Chiguvare

PLASTIC S O L A R CELLS: AN A F F O R D A B L E
ELECTRICITY GENERATION TECHNOLOGY

Z. Chiguvare, Renewable Energy Programme, Department of Mechanical Engineering,

University of Zimbabwe, P. O. Box MP 167, Mr. Pleasant, Harare, Zimbabwe.

ABSTRACT
Polymer photovoltaics has become a very interesting area of research given the success
of polymer electronic devices like displays, field effect transistors and light emitting
diodes. We developed bulk heterojunction polymer-fullerene solar cells, with a
poly(3hexyl)thiophene and a soluble fullerene derivative [6,6]-phenyl-C61 butyric acid
methyl ester, P3HT:PCBM blend as the active layer, that yielded above 2.5 % energy
conversion efficiencies at standard test conditions. The solar cells were characterized by
analyzing current-voltage characteristics at various temperatures, from 80 to 400 K, and
measuring their external quantum efficiencies at room temperature. We discuss the ori-
gin of open circuit voltage observed and estimate that the upper limit of open circuit
voltage for P3HT: PCBM based polymer heterojunction solar cells is 1.2 V. The highest
current density measured was 8.5 mA/cm 2, while the energy conversion efficiency gave
2.71% for 1001nW/cm 2 white light intensity, AM1.5 spectrum at 300K. A maximum
external quantum efficiency of 65 % was also determined for monochromatic light of
wavelength 550 nm. Some of the major challenges in efficiency improvement of such
solar cells are discussed.

Keywords: Polythiophene; Fullerene; Bulk heterojunctions; Solar cells; Temperature

dependence; Light intensity dependence; Quantum efficiency.

1.0 I N T R O D U C T I O N
The widespread use of solar photovoltaic power has been elusive because it can be diffi-
cult and costly to manufacture the commercial photovoltaic cells, which are made of inor-
ganic crystals such as silicon. A novel approach to generate electricity from solar energy is
that of using organic polymer materials, that can be processed as easily as plastics, as light
absorbers. Unlike today's semiconductor-based photovoltaic devices, plastic solar cells can
be manufactured in solution in a beaker without the need for clean rooms. They do not
require the high deposition temperatures or complex processing as required in inorganic
devices, and they can be deposited onto large flexible substrates. This provides design
options that could lower the cost of using the cells. Unfortunately, lagging energy conver-
sion efficiencies has held their application back. The best organic cells convert a little
more than 2 percent of sunlight into electric current, while commercial inorganic cells
reach efficiencies of 20 percent. Inorganic cells, such as those based on silicon or on thin
films of CdTe or Cu(In,Ga)Se2, can display efficiencies greater than 15 percent.
Poly(3hexylthiophene) (P3HT) and similar plastic semiconductors currently are a hot
area of research in solar cell technology (Brabec et al 2003), but by themselves these

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plastics achieve very low light-conversion efficiencies. This has stimulated further in-
vestigations of new cell structures such as interpenetrating networks of donor and accep-
tor-type materials.

In this article a description of the development of an organic solar cell based on inter-
penetrating networks of P3HT and PCBM, a soluble Fullerene derivative, is given. The
measured temperature and illumination dependent J - V characteristic curves as well as
calculated efficiencies and fill factors are presented. Further, the general tendencies are
discussed and recommendations on further improvement are suggested.

2.0 T H E O R Y
The efficiency of solar cells depends on their capability for the absorption of photons,
charge carrier generation, separation and transport to the electrodes. Interpenetrating
conjugated polymer-Fullerene (donor-acceptor) networks, also referred to as bulk het-
erojunctions, are a very promising approach for the improvement of efficiency of poly-
mer solar cells. Photovoltaic devices based on these interpenetrating networks provide
increased charge carrier-generating interfaces, as compared to bi-layer photovoltaic de-
vices. A simplified schematic of the principle of operation of a solar cell based on inter-
penetrating networks of donor (polymer) and acceptor (fullerene) is shown in Fig. 1.
Light
r-1

[]
Indium Tin Oxide electrode I

Losses ~ : ~ : i ~:~.
D-A Electron
...............................................transfer
......... !ii i iii!!iiii!i
i l iiiiiiii!iiiii!, /
Exciton creation

Aluminium electrode

Fig. 1.A simplified diagram showing the photovoltaic effect in a bulk heterojunction
solar cell based on conjugated organic polymer absorber material.

The general scheme of the charge carrier generation processes in non-degenerate conju-
gated polymers (without acceptor) can been described as follows: The mobile charge car-
riers responsible for the photocurrent are produced as a result of the dissociation of primar-
ily generated singlet excitons due to interchain interaction, presence of Oxygen, (Anto-
niadis et al 1994, Bath et al 1997, Barth and B~issler 1997) or impurities, or a Schottky
interface at metal electrodes. Nevertheless, the charge carrier generation yield remains

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 Chiguvare

low, since other competitive processes, for example, photoluminescence and non-radiative
recombination also occur. The charge carrier generation yield can be enhanced by the
presence of a strong acceptor species, such as e.g. C60 molecule (Sariciftci 1995). The
process of charge separation in polymer:fullerene composites is ultra fast, and can occur
within 40 fs in PPV:PCBM composites (Brabec et al 2001), whereas the electron back
transfer is much slower (Brabec et al 1995). This results in effective formation of a me-
tastable charge-separated state. The photoinduced charge transfer is dependent upon the
electronic overlap of the donor ( D ) - acceptor (A) pair of molecules. A simple scheme for
the electron transfer mechanism is as follows: First the donor is excited, the excitation is
delocalised on the D-A complex before charge transfer is initiated, leading to an ion radi-
cal pair and finally charge separation can be stabilised possibly by carrier delocalisation on
the D + (or A-) species by structural relaxation. (Sariciftci 1995).
Symmetrical electrodes on such a film produce no voltage (Chiguvare, 2005), therefore
there is need to select asymmetrical electrodes in such a way as to provide minimal re-
sistance to the collection of the generated charge carriers. For efficient charge collection
from the absorber layer to an external circuit, both the positive and negative electrodes
must form ohmic contacts with the donor and acceptor networks, respectively. If this is
not the case, charge collection would be limited depending on the nature of potential
barriers built up at the contacts. The negative electrode must form an ohmic contact with
the electron transport level of the blend, typically the lowest unoccupied molecular or-
bital (LUMO) of PCBM. The positive electrode must first filter the charge carriers, i.e.,
block the passage of electrons and allow only holes to travel through it. In this context
PEDOT:PSS must form an ohmic contact with the hole transport level of the blend,
which is typically the highest occupied molecular orbital (HOMO) of the polymer. The
(PEDOT:PSS) / (P3HT:PCBM) interface is therefore the charge carrier separating inter-
face while the P3HT/PCBM heterojunctions provide exciton dissociating interfaces,
which on their own cannot generate a voltage. The ITO is needed since it is easier to
contact with external wires as compared to the PEDOT:PSS from our experimental
point of view.
The energetic picture of the operation of a P3HT:PCBM solar cell is shown in Fig. 2. We
observed that the PCBM also absorbs light and provides an alternative path of exciting the
blend. In this case electron transfer occurs from the P3HT LUMO to PCBM LUMO. In
either case, the result is the formation of a positive polymer radical and a negative PCBM
radical. However, although the ITO/PEDOT:PSS interface is ohmic, a small loss of Voc
may be observed due to band bending which may unavoidably occur at that interface.

3.0 M A T E R I A L S A N D M E T H O D S
P3HT is a conjugated polymer with an absorption spectrum that shows an onset at
around 2.14 eV. This amount of energy can be transferred to the electrons forming the
covalent bonds by several mechanisms, one of which is visible and ultraviolet light. It
is therefore possible to dislodge an electron from a double bond by absorption of
sunlight. It has been shown that a high electron affinity species such as PCBM, in the
neighbourhood may attract the dislodged electron within 40 fs, and hence create a me-
tastable charge separated state. Electron transfer was shown to occur in the case of the
developed solar cell by strong quenching of photoluminescence of P3HT in the presence

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of PCBM. Fig.3 shows the formulae of the materials used as donor and acceptor in the
developed bulk heterojunction polymer solar cell.

-2.5
LUMO (P3HT)
-3.0

-3.5
LUMO (PCBM)
~" -4.o

>4.5 AI

~-5.0 ITO HOMO (P3HT)

W
PEDOT'PSS
-5.5

-6.0

Positive Hole trans-

HOMO (PCBM) . . . . .

Active layer
1 Negative
ectrode
electrode port layer Polymer-fullerene blend

Fig. 2. Simplified energetic diagram of the photovoltaic process in an organic solar cell:
Absorbed photons with energy hv > 2.14 eV excite electrons from HOMO(P3HT)
5.14 eV into LUMO(P3HT) ~ 5.14 eV, which are then transferred to LUMO
(PCBM) ~ 4.2 eV, from which they can be collected by a negative A1 electrode
with workfunction q) ~ 4.28 eV. Holes are collected, via PEDOT:PSS of work-
function ~ 5.0 eV, by positive ITO electrode with workfunction ~ 4.8 eV. The red
arrows indicate an alternative path of photo-induced electron transfer.

ITO/PEDOT:PSS/P3HT:PCBM/A1 heterojunction solar cells were prepared in a Nitro-

gen atmosphere of a glove box and characterised. First, a thin layer of polyethylene-
dioxythiophene doped with polystyrene-sulfonic acid (PEDOT:PSS) (Baytron P, Bayer
AG, Germany) was spin coated on patterned clean ITO coated glass substrates in order
to smoothen the surface of ITO and hence avoid possible short circuits due to the spiky
roughness of the ITO surface. PEDOT:PSS is known as a good hole transport material,
and assures better hole collection from the active layer onto the ITO electrode, espe-
cially if its Fermi level lies between the workfunction of ITO and the HOMO level of
the polymer. An active layer consisting of a mixture of P3HT:PCBM in a 1:1 mass ra-
tio, dissolved in Chloroform, 5g/ml, was then spin coated on top of the dry PEDOT:PSS
film. Finally, 100 nm A1 contacts were deposited on the active layer by thermal evapora-
tion at low rate in a high vacuum of better than 1.10 .6 mbar in all cases. The device
structure is shown schematically in Fig. 4.

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 Chiguvare

\ . O
hv > E c
(CH2)6CH3 CH3
/

$ *'

Poly(3 hexylth io ph ene-2.5d iyl) [6,6]-phenyI-C61 butyric acid methyl

(P3HT) ester (PCBM)

Fig. 3 Formulae of the materials used as donor and acceptor in the developed bulk het-
erojunction polymer-fullerene solar cell. Light of sufficient energy excites both
P3HT and PCBM and ultra fast electron transfer to PCBM occurs.

~ , i ~ , - ' ~ ~ - - - ~ Aluminium electrode

P3HT:PCBM blend (1 :1)
PEDOT:PSS
.... . . .
i~ :i i iii:i:iii::ili! ~//~,~,, ~ Indium Tin Oxide
!
Glass substrate

Light
Fig. 4 Device structure of a P3HT-PCBM solar cell

After fabrication the solar cells were thermally annealed on a hot plate at 120~ in a nitro-
gen glove box for 2 minutes. Temperature and illumination dependent current voltage
characteristics were obtained by utilising an Advantest Source Measure Unit (Advantest
TR 6143), with the solar cell placed in a liquid-Nitrogen-cooled Cryostat at better than 10-
5 mbar vacuum. A 150W Xenon lamp (Osram XB0 150W/XBR) was used as the illumina-
tion source with a water filter placed in the light path to approximate the AM1.5 solar
spectrum. The light intensity reaching the device inside the cryostat was calibrated to 100
mW/cm 2 and neutral filters were used to vary the intensity. Quantum efficiency measure-
ments were performed under normal atmosphere at room temperature.

4.0 RESULTS AND DISCUSSION

Typical current density-voltage characteristic curves of an ITO/PEDOT:PSS/
P3HT:PCBM/A1 solar cell have been plotted in a semi logarithmic representation in Fig.
5 at different light intensities from 0.1 mW/cm 2 to 100 mW/cm 2 at T=300 K. The dark
J-V characteristic curves at room temperature show diode-like behaviour with a rectifi-
cation factor of about 3.5 x 103 at + 1.2V at 300K. The rectification is not due to the

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presence of a space charge region as in a p-n junction (or alternatively, due to a Schot-
tky contact), but possibly0 due to the workfunction difference of the two different elec-
trode materials as well as different mobility of electron and holes within the bi-
continuous interpenetrating network of two components. Under illumination, the rectifi-
cation ratio decreases from 400 at 0.1 mW/cm 2 to 16 at 100 mW/cm 2. This is a common
feature of polymer based solar cells, but the underlying reasons remain unclear. We
suggest that this is due to photoconductivity, where light increases the number of charge
carriers participating in the conduction of current.

10 2

1oo S
"~ 10" ~ ~ ; ~ !~----<u---- d a r k
E ..................':;~;~;:iYI .... .---.-.--o.......... O . 1 m W I c m 2

-13 1O 2 ~'='~;:~.~s~o ~ --~ + 3 m W /c m =

"~
~ 1 04 ~ ?';s, '~' ........::....... 10 m W / c m '
~_ % ~ ;i .........:t..........20 m W / c m '
10 -4 ~,~' ,}! :: ..... 50 m W / c m 2
Q') V .......9 ..........1 0 0 m W / c m 2
10 -~
-0,25 0,00 0,25 0,50 0,75 1,00
Voltage (V)

Fig. 5 Illumination dependent Current density - Voltage characteristics of a typical

ITO/PEDOT:PSS/P3HT:PCBM/A1 solar cell at 300 K.

For this cell, some values obtained for the main parameters such as power conversion
efficiency, ~/, open-circuit voltage, Voc, short-circuit current density, Jsc, and fill factor,
FF, obtained for different temperatures are shown in Table 1. All the values indicated
were obtained at 100 mW/cm 2 white light intensity.

Table 1. OutPut characteristics of a typical ITO/PEDOT:PSS/P3HT-PCBM/A1 solar cell.

Temperature Jsc Voc FF q
(K) (mA/cm ~) (V) (%) (%)
80 1.56 0.72 18.27 0.21
100 2.31 0.70 19.39 0.31
120 2.76 0.69 20.07 0.38
140 3.75 0.68 21.54 0.55
160 4.50 0.67 22.98 0.69
180 5.48 0.67 25.10 0.92
200 6.33 0.66 28.38 1.19
220 7.41 0.65 35.95 1.73
240 7.83 0.62 41.76 2.03
260 8.04 0.61 45.38 2.23
280 8.12 0.60 49.81 2.43
300 8.50 0.59 53.98 2.71
340 8.41 0.57 57.93 2.78
360 8.26 0.56 58.73 2.72
380 8.12 0.55 58.19 2.60

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 Chiguvare

Figure 6 shows the dependence of short circuit current density on temperature, for different
illumination intensities. We observed an increase of short circuit current density with tem-
perature, which tends to saturate to some maximum value around 300 K and remains con-
stant. The Jsc, being thermally activated at low temperatures, saturates and becomes nearly
temperature independent at elevated temperatures, clearly indicating that the charge carriers
traverse the active layer without significant losses. The short circuit current density increases
almost linearly with light intensity, for all the intensities considered in the experiment. This
suggests that concentrated light may give higher current, and could be considered as a way
of harvesting more electric power from such solar cells.
Figure 7 shows the dependency of open circuit voltage on temperature, for different
incident light intensities. The open circuit voltage of a solar cell based on
ITO/PEDOT:PSS/P3HT: PCBM/A1 decreases almost linearly when the temperature is
increased from 80 K to 380 K. The linear decrease with increase in temperature is con-
sistent with inorganic solar cell theory. Voc also increases with incident light intensity,
and tends to saturate at high intensities: the curves of Fig. 7 are closer together for high
intensities. However, for all the intensities considered, the Voc increases, and a maxi-
mum may be reached at higher than 100. The highest recorded open circuit voltage
value of 0.72 V was obtained at 80 K, at 100 mW/cm 2 white light, normal incidence.
We suggest that the open circuit voltage is dependent on the energetic levels of p and n
dopants and on their concentrations within the donor and acceptor materials. PCBM
introduces a transport level in the band gap of P3HT in the same fashion as an n dopant
does for inorganic semiconductors. PSS on the other hand, introduces a transport level
in PEDOT making it a p-type material. The junction formed should therefore be ex-
pected to behave like a p-n junction, and the open circuit voltage is determined by the
transport level of the n type material (P3HT:PCBM) and the transport level of the p type
material (PEDOT:PSS) which both tend to pin the electrode work-functions to their
respective transport levels.
The upper limit of open circuit voltage is determined by the energetic difference be-
tween the electron affinity of PEDOT:PSS and the LUMO of PCBM, which gives about
1.2 V. This can only be obtained at zero Kelvin. Extrapolation of the 100 mW/cm 2
curve of Fig. 7 yields a 0.76 V open circuit voltage at zero K.

The results also indicate an increase of energy conversion efficiency with increase in
temperature (see Table 1), which saturates at about 280 K, remains constant, and is fol-
lowed by a decrease after 380 K. This suggests an optimum operating temperature
range from about 280 K to 380 K. The highest efficiencies were recorded at 3 mW/cm 2
white light intensity for all temperatures, suggesting that at higher intensities, although
the charge carriers are generated, the material has poor transport properties and cannot
transport them effectively. The highest achieved efficiency at 300K, 100 mW/cm 2
white light intensity for our devices was 3.1%. A maximum external quantum effi-
ciency of 65 % was also determined for monochromatic light of wavelength 550 nm.
We believe that there is still scope for improvement of the efficiency of P3HT:PCBM
based solar cells. Siemens Solar reported an achievement of 5 % efficiency for similar
cells in December 2003. If repeatable on an industrial scale, then the cells will be slowly

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International Conference on Advances in Engineering and Technology

introduced in small consumer electronic gadgets such as calculators, mobile phone bat-
tery chargers, watches, etc., in the near future.

12 ' I ' I ' I ' I ' I ' I ' I

- - - o - - 0.1 m W / c m ~
-----o-- 1 m W / c m 2
IE 10
3 mW/cm ~
O
---?-- 10 m W / c m ~
E 8 20 m W / c m 2 ~_~/~-~-~b
--~-- 50 m W / c m 2 / b/
--I>-- 100 m W / c m 2 . ~ / ~
9B
r
6 /
"~ 4 .I> / <]/<]/<] /

/ ~<<]/<]/

~- 2 D/~/<l/r>-- , " , ~ 9 - - ^0 0 ~ 0 - - 0 - - 0 - - ~ - - 0 ~ 0 - - 0 - - 0

o
0 !

50 1 O0 150 200 250 300 350 400

Temperature (K)
Fig. 6 Temperature dependent short circuit current density of typical
ITO/PEDOT:PSS/P3HT:PCBM/A1 solar cell at different temperatures.

' i ' I ' i , i ' i ' i ' i

0,7 - ~ ~
>
v
(::!) 0,6
E~
05 ~o~
o ~
~..~__&-~.~ O
O
> 0,4

O.I m W / c m 2 ............ \%
0
0
(-
0,3

0,2
--o-- 1 mW/cm 2
3 mW/cm 2
~o
oL o
10 mW/cm 2
Q. 20 mW/cm 2
0 o,1 50 mW/cm =
1 O0 mW/cm 2
0,0 . . . . . . .
50 160 1;0 260 2;0 360 3;0 460
Temperature (K)

Fig. 7 Temperature dependent open circuit voltage of a typical ITO/PEDOT:PSS/

P3HT:PCBM/A1 solar cell at 300 K, at different incident light intensities.

5.0 C O N C L U S I O N S
A configuration of an ideal donor/acceptor heterojunction solar cell that consists of an
interpenetrating network of donor and acceptor as the absorber layer has been fabricated
and characterised by means of temperature and illumination dependent current density-

402
 Chiguvare

voltage characteristics. We stress however the need of a homogeneous mixture of donor

and acceptor to ensure sufficient electronic overlap between molecules of the D-A
blend, and propose an optimum mixture ratio of 1:1 by mass. Junction formation proce-
dures that should eliminate any possibility of contact with oxygen or other contami-
nants, is another possible way of improving the efficiency of solar cells based on P3HT.

6.0 ACKNOWLEDGEMENTS
I acknowledge the contributions of the following: V. Dyakonov, J. Parisi, and the PV
research group of the University of Oldenburg in Germany, where all the experiments
were carried out. Acknowledgements also go to the GTZ and DAAD - Germany for
funding the research.

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