The effect of anneal, solar irradiation and humidity on the

adhesion/cohesion properties of P3HT:PCBM based inverted polymer

solar cells
Stephanie R. Dupont1, Eszter Voroshazi2,3, Paul Heremans2,3, Reinhold H. Dauskardt1
1

Department Materials Science and Engineering, Stanford University, Stanford, Ca, USA
2
imec, Organic Photovoltais, Leuven, Belgium
3
Katholieke Universiteit Leuven, ESAT, Leuven Belgium

Abstract We use a thin-film adhesion technique that

enables us to precisely measure the energy required to separate
adjacent layers in OPV cells. We demonstrate the presence of
weak interfaces in prototypical inverted polymer solar cells,
either prepared by spin, spray or slot-die coating, including
flexible and non flexible solar cells. In all cases, we observed
adhesive failure at P3HT:PCBM/PEDOT:PSS interface,
indicating the intrinsic material dependence of this mechanism.
The impact of temperature, solar irradiation and humidity on the
adhesion and cohesion properties of this particular interface is
discussed. First, we have found that post-deposition annealing
increases the adhesion significantly. Annealing changes the
morphology in the photoactive layer and consequently alters the
chemical properties at the interface. Second, solar irradiation on
fully encapsulated solar cells has no damaging but in contrast an
enhancing effect on the adhesion properties, due to the heat
generated from IR radiation. Finally, the synergetic effect of
stress and an environmental species like moisture greatly
accelerates the decohesion rate in the weak hygroscopic
PEDOT:PSS layer. This results in a loss of mechanical integrity
and device performance. The insight into the mechanisms of
delamination and decohesion yields general guidelines for the
design of more reliable organic electronic devices.
Index Terms mechanical reliability, adhesion, cohesion,
environmental effects, annealing, humidity, solar irradiation

I.

INTRODUCTION

Organic photovoltaic (OPV) devices are one of the most

promising applications of organic semiconductors as these
materials are compatible with flexible plastic substrates
resulting in a light weight, inexpensive and decorative product
using roll-to-roll module fabrication. The current state-of-theart small size cells have reached over 10 % power conversion
efficiency (PCE) and therefore achieved one of the critical
milestones for market introduction [1]. While the electrical
failure mechanisms in OPVs have been extensively
investigated, little is known about their mechanical stability,
which is an equally important and critical factor determining
their long term reliability. The combination of the thin-film
stresses present in organic solar cells, including shrinkage,
thermal, and growth stresses, together with other possible

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mechanical handling and operation stresses provide the

mechanical driving force for delamination of weak interfaces
or decohesion of weak layers. This leads to a loss of
mechanical integrity and device performance.
In this study, we demonstrate the presence of weak
interfaces in inverted polymer:fullerene solar cells, either
prepared by a spin, spray or slot-die coating, including flexible
and non flexible solar cells. We will discuss the impact of
temperature, solar irradiation and humidity on the adhesion
and cohesion properties of poly(3-hexylthiophene) and 1-(3methoxycarbonyl)-propyl-1- phenyl-(6,6)C61 blends (P3HT:
PCBM) based inverted polymer solar cells. The choice of
inverted device architecture is motivated by their intrinsic air
stability, compatibility with roll-to-roll processing without
affecting device efficiency, proving the industrial relevance of
this device architecture.
II.

EXPERIMENTAL

A. Solar Cell Preparation

Zinc oxide (ZnO) precursor was deposited from solution on
the previously cleaned indium tin oxide coated substrates. A
250nm active layer composed of 1:1 wt% mixture of
P3HT:PCBM was deposited either from o-dichloro-benzene
based solution or an engineered ink [2]. A thin poly(3,4ethylenedioxythiophene) poly(styrene-sulfonate) (PEDOT:
PSS) layer was deposited from solution prior to metallization a
silver (Ag) layer by either thermal evaporation or screen
printing. Spin-coated and spray-coated cells were prepared on
glass substrates, while slot-die coated cells were processed on
a flexible PET substrate. Further details about the processing
by conventional spin-coating, spray-coating and roll-to-roll
slot-die coating are described elsewhere [3, 4].
B. Thin-film adhesion testing
The critical adhesion or cohesion energy, Gc (J/m2) is the
energy needed to cause delamination between layers or failure
of a weak layer, respectively. This property is typically
strongly dependent on the material, mechanical and processing
properties. We applied a double cantilever beam (DCB) based

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to a stress-enabled chemical reaction between a chemical

species in the environment and strained bonds at the crack
front [8]. Environmentally assisted debonding generally
occurs at driving forces well below the Gc of an interface and
is a time-dependent process controlled by rate limiting steps at
the crack front. During subcritical characterization, the crack
growth rate, da/dt is measured in function of the applied
driving force, G, using load relaxation techniques and
compliance methods [5].
Illustration of the double cantilever beam (DCB) test
Fig. 1.
specimen

technique, illustrated in Fig. 1, to

measure the adhesion
energy, whereby the inverted solar cells were epoxy bonded in
between two elastic beams. This well-established industrial
technique has the advantage of providing quantitative and
reproducible measurement, as demonstrated in previous
studies [5, 6]. The specimens were tested in a thin-film
adhesion testing system (Delaminator DTS, Menlo Park, CA)
from which a load versus displacement curve was recorded.
Finally, Gc can be expressed in terms of the critical load at
which crack growth occurs, Pc, the corresponding crack
length a, the plain strain elastic modulus, E and the specimen
dimensions; width, b and half- thickness, h. The fracture
energy was calculated from (1) [7].

12 Pc 2 a 2
h
Gc = 2
1 + 0.64
3
B E 'h
a

(1)

All testing were carried out in laboratory air environment at

~25C and ~45% relative humidity.
Unlike critical debonding, environmentally assisted
debonding arises from synergistic effects involving both
mechanical loads and an environmental species. This is

Fig. 3. Adhesion energy as a function of annealing time and

temperature (spin coated).

C. Surface Characterization Techniques

Following mechanical testing, x-ray photo spectroscopy
(XPS, PHI 5000 Versaprobe), contact angle (CA)
measurements and atomic force microscopy (AFM, XE-70)
were used to determine the location of the fracture path and to
investigate the physics and chemistry of the degradation
processes.
III.

RESULTS AND DISCUSSION

For all three deposition techniques, adhesive failure was

observed by XPS and CA between the P3HT:PCBM and
PEDOT:PSS. The PCE and Gc values for the different
deposition techniques are shown in Fig. 2. Although the
different processing methods involved different solvents, the
failure path is independent of the deposition technique. We
observed a lower adhesion energy in case of the flexible slotdie coated solar cells. We attribute this to the fact that these
solar cells are processed in a roll-to-roll process.
A. Anneal
Fig. 2. The adhesion energy and PCE is shown as a function of the
various deposition techniques applied for the P3HT:PCBM and
PEDOT:PSS layers.

sometimes known as subcritical cracking and is generally due

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Encapsulated inverted polymer solar cells were

systematically annealed at various temperatures and annealing
times. It is well known that annealing the morphology in the
photoactive layer changes. The P3HT chains form ordered
crystalline domains and the PCBM molecules diffuse
outwards into segregated PCBM clusters [9]. Additionally

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vertical phase separation in the BHJ takes place [10] and

consequently, annealing alters the chemical properties at the
interface. We have found that post-deposition annealing time
and temperature increased the adhesion significantly for both
the spin coated as well as the flexible slot-die coated inverted
solar cells. The latter is extensively described in one of our
previous studies [11]. Here we focus on spin coated devices,
and measured the increased adhesion energy as a function of
time and annealing temperatures shown in Fig. 3.

along with temperature and mechanical loads. Due to its

B. Solar Irradiation
To study the effect of sunlight, fully encapsulated spin
coated solar cells were exposed to 1 sun intensity and AM
1.5G spectrum illumination in an ATLAS Suntest XXL
system under 40 %RH and 40 C. Under these conditions the
samples were exposed to particularly harmful UVA
illumination. The PCE and Gc were regularly measured and
shown in Fig 4.

Fig. 5. Crack growth rate measured

environments as a function of applied G.

in

various

humidity

hygroscopic nature, water easily diffuses through the layer and

breaks the hydrogen bonds formed between PEDOT:PSS
grains resulting in an accelerated decohesion rate.
IV.

Fig. 4. The adhesion energy (blue, squares) and PCE (%) (red,
triangles) as a function of simulated AM1.5G exposure time.

While the short-circuit current decreased in the first 50 h,

the increase of fill factor attributed to the increased
conductivity of ZnO, lead to only 5-10% decrease in PCE over
500 h. In the meantime, an increase of adhesion energy with
exposure time was observed. Solar irradiation in absence of air
has no damaging effect on the mechanical properties of this
interface, but in contrast improved the adhesion energy.
Illumination inherently also heated the samples to a
temperature of 40C-45C, owing to IR radiation present in
the solar spectrum. This long time annealing process as earlier
described enhanced the adhesion at the respectively interface.

SUMMARY

In summary, we have found that the P3HT:PCBM/

PEDOT:PSS interface is the weakest in inverted polymer
solar cells, independent of the deposition technique. Annealing
can be used as a method during processing to make this
interface stronger. Solar irradiation on fully encapsulated solar
cells has no damaging but in contrast an enhancing effect on
the adhesion properties, due to the heat generated from IR
irradiation. Finally, the synergetic effect of mechanical loads
and humidity can greatly accelerate the damage evolution and
decohesion of the hygroscopic PEDOT:PSS layer. Increased
decohesion under high humidity conditions constitutes an
important concern for the reliability and the need for device
packaging. This study provides insights into the mechanisms
of delamination and decohesion and yields guidelines for the
design of more reliable organic devices.
ACKNOWLEDGEMENTS
We acknowledge C. Girotto for his assistance with the spraycoated sample preparation. This research was supported by the
Center for Advanced Molecular Photovoltaics (CAMP)
supported by King Abdullah University of Science and
Technology (KAUST) under award no. KUS-C1-015-21.

C. Humidity
The environmentally assisted crack growth rate curves,
da/dt (m/s) are shown in Fig. 5 as a function of the applied
driving force, G (J/m2), measured in various relative humidity
environments. CA and XPS confirmed a cohesive failure path
in the PEDOT:PSS layer. The cohesion of the PEDOT:PSS
conductive polymer was significantly influenced by moisture

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