PVab tends to aggregate strongly when
intermixed with PCBM in common solutions, leading to an
increased crystallinity.11,14 Intermixed regions originate from
a nanoscale phase separation between locally aggregated AnE-
PV and PCBM phases or even intimately mixed “intercalated”
phases between PCBM and the disordered polymer.15 The sat-
uration current-densities of the intermixed phase is in the order
of 1011 mAcm2, whereas the phase separated regions exhib-
ited minimum saturation current-densities on the order of
1016 mAcm2. Thus, the maximum change in saturation
current-density that is induced by phase separation amounts to
five orders of magnitude. The difference in activation energy
(dE in Figure 4) can be calculated according to Eq. (5) by the
ratio of the minimum and maximum saturation current-
densities. As the material in the phase separated regions is in
mainly the donor, dE equals the electron transfer energy that is
lost in terms of the open-circuit voltage. The calculation based
on Eq. (5) yields electron transfer energies of dE  600 meV,
which is in good agreement with spectral shift between donor
and CTE emission in the electroluminescence spectrum in
Figure 3.
Using the method presented here allows calculation of
parameter images from only two EL images. Furthermore,
the different parameters are efficiently separated from each
other, allowing, e.g., to study the phase separation by ELI in-
dependently from local series resistance effects. The deduced
phase separation was confirmed by spectral selection of the
EL signal using an optical filter. This spectral selection
method suffers inevitably from regions with very large series
resistances as they exhibit very low EL intensities.
Furthermore, the use of optical filters increases the optical
path causing a change in the field of view and blurring of
one of the images if the focal point is changed larger than
the depth of focus allows.
Appl. Phys. Lett. 107, 073302 (2015)
In conclusion, we presented a method for quantitative
analysis of EL images from thin film solar cells. The method
is based on the computational evaluation of two images and
allows calculation of the local current-density, series resist-
ance, and saturation-current density. The images can be effi-
ciently calibrated to absolute values by relating the integral
local EL intensity to the total current through the solar cell.
Applied to ELI measurements on a polymer solar cell based
on an anthracene-containing PPE-PPV copolymer blended
with PCBM, a considerable reduction in saturation current-
density due to phase separation of materials was found. This
reduction of the saturation current-density correlates well
with the different activation energies of charge carriers
within the pristine donor phase and the D/A-interface.
Analyzing the spread in saturation current-densities calcu-
lated by our method, the difference in activation energy was
calculated to about 600 meV, which is in accordance with
the spectral positions of the respective EL emission spectra.
Whereas the phase separation of the sample studied here
occurred on a microscopic scale, the method can also be
applied for studying finer phase separation within Abbe’s
limit by obtaining EL images using a microscope.
Furthermore, a quantitative analysis of ELI data is highly
useful for degradation studies as it principally allows selec-
tive quantitative characterization of the active layer as well
as the electrodes and their associated interfaces. It is thus
also possible to study morphological degradation, if the scale
of phase separation exceeds the optically resolvable dimen-
sions obtained by the setup used for imaging.
We thank Daniel A. M. Egbe (LIOS, Linz, Austria) for
providing the polymer used in this study. The authors thank
the Federal Ministry of Education and Research (BMBF) for
financial support of the project “AIMS in OPV” (Contract
No. 03EK3502) and the Deutsche Forschungsgemeinschaft
(DFG) for financial support in the framework of the priority
program SPP1355. M.S. gratefully acknowledges financial
support within the scholarship program of the German
Federal Environmental Foundation (DBU). C.K.
acknowledges financial support by the Thuringian federal
graduate school program “PhotoGrad.” We thank the
Thuringian Ministry of Culture for financial support in the
framework of FIPV II.
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