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FULL PAPER

DOI: 10.1002/adfm.200800439

Effect of Oligothienyl Chain Length on Tuning the Solar Cell

Performance in Fluorene-Based Polyplatinynes**
By Li Liu, Cheuk-Lam Ho, Wai-Yeung Wong,* Kai-Yin Cheung, Man-Kin Fung, Wai-Ting Lam, Aleksandra
B. Djurisˇic´,* and Wai-Kin Chan

A series of solution-processable and strongly visible-light absorbing polyplatinynes containing oligothienyl–fluorene ring hybrids
were synthesized and characterized. These rigid-rod organometallic materials are soluble in polar organic solvents and show
intense absorptions in the visible spectral region, rendering them excellent candidates for bulk heterojunction polymer solar cells.
The photovoltaic behavior depends significantly on the number of thienyl rings along the polymer chain, and some of these
polymer solar cells show high power conversion efficiencies (PCEs) of up to 2.9% and a peak external quantum efficiency to 83%
under AM1.5 simulated solar illumination. The effect of oligothienyl chain length on improving the polymer solar cell efficiency
and on their optical and charge transport properties is elucidated in detail. At the same blend ratio of 1:5, the light-harvesting
capability and PCE increase markedly with increasing number of thienyl rings. The power dependencies of the solar cell
parameters (including the short-circuit current density, open-circuit voltage, fill-factor, and PCE) were also examined. The
present work opens up an attractive avenue to developing conjugated metallopolymers with broad and strong solar energy
absorptions and tunable solar cell efficiency and supports the potential of metalated conjugated polymers for efficient power
generation.

1. Introduction lightweight solar energy conversion platform as compared to

The need to develop inexpensive renewable energy sources
stimulates intensive scientific research for efficient, low-cost,
and lightweight photovoltaic devices.[1] Polymer-based organic
photovoltaic systems hold the promise for a cost-effective,
[*] Prof. W.-Y. Wong, Dr. L. Liu, Dr. C.-L. Ho
Department of Chemistry and Centre for Advanced Luminescence
Materials, Hong Kong Baptist University
Waterloo Road, Kowloon Tong, Hong Kong (P. R. China)
E-mail: rwywong@hkbu.edu.hk
Dr. L. Liu
Ministry of Education Key Laboratory for the Synthesis and
Application of Organic
Functional Molecules and School of Chemistry and Chemical
Engineering
Hubei University, Wuhan 430062 (P. R. of China)
Dr. A. B. Djurišić, K.-Y. Cheung, M. K. Fung, W. T. Lam
Department of Physics, The University of Hong Kong
Pokfulam Road, Hong Kong (P. R. China)
E-mail: dalek@hkusua.hku.hk
Prof. W.-K. Chan
Department of Chemistry, The University of Hong Kong
Pokfulam Road, Hong Kong (P. R. China)
[**] This work was supported by a CERG Grant from the Hong Kong
Research Grants Council (HKBU 202607P) and a Faculty Research
Grant from the Hong Kong Baptist University (FRG/06-07/II-63) (to
W.-Y. Wong). Financial support from the National Natural Science
Foundation of China (20671033) (to L. Liu) and from the Strategic
Research Theme, University Development Fund, and Seed Funding
Grant and Outstanding Young Researcher Award from the University
of Hong Kong (to A. B. Djurišić) is also acknowledged. Supporting
information is available online at Wiley Interscience or from the
author.
the inorganic semiconductors and have potential use in large-
area flexible devices.[2] They are often based on polymer
donors and molecular acceptors in blends, so-called bulk
heterojunctions.[3] Encouraging progress has been made over
the past few years in the research area of photovoltaic solar
cells using organic polymers but many issues of materials and
device development remain to be resolved. In particular,
poly(3-hexylthiophene)/[6,6]-phenyl-C61-butyric acid methyl
ester (P3HT/PCBM) solar cells have attracted a great deal of
attention recently as a result of promising reports of these
devices with efficiencies approaching 5–6%.[4] The current
state-of-the-art in the field is critically examined with a focus on
improving or optimizing the electronic and morphological
interactions of the polymer and the fullerene. One attractive
alternative lies in the development of polymer solar cells
(PSCs) that are based on the exploitation of strongly absorbing
conjugated metallopolymers as the electron donors in bulk
heterojunction devices.[5] Power conversion efficiencies of over
4% have recently been achieved by blending metallopolyynes
of platinum with electron-accepting PCBM.[5a] However, in
order for this photovoltaic technology to find viable applica-
tions, we still need to develop novel materials to obtain solar
cells with efficiency exceeding 10% (threshold for commercial
applications).[6] Some possible approaches involve the
increased coverage of the solar spectrum and hence an
enhancement in the power conversion efficiency (PCE) of solar
cells by extending the absorption to longer wavelengths,
increasing the absorption coefficients (emax) and optimizing the
charge transport properties for forming efficient blends with
fullerenes in bulk heterojunction cells.[3,4a,4h,6]

2824 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2008, 18, 2824–2833
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L. Liu et al. / Fluorene-Based Polyplatinynes in Solar Cells

FULL PAPER
In order to optimize solar spectrum coverage and charge transport and absorption capability, we are thus in a great
mobility, both in single and tandem solar cells, structural demand for a new class of conjugated polymers with tunable
optimization of a greater variety of functional materials is of functional properties for PSCs. It is known that polyfluorenes
considerable interest to expand the flexibility of solar cell have been widely used to prepare polymer photovoltaic
design.[5b,6b,7] In particular, the development of classes of devices and photodiodes.[10] However, the devices are mainly
polymers with tunable functional properties which can be absorbing at short wavelengths due to their large bandgaps.
processed under similar conditions is of pivotal importance, Polyfluorene copolymers generally exhibit high charge carrier
since it would simplify the process of cell design and mobility and stability.[11] They also normally have a liquid-
optimization.[7f] To date, conjugated organic polymers contain- crystalline state at elevated temperatures that can facilitate
ing metal centers have evolved as a promising new class of polymer chain alignment and can be used to induce higher
materials to capture energy from the Sun[8] and among these, order in the material, to give an even higher mobility possibly
metal alkynyls are suitable architectural chromophores in this with polarized emission.[12] Inclusion of various thiophene
research frontier.[5,8d–k]] This interest derives from the fact that fragments into the fluorene unit is likely to further expand the
incorporation of heavy metals into an organic framework can spectral width of absorption appropriate for sunlight harvest-
elicit significant influence on their electronic and optical ing. Following this line, we report here the synthesis,
properties.[9] Recently, we have clearly demonstrated efficient characterization and photovoltaic behavior of some strongly
solar cells based on platinum(II) metallopolyyne/PCBM bulk visible-light-absorbing and bandgap-tunable metallopolyynes
heterojunctions.[5] While further improvements in the solar cell containing the bis(oligothienyl)-2,7-fluorene spacers, and PSCs
performance are anticipated with optimization of the proces- derived from them showed high PCEs of up to 2.9%. The work
sing conditions and device structure, a design limit would allows an effective means of chemically tuning the PCE by
ultimately be reached, as determined by the charge mobilities modulating the number of thienyl rings in the organic
and energy levels of the material. For a rational design of solar chromophore, which changes the absorption features and
cells with a greater flexibility in such properties as charge charge carrier mobilities of the resulting metallopolymers.

C8H17 C8H17 C8H17 C8H17 C8H17 C8H17

(i) (ii) (iii)
Br Br Br Br Br Br
S S S S

L0-2Br L1-2Br
C8H17 C8H17 C8H17 C8H17
(ii) (ii)
Br Br Br Br
(iii) S 2 S 2 (iii) S 3 S 3

L2-2Br L3-2Br

C8H17 C8H17

Br Br
S m S m

m = 0−3
(iv)

C8H17 C8H17 C8H17 C8H17

(v)
Me3Si SiMe3 H H
S m S m S m S m

m=0 L0
m=0 L0-2TMS
m=1 L1
m=1 L1-2TMS
m=2 L2
m=2 L2-2TMS (vi) m=3 L3
m=3 L3-2TMS (vii)

PEt3 C8H17 C8H17 PEt3 PBu3 C8H17 C8H17

Ph Pt Pt Ph Pt
S m S m S m S m
PEt3 PEt3 PBu3 n

m = 0 M0 m=0 P0
m = 1 M1 m=1 P1
m = 2 M2 m=2 P2
m=3 P3

Scheme 1. Synthetic pathways to oligo(thiophene)–fluorene derived ligand precursors and their platinum compounds. Conditions and reagents: (i)
C8H17Br, [nBu4N]Br, NaOH; (ii) 2-thienylboronic acid, Pd(PPh4)3, THF, 2 M K2CO3; (iii) NBS, CH2Cl2; (iv) Me3SiC
CH, CuI, Pd(OAc)2, PPh3, Et3N; (v)
K2CO3, MeOH/Et2O; (vi) trans-[PtPh(Cl)(PEt3)2], CuI, Et3N; (vii) trans-[PtCl2(PBu3)2], CuI, Et3N.

Adv. Funct. Mater. 2008, 18, 2824–2833 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.afm-journal.de 2825

FULL PAPER
2. Results and Discussion
2.1. Synthetic Strategies and Chemical Characterization
The chemical structures of new platinum(II) polyyne
polymers P0–P3 and their selected well-defined model
compounds M0–M2 are shown in Scheme 1. The dibromo
precursors (L1-2Br, L2-2Br, and L3-2Br) can be obtained from
L0-2Br by successive coupling of 2-thienylmagnesium bromide
with the corresponding fluorene-based dibromide of the lower
generation. Conversion of the dibromide derivatives to their
corresponding diethynyl congeners can be readily achieved
following the typical organic synthetic protocols for alkynyl-
ation of aromatic halides.[13] The Pt compounds were prepared
by the Sonogashira-type dehydrohalogenative reaction
between each of the diethynyl precursors and suitable platinum
chloride precursors.[8d–k,14] The feed mole ratio of the
platinum precursors and the diethynyl ligands were 2:1 and
1:1 for the dimer and polymer syntheses, respectively, and each
product was carefully purified to remove ionic impurities and
catalyst residues. The use of long octyl chains on fluorene is
crucial in increasing the solubility and improving the solution
processability/tractability of these metallopolymers. The
diplatinum complexes were used as good molecular model
systems for the corresponding polymers in terms of their
spectroscopic and photophysical properties. The polymers can
be purified by silica column chromatography and repeated
precipitation and isolated in good yield and high purity. Yields
of the polymers are between 55 and 86%. All of these Pt
compounds are thermally and air stable and soluble in common
chlorinated hydrocarbons and toluene. P0–P3 can cast tough,
free-standing thin films from their solutions readily but their
solubility tends to decrease gradually as m increases. Gel-
permeation chromatography (GPC) on P0–P3 suggests their
polymeric nature. The relatively narrow polydispersity in
molecular weights is consistent with the proposed linear
structure from the condensation polymerization. The number-
average molecular weights (Mn) of P0–P2 calibrated with
polystyrene standards range from 18 580 to 19 340 with a
calculated degree of polymerization of 14–19 (19–70 het-
erocyclic rings in total, respectively) (Table 1). The synthetic
yield is lower for P3 than the others because a certain portion
of the former polymer formed (m ¼ 3) was organic insoluble.
As a consequence of the poorer solubility of P3, the molecular
weight of the soluble fraction is believed to be relatively low
Table 1. Photophysical data of P0–P3.
Polymer Mw [a] Mn [b]
P0 46 120 19 340
P1 81 440 18 835
P2 59 700 18 580
P3 14 390 7660
[a] Weight-average molecular weight. [b] Number-average molecular weight. [c] Degree of polymerization based on Mn. Polydispersity values are given in parentheses.
[d] Fluorescence quantum yield and lifetime (FF in % and tF in ns) are shown in parentheses. FF data were measured in CH2Cl2 relative to quinine sulfate (FF ¼ 0.54).[22] The
asterisk indicates a shoulder or a weak peak.
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L. Liu et al. / Fluorene-Based Polyplatinynes in Solar Cells
but it still represents a soluble Pt polyyne consisting of seven
aromatic rings in the repeat unit (i.e., around 35 aryl rings along
the polymer chain on average based on Mn). The structures
were unequivocally characterized using elemental analyses,
mass spectrometry, IR and NMR spectroscopies (see Section
4).
2.2. Photophysical and Electrochemical Characterization
The absorption and emission spectra of the polymers and
model complexes were measured in CH2Cl2 solutions at 293 K
(Figs. 1 and 2). The absorption of P0–P3 is each dominated by
an intense band peaking at 399–457 nm, and these polymers
emit strong fluorescence from the singlet excited states at
439–515 nm under ambient conditions. The absorption and
emission properties of the model diplatinum compounds are
very similar to those of their polymeric congeners [see
Supporting Information (SI)]. The nonstructured absorption
is characteristic of many p-conjugated polymers and arises in
part from the distribution of the conjugation lengths.[10a] Due
to the presence of an extended p-electron delocalized system
through the rigid oligothiophene–fluorene segment, the
bandgaps of P0–P3 vary from 2.93 to 2.33 eV with the value
for orange-red P3 having extended absorption being signifi-
cantly reduced by ca. 0.60 eV relative to the pale-yellow purely
fluorene-based P0. We think that the conjugative interaction
along the oligothienyl–fluorene unit is remarkably enhanced
by the extensive p-delocalization in the polymer backbone
containing the electron-rich Pt ion. However, the extent of red-
shifts induced by increasing m is less pronounced and there
would be little benefit in extending the p-conjugation length by
increasing m too much given the increased synthetic
complication and much reduced product yields. A linear
oligothienyl chain length dependence of Eg can be rationalized
from the plot of Eg against reciprocal chain length (1/m) and a
limiting value for Eg is estimated to be ca. 2.22 eV for m ¼ 1
(Fig. 3).[15] The measured photoluminescence lifetimes for P0–
P3 for the main peaks are all very short (ca. 0.50–0.96 ns) at
293 K, characteristic of the spin-allowed singlet emission.
These results together with the small Stokes shift observed
preclude the emitting state as a triplet but a singlet excited state
instead.[8d–8k] While a weak triplet emission at 549 nm (with a
triplet emissive lifetime tP of ca. 65.7 ms at 77 K) is apparent in
the room temperature PL spectrum of P0, we observed no such
DP [c] labs in CH2Cl2 [nm] lem in CH2Cl2 [nm] [d]
19 (2.4) 307, 399 439 (1.98, 0.82), 549
16 (4.3) 420, 439 462, 486 (2.03, 0.96)
14 (3.2) 446, 463 495, 523 (5.84, 0.50)
5 (1.9) 457 515, 546 (5.97, 0.70)
Adv. Funct. Mater. 2008, 18, 2824–2833
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L. Liu et al. / Fluorene-Based Polyplatinynes in Solar Cells

FULL PAPER
a 3.0
1.0 % (P0)
% (P1) 2.8
0.8 % (P2)
% (P3)
Absorbance (a.u.)

0.6 2.6

Eg (eV)
2.22 eV
0.4
2.4

0.2
2.2
0.0

2.0
300 400 500 600 700 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Wavelength (nm) Inverse chain length (1/m)
b Figure 3. Relationship of Eg and 1/m for the metallopolyynes.
0.30
P0
0.25 P1
P2
Absorbance (a.u.)

P3
0.20 emission over the measured spectral window between 1.2 and
3.1 eV for P1–P3. The assignment of a triplet emission for the
0.15 lower-energy feature of P0 can be confirmed by a low-
temperature spectrum as well in which the peak intensity
0.10 increases significantly with decreasing temperature.[8d–8k]
Likewise, this also applies to the series of model complexes
0.05
and M0 shows a similar behavior at 546 nm (tP ¼ 56.3 ms at
77 K) (see SI). Considering the energy gap law for nonradiative
0.00
300 400 500 600 700 decay for Pt-containing conjugated polyynes and their model
Wavelength (nm) diynes,[16] there is a trade-off between the bandgap and the
phosphorescence radiative decay rate in this system. The
Figure 1. Absorption spectra of P0–P3 a) in CH2Cl2 at 293 K (conc. ca. nonradiative decay rate (knr)P from the triplet state increases
105 M) and b) as thin films.
exponentially with decreasing triplet–singlet energy gap
according to the expression (knr)P / exp(CDES–T), where
DES–T is the energy gap for the T1–S0 transition and C is a term
controlled by the molecular parameters and vibrational
modes.[16] Hence, a high-bandgap polymer such as P0 would
be triplet-emitting but lower bandgap values for P1–P3 would
be detrimental for efficient phosphorescence. In addition, the
fully extended heteroaryl rings in the ligand chromophore
1.0 P0 greatly reduces the influence of heavy metal ion which is
P1 mainly responsible for the intersystem crossing and phosphor-
0.8 P2
Absorbance (a.u.)

escence process. Therefore, we consider a charge-transfer (CT)

P3
excited state instead of the triplet state to contribute to the
0.6 efficient photoinduced charge separation in the energy
conversion for P0–P3, which is different from the Pt-
0.4 monothiophene polyyne-based blends where charge separa-
tion takes place via the triplet state channel of the
T1
0.2 polymer.[8d,8e] From these results, we attribute the localized
states centered at 2.40–2.90 eV to a strong CT-type interaction
0.0 for the polymers. The CT nature of the transition is also
consistent with the solvent dependent emission spectra of these
400 500 600 700
Pt polyynes. For instance, P2 exhibited a positive solvato-
Wavelength (nm) chromism with a red-shift of the peak maximum of 12 nm
Figure 2. PL spectra of P0–P3 at 293 K. The peak at 549 nm for P0 is due to from toluene (lem ¼ 492 nm) to CH2Cl2 (lem ¼ 504 nm), which
the phosphorescence emission from the T1 triplet excited state. suggests a more polar excited state.

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Table 2. Physical data and solar cell performance of P0P3/PCBM (1:5) best devices.

Polymer Eg [eV] [a] Eox [V] Ered [V] EHOMO [eV] ELUMO [eV] VOC [V] JSC [mA cmS2] FF Max. PCE [%] Max. EQE [%]

P0 2.93 (2.97) 1.16 0.86 5.88 3.86 0.77 (0.74) 1.21 (1.22) 0.38 (0.37) 0.36 (0.33) 14.0
P1 2.60 (2.67) 1.13 0.85 5.85 3.87 0.95 (0.95) 2.73 (2.50) 0.59 (0.58) 1.54 (1.36) 25.9
P2 2.43 (2.50) 1.07 0.85 5.79 3.87 0.95 (0.94) 4.39 (4.05) 0.60 (0.56) 2.47 (2.11) 55.7
P3 2.33 (2.41) 1.01 0.83 5.73 3.89 0.89 (0.89) 7.56 (6.59) 0.43 (0.41) 2.88 (2.41) 83.2

The numbers in brackets denote average from 11 to 16 devices. [a] Optical bandgaps determined from the onset of absorption in solid state. The corresponding values
obtained from the solution phases are shown in parentheses.

The highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO) levels of P0–P3
were calculated using the redox potentials determined from
electrochemical measurements using cyclic voltammetry. The
experiments were performed by casting the polymer films on
the glassy-carbon working electrode with a Ag/AgCl wire as
the reference electrode, at a scan rate of 50 mV s1. The solvent
in all measurements was deoxygenated MeCN, and the
supporting electrolyte was 0.1 M [nBu4N]BF4. The relevant
data are collected in Table 2. From the onset values of oxidation
potential (Eox) and reduction potential (Ered), the HOMO
and LUMO levels of the polymers were calculated according
to the following equations EHOMO ¼ (Eox þ 4.72) eV and
ELUMO ¼ (Ered þ 4.72) eV (where the unit of potential is V vs.
Ag/AgCl).[17] It is evident that the presence of electron-
donating thiophenes on both sides of fluorene ring changes the
Al served as the electron collecting electrode. We consider that
enhancing the absorption coefficient of the band by increasing
the conjugation chain length with oligothienyl rings is an
effective way to improve the cell performance. The facile
functionalization of thiophene groups also offers relatively
efficient synthetic solutions to solubility, polarity and bandgap
tuning. A considerable increase in the short-circuit current
density (JSC) and PCE can be observed in P2 and P3 relative to
P0 and P1 (Fig. 4a). The results are shown for 1:5 blend ratio
a 2
0
J (mA cm )

-2
−2

electrical properties of the polymers. The fluorene in the

polymer mainly affects its reduction (n-doping) process, and the
thiophene ring mainly influences the oxidation potential of the -4
polymer. The oxidation potential of P0–P3 is reduced as a result
of the thiophene ring extension, and each of them shows an P0
-6
irreversible thienyl oxidation at 1.16, 1.13, 1.07, and 1.01 V, P1
respectively, which agrees with the phenomenon that formation P2
-8 P3
of the heteroaromatic cation radicals is favored by increased
conjugation length.[18] The electrooxidation of oligothiophenes
0.0 0.2 0.4 0.6 0.8 1.0
is often irreversible because the electrogenerated cations
readily undergo rapid coupling reactions leading to higher V (V)
oligomers or polymers. The stability of these radical cations b
80 -2
increases and the anodic wave becomes more reversible when P0:PCBM (1:5) 1.0 mA cm
the oligothienyl chain length m becomes longer.[18] Hence, the P1:PCBM (1:5) 2.1 mA cm -2

HOMO levels tend to be elevated with increasing m from P2:PCBM (1:5) 4.0 mA cm -2
60
P0 (5.88 eV) to P3 (5.73 eV). The irreversible waves P3:PCBM (1:5) 6.0 mA cm -2
EQE (%)

within the narrow range of 0.83 to 0.86 V for P0–P3 are

attributed to the reduction of the dioctylfluorenyl moiety in each 40
case which are relatively insensitive to m in the polymers
with the reduction potential showing only a minute decrease as
m increases from 0 to 3.[10a] 20

2.3. Polymer Photovoltaic Behavior

0
Polymer solar cells were fabricated by using each of P0–P3 400 500 600 700 800
as an electron donor and PCBM as an electron acceptor Wavelength (nm)
(Table 2). The hole collection electrode consisted of indium
Figure 4. a) J–V curves of solar cells with P0–P3/PCBM (1:5) active layers
tin oxide (ITO) with a spin-coated poly(3,4-ethylene- under simulated AM1.5 solar irradiation. b) EQE wavelength dependencies
dioxythiophene)/poly(styrene sulfonate) (PEDOT/PSS), while of solar cells with P0–P3/PCBM (1:5) active layers.

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a 1E-3 PCE of up to 2.47–2.88% can be obtained for P2 and P3
P0 (Eg  2.43 and 2.33 eV, respectively) under illumination of an
P1 AM1.5 solar simulator, which can compete with that of the
P2 lower-bandgap P3HT-based devices (Eg  1.9–2.0 eV) fabri-
P3
cated without additional processing (annealing or TiOx layer)
µh (cm V s )

both reported in the literature[4a] and obtained by us (see

−1

1E-4
−1

Fig. S10 in SI), as well as other recently reported low-bandgap

materials (Eg < 2.0 eV).[3] The broad external quantum
2

efficiency (EQE) curves for P2 and P3 cover the spectrum

up to 800 nm with a maximum of 55.7 and 83.2%, respectively
(Fig. 4b). Both the VOC and FF values of P1- and P2-based
solar cells (1:5) are quite close to each other. At the same blend
1E-5
100 150 200 250 300 350 400
ratio of 1:5, the PCE increases sharply from P0 to P3 (i.e.,
1/2 1/2 −1/2 P0 < P1 < P2 < P3) and it is remarkable to see that the light-
E (V cm )
harvesting ability of P3 (with its commensurately high charge
b 1E-3
mobilities and favorable light absorption characterisitics) can
be increased by eight times relative to P0 simply by adding
altogether six thienyl rings along the main chain. This is in
agreement with increased maximum absorption with increas-
ing m from M0 to M2 (see Table S2 in SI), resulting in higher
µe (cm V s )
−1

PCE for the polymers. We observe that the shift of the

−1

1E-4 absorption peak is less pronounced in 1:4 and 1:5 blend films
2

1E-5
100 200 300
1/2 −1/2
E1/2 (V cm ) P3 could be due to the difference in phase separation in the
Figure 5. The comparison between a) hole (mh) and b) electron (me)
mobilities in P0–P3/PCBM blends obtained by the SCLC modeling.
(for cell performance dependence on blend ratio for P1 and P2,
see Fig. S10 in SI). The increase in the number of rings is also
expected to result in an increase of the intrachain mobility
because of more extended p-conjugation. Since a clear trend in
the increase in the mobility is observed for the blend films
(according to the results obtained by the space-charge-limited
current (SCLC) shown in Fig. 5) within the series, it is
likely that intrachain mobility significantly contributes to the
bulk properties. Similar trends have been previously observed
in monosilanylene–oligothienylene copolymers with dif-
ferent number of thienyl rings.[18d] Both P2 and P3 blends
with PCBM exhibit carrier mobilities of the order of
104 cm2 V1 s1. From Figure 5, we note that each of the
polymer/PCBM blends can exhibit reasonably balanced charge
transport, as required for efficient solar cell performance.[4i]
The mobilities of the blends with P0 and P1 are somewhat
lower, and we can observe that for both electrons and holes, the
mobilities increase with an increasing number of thienyl rings.
Thus, not only optical but also charge transport properties can
be tuned by changing the length of oligothienyl chain. The fill
factor (FF) ranges from 0.38 to 0.60 for the best devices. A high
P0 (see Fig. S8 in SI) than in the neat polymer films (Fig. 1b).
P1 Accordingly, the shape of the EQE curve follows the shape of
P2 the absorption of the blend. Although the device from P3
P3
shows a great enhancement of JSC (7.56 mA cm2) compared to
other devices, it reveals a decrease in FF. Since there was no
significant difference in the measured film thickness of P0–P3/
400 PCBM, a possible reason for the observed decrease in FF for
film, which requires further morphological study.
Yet, higher PCEs with excellent solution-processability are
notoriously difficult to achieve with the pure organic polymers.
Hence, the need to improve PCE to the practical level requires
the implementation of new materials and we think a new
venture to capture sunlight for power generation involves
putting metals into the conjugated organic polymers. The
generally good solubility of platinum(II) acetylide polymers
over their purely organic poly(heteroaryleneethynylene)s
favors the advance of organometallic PSCs. The novel
approach reported here can provide a useful avenue to PCE
enhancement by extending the absorption to longer wave-
lengths and metal incorporation without the necessary
involvement of the more abundant triplet excitons in the
energy conversion.[8f,8h]
To study the performance of PSCs, it is vital to understand
which mechanisms control the J–V characteristics of a given
device and the fate of the photogenerated electrons and holes.
So, the influence of light intensity on the solar cell parameters
is very informative for analyzing internal recombination
losses.[19] The J–V curves for P3 under different excitation
powers and the power dependence of the solar cell parameters
are shown in Figures 6 and 7, respectively. The JSC exhibits a
linear dependence on the optical power, while VOC shows some
increase and then saturates at higher intensity, which is
expected.[20] The almost linear photocurrent dependence on

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 16163028, 2008, 18, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.200800439 by Universidad De Guadalajara, Wiley Online Library on [26/10/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
L. Liu et al. / Fluorene-Based Polyplatinynes in Solar Cells
FULL PAPER

2 in the blend morphology, and such a study is currently under

active investigation.
0

-2 3. Conclusions
J (mA cm )
−2

100mW
90mW In summary, we have found a versatile system for preparing
-4 80mW
70mW fluorene-based conjugated metallic copolymers with tunable
60mW optical absorption, electrochemical and electronic properties
-6 50mW for PSCs. The photophysical, charge-transporting, and elec-
40mW
30mW trical properties of our organometallic polymers (Eg > 2.3 eV)
-8 20mW can be easily manipulated by variation of the oligothienyl chain
10mW length. This in turn can improve the performance of the
0.0 0.2 0.4 0.6 0.8 1.0 resulting PSCs through extending the oligothienyl chain length
V (V) in strongly absorbing polyplatinynes with the solubilizing
dialkylfluorene group, and we have prepared highly efficient
Figure 6. J–V curves of the P3/PCBM (1:5) device for different illumina-
tion. solar cells with respectful PCE of up to 2.9% and peak EQE to
83% under simulated AM1.5 solar illumination. Polymers P2
and P3 represent new examples of how structural optimization
of an organometallic polymer can lead to materials with high
the light intensity for voltage approaching VOC does not give a absorption coefficients that can better absorb solar radiation,
slope of  34, which indicates the absence of space-charge- while retaining high voltages and charge-carrier mobilities.
limited device performance and that the charge-carrier losses Since the bandgap of the polymers is not very low
in the absorber bulk are dominated by monomolecular (Eg > 2.3 eV), this illustrates the importance of extended
recombination under short-circuit conditions. The PCE only overlap with the solar spectrum to gain broader coverage while
decreases slightly with the illumination intensity, reaching a also retaining high absorption coefficients at relevant wave-
peak of 2.96% at 20 mW cm2. The FF shows a maximum of lengths and suitable energy levels for interaction with PCBM in
0.46 at a low power level of 20 mW cm2 but drops gradually at order to achieve high efficiency. Given the performance and
higher light intensities, in agreement with previously reported processing advantages, this work has great potential to excel
power dependence of FF in a bulk heterojunction cell.[21] The for the realization of more practical devices even without the
obtained results clearly demonstrate the potential of metalated need for exploiting the triplet excited states in promoting an
conjugated polymers in the design of next generation, stable, efficient photoinduced charge separation. It clearly sets out a
high-efficiency photovoltaic systems. It is expected that rarely explored strategy toward an effective tuning of the solar
optimization at all levels of device construction and composi- cell efficiency and charge transport properties in conjugated
tion will result in further improvements in the efficiency. Also, metallopolymers for the next stage of development for
the dependence of solar cell performance on molecular weight polymer-based solar power generation.
should not be overlooked, which can cause significant changes

4. Experimental
10 1.0
General: Solvents were carefully dried and distilled from appro-
8 0.8 priate drying agents prior to use. Commercially available reagents were
used without further purification unless otherwise stated. All reagents
for the chemical syntheses were purchased from Aldrich or Acros
6 0.6 Organics. PCBM and regioregular P3HT (Mw 20 000–50 000) were
purchased from American Dyes. PEDOT/PSS (Baytron VPAI 4083)
was purchased from H. C. Starck. Reactions and manipulations were
4 0.4 carried out under an atmosphere of prepurified nitrogen using Schlenk
techniques. All reactions were monitored by thin-layer chromato-
graphy (TLC) with Merck precoated glass plates. Flash column
2 0.2 chromatography and preparative TLC were carried out using silica gel
-2
JSC (mA cm ) VOC (V) from Merck (230–400 mesh). Infrared spectra were recorded as CH2Cl2
PCE (%) solutions using a Perkin-Elmer Paragon 1000 PC or Nicolet Magna 550
FF (%)
0 0.0 Series II FTIR spectrometer, using CaF2 cells with a 0.5 mm path
0 20 40 60 80 100 length. Fast atom bombardment (FAB) mass spectra were recorded on
−2
Power density mW cm a Finnigan MAT SSQ710 system. NMR spectra were measured in
CDCl3 on a Varian Inova 400 MHz FT-NMR spectrometer and
Figure 7. Power dependencies of open-circuit voltage (VOC), short-circuit chemical shifts are quoted relative to tetramethylsilane for 1H and 13C
current density (JSC), FF, and PCE for the P3/PCBM (1:5) cells. nuclei and H3PO4 for 31P nucleus.

2830 www.afm-journal.de ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2008, 18, 2824–2833

L. Liu et al. / Fluorene-Based Polyplatinynes in Solar Cells
Physical Measurements: UV/Vis spectra were obtained on an HP-
8453 diode array spectrophotometer. The solution emission spectra
and lifetimes of the compounds were measured on a Photon
Technology International (PTI) Fluorescence QuantaMaster Series
QM1 spectrophotometer. The phosphorescence quantum yields were
determined in degassed CH2Cl2 solutions at 293 K against quinine
sulfate in 0.1 N H2SO4 (FF ¼ 0.54) [22]. The decay curves were
analyzed using a Marquardt-based nonlinear least-squares fitting
routine and were shown to follow a single-exponential function in each
case according to I ¼ I0 þ A exp(t/t). The CV measurements were
carried out at a scan rate of 50 mV s1 using a eDAQ EA161
potentiostat electrochemical interface equipped with a thin film coated
ITO covered glass working electrode, a platinum counter electrode
and a Ag/AgCl (in 3 M KCl) reference electrode. The solvent in all
measurements was deoxygenated MeCN, and the supporting electro-
lyte was 0.1 M [nBu4N]BF4. Thin polymer films were deposited on the
working electrode by dip-coating in chlorobenzene solution
(6 mg mL1). The onset oxidation and reduction potentials were used
to determine the HOMO and LUMO energy levels using the equations
EHOMO ¼ [(Eonset, ox (vs. Ag/AgCl)  Eonset (N.H.E. vs. Ag/AgCl)]  4.50 eV
and ELUMO ¼ [(Eonset, red (vs. Ag/AgCl)  Eonset (N.H.E. vs. Ag/
AgCl)]  4.50 eV, where the potentials for N.H.E. versus vacuum and
N.H.E. versus Ag/AgCl are 4.50 and 0.22 V, respectively [17].
Synthesis of Platinum Model Complexes M1–M2: Both of them
were synthesized following the dehydrohalogenating coupling between
trans-[PtPh(Cl)(PEt3)2] [23] and the corresponding diterminal alkynes
L1–L2. M0 was prepared from L0 according to the reported method
[14j]. A typical procedure was given for M1 starting from L1.
To a stirred mixture of L1 (30.0 mg, 0.05 mmol) and trans-
[PtPh(Cl)(PEt3)2] (54.0 mg, 0.10 mmol) in Et3N (30 mL) and CH2Cl2
(30 mL) was added CuI (5.00 mg). The solution was stirred at room
temperature under nitrogen over a period of 12 h, after which all
volatile components were removed under vacuum. The crude product
was taken up in CH2Cl2 and purified on preparative silica TLC plates
with CH2Cl2/hexane (2:3, v/v) as eluent. The product M1 was obtained
as a pale yellow solid (40.9 mg, 50%). IR (KBr): n(C C) 2082 cm1.
1
H NMR (CDCl3): d [ppm] 7.60–7.58 (d, 2H, J ¼ 8.0 Hz, Ar), 7.51–7.45
(m, 4H, Ar), 7.32–7.30 (d, 4H, J ¼ 7.2 Hz, Ar), 7.15–7.14 (d, 2H,
J ¼ 3.6 Hz, Ar), 6.97–6.94 (t, 4H, J ¼ 7.2 Hz, Ar), 6.84–6.80 (m, 4H, Ar),
1.98–1.94 (m, 4H, alkyl), 1.76–1.71 (m, 24H, alkyl), 1.13–1.00 (m, 56H,
alkyl), 0.80–0.76 (t, 6H, J ¼ 6.8 Hz, alkyl), 0.64 (m, 4H, alkyl). 13C NMR
(CDCl3): d [ppm] 151.48, 141.00, 139.71, 139.06, 133.48, 129.60, 127.96,
127.32, 124.34, 122.43, 121.30, 119.77, 119.50 (Ar), 102.48, 109.88
(C C), 55.11 (quat. C), 40.43, 31.74, 30.00, 29.68, 29.20, 23.70, 22.56,
15.11, 14.04, 8.03 (alkyl). 31P NMR (CDCl3): d [ppm] 11.11
(1JP––Pt ¼ 2610 Hz). FAB-MS: m/z 1617 (Mþ). Anal. calcd. for
C77H114P4Pt2S2: C 57.16, H 7.10; found: C 57.10, H 6.98.
M2: Yellow solid. Yield: 66%. [Eluent: CH2Cl2/hexane (2:3, v/v)].
IR (KBr): n(C C) 2080 cm1. 1H NMR (CDCl3): d [ppm] 7.65–7.63 (d,
2H, J ¼ 8.0 Hz, Ar), 7.57–7.50 (m, 4H, Ar), 7.31–7.29 (d, 4H, J ¼ 7.2 Hz,
Ar), 7.25 (s, 2H, Ar), 7.07 (d, 2H, J ¼ 4.0 Hz, Ar), 6.99–6.94 (m, 6H, Ar),
6.80 (m, 2H, Ar), 6.76 (d, 2H, J ¼ 3.6 Hz, Ar), 2.01–1.97 (m, 4H, alkyl),
1.77–1.69 (m, 24H, alkyl), 1.13–1.02 (m, 56H, alkyl), 0.79–0.75 (t, 6H,
J ¼ 7.2 Hz, alkyl), 0.65 (m, 4H, alkyl). 13C NMR (CDCl3): d [ppm]
151.94, 143.03, 140.36, 139.28, 137.48, 133.76, 133.28, 127.95, 127.60,
124.69, 123.80, 123.74, 123.42, 121.60, 120.29, 119.85 (Ar), 110.00,
102.44 (C C), 55.49 (quat. C), 40.64, 32.01, 30.20, 29.93, 29.43, 23.95,
22.82, 15.35, 14.30, 8.28 (alkyl). 31P NMR (CDCl3): d [ppm] 11.10 (1JP–
Pt ¼ 2610 Hz). FAB-MS: m/z 1783 (Mþ). Anal. calcd. for
C85H118P4Pt2S4: C 57.29, H 6.67; found: C 57.10, H 6.54.
Synthesis of Platinum Metallopolyynes P0–P3: The polymers
were prepared by the dehydrohalogenative polycondensation
between trans-[PtCl2(PBu3)2] [24] and each of L0–L3 under very
similar conditions. A typical procedure was given for P1 starting from
L1.
Polymerization was carried out by mixing L1 (66.4 mg, 0.11 mmol),
trans-[PtCl2(PBu3)2] (73.8 mg, 0.11 mmol) and CuI (3.00 mg) in Et3N/
CH2Cl2 (30 mL, 1:2, v/v). After stirring at room temperature overnight
Adv. Funct. Mater. 2008, 18, 2824–2833 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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FULL PAPER
under nitrogen for 20 h, the solution mixture was evaporated to
dryness. The residue was redissolved in CH2Cl2 and filtered through a
short silica column using the same eluent to remove ionic impurities
and catalyst residues. After removal of the solvent, the crude product
was purified by precipitation in CH2Cl2 from MeOH twice. Subsequent
washing with hexane and drying in vacuo gave a yellow solid of P1
(114 mg, 86%). IR (KBr): n(C C) 2087 cm1. 1H NMR (CDCl3): d
[ppm] 7.60 (d, 2H, J ¼ 8.0 Hz, Ar), 7.50–7.46 (m, 4H, Ar), 7.16 (d, 2H,
J ¼ 3.6 Hz, Ar), 6.82 (d, 2H, J ¼ 3.2 Hz, Ar), 2.16–2.12 (m, 12H, alkyl),
1.96 (m, 4H, alkyl), 1.62–1.60 (m, 12H, alkyl), 1.53–1.45 (m, 12H, alkyl),
1.17–1.03 (m, 20H, alkyl), 0.98–0.94 (m, 18H, alkyl), 0.78 (t, 6H,
J ¼ 7.0 Hz, alkyl), 0.66 (m, 4H, alkyl). 13C NMR (CDCl3): d [ppm]
151.77, 141.72, 140.02, 133.63, 128.78, 128.51, 124.63, 122.64, 120.11,
119.75 (Ar), 115.80, 102.10 (C C), 55.31 (quat. C), 40.65, 31.97, 30.26,
29.92, 29.45, 29.39, 28.06, 27.07, 26.61, 24.71, 24.64, 24.58, 24.40, 24.24,
24.07, 22.80, 17.74, 14.28, 14.10, 13.83 (alkyl). 31P NMR (CDCl3): d
[ppm] 4.46 (1JP–Pt ¼ 2319 Hz). Anal. calcd. for (C65H98P2PtS2)n:
C 65.02, H 8.23; found: C 65.10, H 8.08.
P2: Yellow solid. Yield: 75%. IR (KBr): n(C C) 2086 cm1. 1H
NMR (CDCl3): d [ppm] 7.65 (d, 2H, J ¼ 8.0 Hz, Ar), 7.57–7.51 (m, 4H,
Ar), 7.24 (d, 2H, J ¼ 2.0 Hz, Ar), 7.08 (m, 2H, Ar), 6.98 (m, 2H, Ar),
6.75–6.74 (m, 2H, Ar), 2.11 (m, 12H, alkyl), 2.00 (m, 4H, alkyl), 1.59–
1.52 (m, 12H, alkyl), 1.51–1.45 (m, 12H, alkyl), 1.17–1.04 (m, 20H,
alkyl), 0.97–0.93 (t, 18H, J ¼ 7.2 Hz, alkyl), 0.79–0.76 (t, 6H, J ¼ 7.0 Hz,
alkyl), 0.66 (m, 4H, alkyl). 13C NMR (CDCl3): d [ppm] 151.71, 143.02,
140.15, 137.06, 134.00, 133.01, 128.07, 124.51, 123.75, 123.52, 123.16,
120.07, 119.64 (Ar), 116.20, 101.60 (C C), 55.24 (quat. C), 40.38, 31.76,
29.94, 29.18, 29.13, 26.36, 26.06, 24.47, 24.40, 24.33, 24.14, 24.00, 23.80,
22.57, 14.04, 13.85 (alkyl). 31P NMR (CDCl3): d [ppm] 4.47
(1JPPt ¼ 2308 Hz). Anal. calcd. for (C73H102P2PtS4)n: C 64.24,
H 7.53; found: C 64.02, H 7.44.
P0 [14j]: Pale yellow solid. Yield: 84%. IR (KBr): n(C C) cm1. 1H
NMR (CDCl3): d [ppm] 7.44 (d, 2H, J ¼ 8.0 Hz, Ar), 7.19 (s, 4H, Ar),
2.18 (m, 12H, alkyl), 1.64 (m, 12H, alkyl), 1.46–1.43 (m, 12H, alkyl),
0.94–0.91 (m, 18H, alkyl), 0.82–0.79 (t, 6H, J ¼ 7.2 Hz, alkyl), 0.59 (m,
4H, alkyl), 1.23–1.00 (m, 20H, alkyl), 1.83 (m, 4H, alkyl). 31P NMR
(CDCl3): d [ppm] 3.86 (1JP–Pt ¼ 2344 Hz). Anal. calcd. for
(C57H94P2Pt)n: C 66.06, H 9.14; found: C 65.92, H 9.23.
P3: Orange-red solid. Yield: 55%. IR (KBr): n(C C) 2085 cm1.
1
H NMR (CDCl3): d [ppm] 7.67 (d, 2H, J ¼ 7.6 Hz, Ar), 7.57 (d, 2H,
J ¼ 7.6 Hz, Ar), 7.52 (m, 2H, Ar), 7.29 (d, 2H, J ¼ 3.6 Hz, Ar), 7.14 (d,
2H, J ¼ 3.6 Hz, Ar), 7.08 (d, 2H, J ¼ 3.6 Hz, Ar), 7.00 (d, 2H, J ¼ 3.6 Hz,
Ar), 6.95 (d, 2H, J ¼ 3.6 Hz, Ar), 6.74 (d, 2H, J ¼ 3.6 Hz, Ar), 2.11–1.99
(m, 16H, alkyl), 1.48–1.44 (m, 12H, alkyl), 1.23–0.94 (m, 32H, alkyl),
1.04–0.91 (m, 18H, alkyl), 0.77 (t, 6H, J ¼ 7.0 Hz, alkyl), 0.68–0.66 (m,
4H, alkyl). 31P NMR (CDCl3): d [ppm] 4.48 (1JP–Pt ¼ 2316 Hz). Anal.
calcd. for (C81H106P2PtS6)n: C 63.62, H 6.99; found: C 63.50, H 6.92.
Solar Cell Fabrication and Characterization: The device structure
was ITO/poly(3,4-ethylene-dioxythiophene)/poly(styrene sulfonate)
(PEDOT/PSS)/polymer/PCBM blend/Al. The ITO glass substrates
(10 V per square) were cleaned by sonication in toluene, acetone,
ethanol, and deionized water, dried in an oven, and then cleaned with
UV ozone for 300 s. As-received PEDOT/PSS solution was passed
through the 0.45 mm filter and spin-coated on patterned ITO substrates
at 5000 rpm for 3 min, followed by baking in N2 at 150 8C for 15 min.
The metallopolyyne/PCBM (1:5 by weight, unless specified otherwise)
active layer was prepared by spin-coating the chlorobenzene solution
(6 mg of metallopolyyne and 30 mg of PCBM in 1.8 mL of solvent) at
1000 rpm for 2 min. The substrates were dried at room temperature in
low vacuum (vacuum oven) for 1 h, and then stored in high vacuum
(105–106 Torr) overnight. Al electrode (100 nm) was evaporated
through a shadow mask to define the active area of the devices (2 mm
diameter circle). For comparison purpose, solar cells with P3HT/
PCBM active layers with different blend ratios were also prepared. The
procedure for cell fabrication was the same, except that P3HT/PCBM
solution was prepared in chlorobenzene and stirred overnight in N2 at
40 8C. All the fabrication procedures (except drying, PEDOT/PSS
annealing and Al deposition) and cell characterization were performed
www.afm-journal.de 2831

FULL PAPER
in air. PCE was determined from J to V curve measurement (using a
Keithley 2400 sourcemeter) under white light illumination (at
100 mW cm2). For white light efficiency measurements, Oriel 66002
solar light simulator with AM1.5 filter was used. The light intensity was
measured by a Molectron Power Max 500D laser power meter. For the
measurement of the EQE, different wavelengths were selected with an
Oriel Cornerstone 74000 monochromator, while the photocurrent was
measured with a Keithley 2400 sourcemeter. The light intensity was
measured with a Newport 1830-C optical power meter equipped with a
818-UV detector probe. The charge carrier mobility was determined
from the SCLC modeling [25]. The device structure was ITO/PEDOT/
PSS/blend film/Au for the hole mobility determination, while for
electron mobility determination the device configuration was ITO/Mg/
blend film/LiF/Al. The mobilities were determined by fitting the
measured J–V curves to the SCLC model [25]. The index of refraction
of the material was estimated from the modified Lorentz model fitting
[26] of the ellipsometry data (obtained using JA Woollam V-VASE
ellipsometer) for blend films spin-coated on Si substrates. Surface
roughness correction was not used in the fitting. The mobility
measurements for P2/PCBM blend were also determined by the
time-of-flight (TOF) technique for comparison. The samples for TOF
measurements were prepared by drop-casting, and then dried in
vacuum, followed by the evaporation of a metal electrode in high
vacuum (106 Torr). A nitrogen laser was used to generate pulsed
excitation (l ¼ 337.1 nm). The transient photocurrent was monitored
by an oscilloscope Tektronix TDS 3052B. The mobilities determined
from TOF and SCLC were in good agreement, although the obtained
values were slightly lower from the TOF measurements.
Received: March 28, 2008
Published online: September 1, 2008
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