Polymer International Polym Int 55:473–490 (2006)

Review
Optimization of opto-electronic property
and device efficiency of polyfluorenes by
tuning structure and morphology
Peng Chen,1,2 Guizhong Yang,1,2 Tianxi Liu,1,2∗ Tingcheng Li,2 Min Wang2 and
Wei Huang2
1 Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Department of Macromolecular Science, Fudan University,
220 Handan Road, Shanghai 200433, China
2 Laboratory of Advanced Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China

Abstract: Polyfluorene-based oligomers and polymers (PFs) have been studied intensively as active materials
for organic optoelectronic devices. In this review, the optimization of the opto-electronic property and device
efficiency of polyfluorenes in the field of light-emitting diodes (LEDs) and photovoltaic cells (PVs) by tuning
structure and morphology are summarized in terms of two typical modification techniques: copolymerization and
blending. The relationships between molecular structures, thin film morphologies, opto-electronic properties and
device efficiencies are discussed, and some recent progress in LEDs and PVs is simultaneously reviewed. After
the introduction, the basic knowledge of molecular structures and properties of polyfluorene homopolymers is
presented as a background for a better understanding of their great potential for opto-electronic applications.
Immediately after this, three different opinions on the origin of low-energy emission band at 520–540 nm in
polyfluorene-based LEDs are addressed. Rod–coil block copolymers and alternative copolymers are focused
on in the next section, which are a vivid embodiment of controlling supramolecular structures and tailoring
molecular structures, respectively. In particular, various supramolecular architectures induced by altering coil
blocks are carefully discussed. Recent work that shows great improvement in opto-electronic properties or device
performance by blending or doping is also addressed. Additionally, the progress of understanding concerning the
mechanisms of exciton dynamics is briefly referred to.
 2006 Society of Chemical Industry

Keywords: polyfluorenes; copolymers; blends; structures and morphologies; polymer light-emitting diodes;
photovoltaic cells

INTRODUCTION of electronic products such as mobile phones, digital

The rapid development of organic electronics has
demonstrated that π -conjugated polymers are very
promising materials for the fabrication of low-cost,
yet high-quality novel electronic devices, such as
polymer LEDs (PLEDs) (ultrathin, flexible, full-color
displays) and PVs, due to their easy processability
and semiconducting properties.1 – 3 Typically, the
PLEDs comprise a thin film of light-emitting material
sandwiched between a conducting oxide anode and
a metal cathode. Under an applied bias, electrons
and holes are injected into the emissive layer, where
they recombine to form excitons and emit light upon
radioactive decay.3 In PLED devices, charge injection,
charge transport and light emission may be fulfilled in
only one active layer.4 The rapid development of such
devices has made it possible for the commercialization
cameras, as well as full-color TV displays.1 – 4 PVs
have an overall architecture similar to that of PLEDs,
but the mechanism of operation is opposite to that
of PLEDs. In PVs, photoabsorption leads to the
formation of excitons – bound electron–hole pairs.
Under an electrical field, the charges (electrons and
holes) are eventually collected at the anode and
cathode, respectively, through energy transfer, exciton
dissociation and charge transport.5,6
In past years, a great variety of conjugated
polymers, for instance, polyacteylene, polyani-
line (PANI), polypyrrole, poly(p-phenylenevinylene)
(PPV), polyfluorene, polythiophene and poly
(p-phenylene) (PPP), have been developed, and
their chemical and physical properties have been
well characterized.2,3,7 – 13 Among these polymers,

∗
Correspondence to: Tianxi Liu, Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Department of Macromolecular Science, Fudan
University, 220 Handan Road, Shanghai 200433, China
E-mail: txliu@fudan.edu.cn
Contract/grant sponsor: National Natural Science Foundation of China; contract/grant number: 50403012
Contract/grant sponsor: Program for New Century Excellent Talents (NCET) in University
Contract/grant sponsor: Shanghai Rising-Star Program; contract/grant number: 04QMX1403
(Received 22 August 2005; revised version received 4 October 2005; accepted 24 October 2005)
DOI: 10.1002/pi.1970

 2006 Society of Chemical Industry. Polym Int 0959–8103/2006/$30.00

P Chen et al.
polyfluorene-based oligomers and polymers have been
specially focused upon since the first synthesis of
soluble poly(2,7-fluorene)s via ferric chloride oxida-
tive polymerization in 1989.14,15 With the discovery
of Suzuki- and Yamamoto-type synthesis routes (as
shown in Fig. 1),16,17 the development of these types
of materials has been greatly accelerated.3,10,13,18 – 24
Figure 2 shows some typical chemical structures of
reported PFs. In addition to the fluorene-based
polymers, fluorene-incorporated amorphous molec-
ular materials have already been developed for organic
LEDs (OLEDs). With the traits of structural rigid-
ity and sterical bulkiness of the fluorene moiety, the
glass transition temperature (Tg ) of the resulting amor-
phous molecular materials can be distinctly improved
so that thermally stable amorphous glass above room
temperature is realised. So far, fluorene-incorporated
amorphous molecular materials with uniform amor-
phous films have been broadly reported to function
in specialized roles such as hole transporting, elec-
tron transport, hole blocking and emission in OLEDs.
Moreover, it is expected that increasing the electrical
conductivity of such materials can lead to a decrease
in bulk resistivity in organic PVs except for enhancing
hole injection from the indium–tin oxide (ITO) elec-
trode in OLEDs. Detailed examples can be found in a
recent publication by Shirota.25
Extensive attention to PFs in both academic and
industrial fields is driven by the inherent beauty of their
unique molecular structures as well as their appeal-
ing properties. The next section will give a relatively
Figure 1. Schematics of synthetic methods of PFs: (A) Yamamoto
route; (B) Suzuki route (R, -alkyl).
474
complete yet concise picture of the structures and
properties of polyfluorene homopolymers. For appli-
cations in PLEDs, PF is an especially good blue light
emitter; however, they generally show a greenish emis-
sive band; thus many strategies have been proposed
to tune the opto-electronic properties, for instance
copolymerization, blending or doping, bulky side-
group and end-group attachment, oligomer approach,
dendronization, spiro-substitution, and even hydrogen
bonding.18 – 24,26 – 32 On the other hand, the efficiencies
of PVs are not satisfied owing to the weak ability
of charge collection and transport. It is anticipated
that the outstanding stability and transport properties
of PFs will lead to optimized blends of photovoltaic
systems; that is to say, PF-based blends offer an inter-
esting way to improve the efficiencies of PVs.33
In principle, macroscopically photophysical prop-
erties and device efficiencies of PFs are determined
not only by the individual molecule, but also by the
ensemble of molecules. In conjugated materials, the
molecular structures play a crucial role in the high
occupied molecular orbital (HOMO) and low unoccu-
pied molecular orbital (LUMO) band gap, oxidation
and reduction potentials. Besides, they strongly affect
the supramolecular architectures, which lead to spe-
cific morphologies in the solid state, and the resulting
microscopic structures impact the properties in reverse
by virtue of the complicated local molecular orders
and conformations. Studies by Kim, Muccini, Miller,
Tolbert and Schwartz and their coworkers have pro-
vided a profile of molecular structures.34,35 – 38 On the
other hand, the study on supramolecular architectures
formed by self-assembly or other methods is an attrac-
tive approach to comprehend the impacts of inter-
chain interactions and exciton dynamics in conjugated
materials. Supramolecular nanostructures may have
electronic properties that are intermediate between
molecular aggregates and bulk polymers. For exam-
ple, studies on supramolecular assemblies reveal that
exciton–exciton bimolecular annihilation dominates
the exciton dynamics at high fluence.39 – 41 Besides, the
ordering of organized supramolecular structures at dif-
ferent length scales can determine device efficiencies.
The early work by Stupp, Hadziioannou, Hempenius,
Müller, Jenekhe, Yu and their coworkers revealed
the roles of supramolecular architectures of rod–coil
conjugated block copolymers in their opto-electronic
properties and device efficiencies.42 – 48 In conclusion,
the optimization of device performance of PLEDs
and PVs can be achieved with recourse to the opti-
mization of structures (both molecular structures and
supramolecular structures) and morphologies.
UNIQUE STRUCTURES AND APPEALING
PROPERTIES: WHY ARE POLYFLUORENES
FASCINATING?
The chemical and thermal stabilities of PFs have
been proved to be superior to those of PPV. The
decomposition temperatures of PFs may exceed
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi

Figure 2. The chemical structures of typical PFs.
400 ◦ C.34,49 Due to the tetrahedral σ -bonding at
the C-9 atom, the substituents tend to extend out
of the backbone plane and be locally perpendicular
to the chain-axis. Therefore, substitution at the C-9
position does not greatly increase the steric interactions
between or cause distortion in the conjugated
backbone itself, even though the interaction can
lead to significant twisting of the main chain in PF
derivatives. Furthermore, the C-9 atom provides a
facile site for tuning the solubility, opto-electronic
properties and interchain interactions. Generally, the
side-group at the 9-position can orient in two manners:
perpendicular to the plane with a ‘T’-shaped fluorene
unit, or parallel to the plane with a ‘Y’-shaped fluorene
unit.50 The rigid planarized biphenyl structure bridged
by a methylene group in the fluorene monomer unit
leads to a wide band-gap with blue emission, so that
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi
Optimization of opto-electronic property of polyfluorenes
PFs possess the unique ability to emit color spanning
the entire visible spectrum with high efficiency and
low operating voltage. The photoluminescence (PL)
efficiency may excess 80% in dilute solution and 50%
in thin film.51,52
Poly(9,9-dioctylfluorene) (PFO), a typical member
of the PF family, has been well characterized.
It displays rich phase morphologies, and a slight
conformational change in PFO may dramatically
influence its photophysical properties. In addition to
the normal glassy α-phase, a second phase (i.e., the
so-called β-phase), which is formed as a result of
the n-alkyl crystallization of the side chains, has been
identified.53 – 56 The polymer chains are considered
to be more planar, and with longer conjugation
length in the β-phase than in the α-phase.57,58 The
conjugation length in the β-phase is much longer
475
P Chen et al.
than that in the ladder-type poly(p-phenylene) (LPPP)
and may even extend along the entire chain, so
that individual chains may even ultimately behave
like polydiacetylene quantum wires.59 Moreover, the
π -electron delocalization in the β-phase may give
rise to enhancement by orders of magnitude in
photophysical stability in terms of both increased
lifetime and reduced spectral meander.59 However,
the PL quantum yield would be reduced because
the population of polaron and triplet excitons
in the β-phase determined by the fraction of
planarized chains is significantly larger than in
other phase morphologies.58,60 – 63 The β-phase has
demonstrated a narrow, well-resolved absorption peak
at 2.84 eV (437 nm) and an associated vibronic
structure superimposed upon the bulk absorption
with a reduced Stokes shift.54,58,60,64 Recently,
the structural parameters of the α-phase were
measured to be orthorhombic (a = 2.56 nm, b =
2.34 nm, c = 3.32 nm, space group P21 21 21 ), with
eight chains in the unit cell (each of four fluorene
repeats).65,66 However, at temperatures lower than
130 ◦ C, some shifts were identified from 2.34 to
2.38 nm together with a slight increase of the
b-axis, and a lower symmetry along this axis as
well as a preferred orientation of the a-axis along
film normal were identified. Hence, a previously
unspecified modification of the crystalline phase (α-
phase), α  -phase, was suggested.66 The photoexcited
emission spectra in four different phases remain
highly similar except for minor red shifts in the
emission maximum. In addition, PFO belongs to
typical hairy-rod material consisting of a rigid or semi-
rigid backbone in which a dense set of side-chains is
bonded in a comb-shaped manner.67 Semi-crystalline
PFO can display the nematic phase between 160 ◦ C
and 300 ◦ C.68 – 71 Due to the distinct thermotropic
liquid-crystalline characteristics with chain-axis order
parameters, 0.8 < P2 (cos θ ) < 0.9, PFO melts into a
birefringent fluid state at 170 ◦ C, becomes isotropic
at 270–280 ◦ C, and shows a reversible transition
between liquid-crystalline and isotropic phases. This
interesting property allows for fabrication of polarized
light-emitting devices and solid-state lasers.57,72 – 75
As shown in Fig. 3, PFO displays an absorption
peak at ca 380 nm (3.25 eV) with a relatively narrow
linewidth (full width at half maximum) of 0.6 eV,
which is characteristic of most conjugated polymers,
and relies on the distribution of π -stacking length
to some extent.49,53 The absorption onset defines
an optical gap of 2.95 eV (425 nm). The Stokes
shift is less than 50 meV, which is similar to that
of highly ordered LPPP.49,76 In PL spectrum, PFO
shows a well-resolved structure with peaks at 420,
448 and 472 nm, assigned to the 0–0, 0–1, 0–2
singlet intrachain excitons, respectively, with 0–0
(π ∗ –π ) transition being the most intense.49 In contrast
to the absorption, the emission spectra display a
well-resolved vibronic progression with an energetic
spacing of 180 meV, which indicates the stretching
476
1 1
0.8 0.8
PL intensity (a.u.)
Absorbance
0.6 0.6
0.4 0.4
0.2 0.2
0 0
300 350 400 450 500 550 600 650
Wavelength (nm)
C8H17 C8H17
n
PFO
Figure 3. The absorption and PL spectra of pristine thin films of PFO.
The chemical structure of PFO is given below. Reproduced by
permission of Wiley-VCH Verlag GmbH.119
mode of C=C–C=C substructures of the chains.43,64
When casting into the film from the dilute solution,
there is a red shift of the peaks by 15–20 nm
in the condensed state, with a broader absorption
of 100–250 meV on account of conformational
changes and even formation of aggregation or
excimers.23,24,53,64 One drawback of PFO is that the
human eye is not sensitive to its emissive bands. Thus,
polyindenofluorene containing three coplanar rings is
proposed, which shows a PL emission maximum at
around 430 nm.77 – 80 HOMO (equivalent to the value
of the ionization potential) and LUMO (equivalent
to the value of the electron affinity) energy levels
of PFO in the range of 5.6–5.8 and 2.12–2.6 eV,
respectively, are reported.80 – 82 In addition, PFO
is unipolar with hole mobility much greater than
electron mobility.83 Time-of-flight measurements
reveal that PFO has non-dispersive hole transport
with a hole mobility of 10−4 –10−3 cm2 V−1 s−1 ,
and dispersive electron transport with electron
mobility of 10−3 cm2 V−1 s−1 .82,84,85 However, the
value can be further improved, for example, via
monodomain alignment on a rubbed alignment layer
or novel friction-transfer technique,57,86 although the
alignment extent is subject to the molecular weight.87
Very high mobility, greater than 0.1 cm2 V−1 s−1 ,
has been achieved.88 PFO still exhibits high carrier
mobilities on non-ohmic electrode contact.82 In
addition, PFO is considered to be acidic as its
derivatives clearly show a pK a value lower than that of
water; and after base doping an electrical conductivity
of 10−2 –10−3 S cm−1 was reported in air at room
temperature.89 – 91
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi

EXCITON DYNAMICS: WHAT IS THE ORIGIN OF
THE GREEN EMISSION BAND?
As mentioned above, PFs can emit pure blue light.
However, a green emission band at ca 535 nm
(2.2–2.4 eV) and even fluorescence self-quenching are
often observed, which may result in color impurity
and short device life-time.92 – 99 The low-energy
emission band is more intense in electroluminescence
(EL) spectra than in PL spectra,95,100 and can be
enhanced upon annealing or passage of current.101,102
Initially, the excimers are considered to be responsible
for such phenomena.34,94 – 97,103 – 110 The excimers
are a kind of excited-state complex formed by
the interaction of an excited chromophore with a
dissociative ground-state chromophore. They exhibit
temperature and concentration dependences due
to the interchain interactions. Huang et al. further
proved a Tg dependence for the formation of
excimers.103 Figure 4 depicts the fluorescence spectra
of poly(9,9-dihexylfluorene) (PDHF) films thermally
treated in various manners. The additional emission
peak at about 535 nm becomes much stronger than
that of pristine film after annealing, whether in
an atmosphere of nitrogen or air. This low-energy
emission band can be quenched in a dry ice/methanol
bath, but remains identical with original film in
chlorobenzene solution.
Nevertheless, there remain some doubts when
comparing the molecular structure of PFs to that
of polycarbazoles. X-ray analysis has revealed that
substituents at the N position of poly[2,7-(N-
alkylcarbozole)]s are parallel to the plane of the
repeat unit and should not inhibit strong interchain
interactions, while remote substituents at the C-9
position of PFs should limit interchain interactions.
However, poly[2,7-(N-alkylcarbozole)]s actually do
not show any evidence of aggregate or excimer
1.0
Absorbance
3 0.8
Light Intensity (Norm.)
0.8
0.6
2
0.4
1 Bradley et al., even though the fluorenone defects
0.2
4 alone. The interchain/intersegment interactions are
0.0
400 450 500 550 600
Wavelength (nm)
Figure 4. Fluorescence spectra of PDHF for pristine spin-cast film
(1) and the films annealed at 150 ◦ C in air (2) and annealed at 200 ◦ C
in nitrogen (3). Spectrum 4 was obtained from the film that was first
annealed at 200 ◦ C in air for 3.5 h and then quenched in a
methanol–dry ice bath. Inset: UV-visible absorption spectra of
chlorobenzene solution of pristine PDHF (solid line) and annealed
PDHF film (dashed line) at 150 ◦ C for 3.5 h. Reproduced by
permission of the American Chemical Society.103
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi
Optimization of opto-electronic property of polyfluorenes
formation.89 Also, even for the highly conjugated pla-
nar β-phase conformation, no low-energy emission
was observed before oxidative degradation.63 Surpris-
ingly, the 535 nm emission band does not appear in
the freshly prepared films of PFO via the Suzuki route,
but is only observed after significant oxidation.111 It
has therefore been proposed that the 535 nm emis-
sion band originates from fluorenone keto defects
due to oxidation at the methane bridge.53,64,112 – 114
The fluorenone moieties can trap singlet excitons
and reduce PL efficiency. Some controlled model
compounds containing fluorenone were synthesized
to investigate the role of fluorenone on the green
emission peak.115 – 117 It must be noted that the syn-
thetic strategy can directly impact the characteristics of
the final molecular structures of model systems.115,118
The Yamoto aryl-aryl route facilitates the occurrence
of the side-reaction and thus cannot obtain well-
defined molecular structures, whereas the Suzuki route
does not have such problems. Recent work based on
Suzuki coupling polymerization has been reported by
Jenekhe and coworkers.115 By investigating four statis-
tical copolymers containing 1%, 3%, 5% and 10%
fluorenone and fluorene-fluorenone-fluorene trimer
model compound, the experiments indicate that the
controversial green emission band at 535 nm originates
from the fluorenone defects in single-chain polyfluo-
renes instead of intermolecular aggregates or excimers.
Jenekhe et al. further proposed that the increased
intensity of the green emission with the increase of
intermolecular interactions in solution or solid state
was due to the increased energy transfer from fluorene
segments to the fluorenone moieties. Moreover, some
methods of stabilizing the blue emission of polyfluo-
renes, such as dendronization and blending, were also
suggested to impede the oxidation process that forms
the fluorenone defects. Moses et al. showed that the
oxidation of PFs is strongly catalyzed in the presence
of calcium.119 Additionally, crosslinking sites play an
1.4
1.2 important role in augmenting the green emission as
1.0 they enhance excitation energy migration or energy
transfer to the defects by hindering the twisting of
0.6
0.4 chain segments.120
0.2
0.0
Despite this evidence, the presence of fluorenone
300 400 500 600
Wavelength (nm)
700
defects alone may not be sufficient to produce
the green band emission. Just as suggested by
are concluded to be necessary for the green band
emission, they are considered not to be sufficient
proposed to be required for the appearance of the
650 700 750
green band, and the low-energy peak is attributable to
emission from fluorenone-based excimers rather than
from localized fluorenone π –π ∗ transitions.118 Most
recently, the third interpretation on the undesirable
peak has been suggested. Lazzaroni et al. proposed
that the organized structures lead to significant
long-wavelength emission, while non-organized bulky
substituents retain pure blue emission, by comparing
differently substituted PFs.121 It was thought that
477
P Chen et al.
the microscopic morphology of the films plays an
important role in the luminescence properties. Almost
at the same time, Kallitsis et al. suggested that the
535 nm emission peak cannot be attributed to any
other chemical changes such as the formation of
keto defects but could safely be attributed to the
presence of the flexible segments and consequently to
their influence on the organization of the copolymers;
namely, the microscopic morphology should be
responsible for the 535 nm greenish peak in the
investigations of PF-based block copolymers.122
Hitherto, the problem is still debated. For more
detailed studies on the keto defects, it is suggested that
the reader refers to the work by Scherf and List.53,64
For a better picture of the evolution of studies on
the 535 nm emission band, the introductory section
of the publication by Sims et al. is recommended.
Understanding the nature of the electrical excitation
and excimer dynamics will favor the confirmation
of the true origin of the low-energy emissive
peak. Principal dynamic processes including energy
transfer, charge transport and separation, charge
injection and recombination, exciton formation and
dissociation play significant roles in the characteristics
of conjugated polymers. Recently, Bredas et al.
built up a molecular picture of energy-transfer and
charge-transfer processes in π -conjugated oligomers
and polymers.6 Gadermaier and Lanzani also painted
a comprehensive picture of the elementary processes of
exciton dynamics in conjugated polymers by ultrafast
techniques.123 However, there are still a number of
problems in photophysics to be well understood.
COPOLYMERIZATION: TUNING THE
OPTO-ELECTRONIC PROPERTIES BY
MANIPULATING THE STRUCTURES
As is very usual in polymer chemistry, the copolymer-
ization technique is an effective synthesis strategy to
modify short- or long-range organization in materials
and consequently brings about some novel properties
to materials.89 Copolymers are divided into several cat-
egories, and here our interests are only focused on two
of them: rod–coil block copolymers and alternating
copolymers.
Rod–coil block copolymers: controlling the
supramolecular architectures
As pointed out in the European Materials Research
Society Symposium on Supramolecular Approaches
to Organic Electronics and Nanotechnology (held in
Strasbourg, France, 24–28 May 2004), one of
the approaches to develop electronic devices is
to prepare large domains (several hundreds of
nanometers) by supramolecular organization mainly
through intensive non-covalent interplay.124 Because
of the stiff asymmetry between two blocks, rod–coil
block copolymers provide a very powerful and
fascinating strategy to construct novel supramolecular
architectures with well-defined morphology and
478
functions at the nanometer level. As the conjugated
blocks are incorporated into the copolymers as
the rod segment, the supramolecular structures are
reported to impact the photophysical properties
of conjugated molecules due to the flexible coil
segment. For instance, fast exciton diffusion on chiral
supramolecular assemblies was shown to lead to
exciton trapping and luminescence depolarization.125
Moreover, it is relatively convenient to investigate the
relationship between structures and properties as the
supramolecular structures can be manipulated by the
variation of molecular weight, composition, processing
conditions, and so on.
The concept of rod–coil block polymer with
a donor (D) and an acceptor (A) segment was
proposed for PVs. By covalently linking the donor
and acceptor in the polymer chain, the covalent
bond enables a predefined control over characteristic
length between donor and acceptor and thereby
the extent of phase separation.126 Moreover, the
rod–coil copolymer can self-assemble to form well-
ordered micro/nanostructures through microphase
separation. Thus, the D-A rod–coil copolymer
facilitates the construction of the interpenetrating
and bicontinuous network of D-A hetero-interface
in several nanometers, as it combines the merits of
D-A heterojunctions (HJ) and rod–coil copolymer.
Apparently, the efficiency of PVs is much improved
using D-A rod–coil block copolymers. This has been
well illustrated by the work of Hadziioannou and
coworkers.127 – 131 However, this strategy has not yet
been proven to be applicable to a wide range of
semiconducting polymers.
In PLEDs, the most appealing virtue of conju-
gated polymers over organic small molecules is the
ease of solution processing, which enables the fabri-
cation of simple device structures at low cost. Water
is the cheapest and most common solvent; therefore,
water-soluble rod–coil conjugated polymers are of
special interest. Lu et al. reported conjugated-acidic
and conjugated-ionic block copolymers, the two coil
segments of which are based on poly(methacrylic acid)
and poly[(2-(dimethylamino)ethyl methacrylate)],
respectively.132,133 Aggregates in aqueous solutions
were demonstrated in both cases. Moreover, excimer
formation within PF aggregates was confirmed in
conjugated-ionic block copolymers, which was sup-
ported by an additional emission band at longer wave-
length (500–600 nm) reinforced by strong hydropho-
bic interactions. It was also shown that the increase
in ionic strength of the solution leads to further
decrease in quantum efficiency. Additionally, water-
soluble rod–coil conjugated polymers are also suitable
for biosensors as their supramolecular aggregation
behaviors can be changed under different conditions.
The first observed supramolecular architecture
for PF-based rod–coil copolymers was fibrillar
morphology.24,50,134 – 136 The originally studied sam-
ple was prepared with the attachment of coil
poly(ethylene oxide) (PEO) block by living anion
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi
 Optimization of opto-electronic property of polyfluorenes

polymerization.134 The absorption maximum of the a b

reported block copolymer located at 377 nm was
slightly bathochromically shifted and an additional
peak appeared at 428 nm. The fluorescence spectrum
displayed better resolution than that of PF homopoly-
mers; the intensities of the maxima at 437, 460 and
495 nm were enhanced and the peak at 420 nm was
diminished. These spectral data demonstrated the
increased ordering of the luminescent rods in the
block copolymer and the influences of the coil blocks
on the opto-electronic properties of the rods. Similar c d

fibrillar structures were also observed in other PF-

based rod–coil copolymers coupled with different coil
segments such as polystyrene (PS), which were synthe-
sized by using end-capping reagents in the Yamamoto
polymerization.24,134 The absorption and emission
properties of these copolymers are very similar to
those of the homopolymers. Figures 5 and 6 show the
studied chemical structures and corresponding fib-
rillar morphologies from the solutions, respectively.
However, the origin and determination of fibrillar Figure 6. AFM images of thin deposits on mica (a) from THF; (b) from
THF; (c) from THF; (d) from toluene. The scale bar represents 500 nm
morphology were not understood at that time.
(with permission from reference 136).
Most recently, more detailed information concern-
ing fibrillar morphology has been obtained using
tapping-mode atomic force microscopy (AFM).136,137
The AFM image of the copolymer with fPEO = 0.09
(i.e., the average volume ratio of PEO in the
copolymer) revealed that the width and height of the
fibrils appeared to be constant at about 11 ± 1 nm and
1.0 ± 0.1 nm, respectively, indicating that the fibrils
resemble ribbon more than cylinder. Moreover, the
AFM experiments implied that the formation of fibrils
(a) 11.8 nm
is driven by the π -stacking supramolecular interac-
tions between the conjugated segments in the core
of the ribbons. The formation of fibrillar morphol-
ogy is expected to be a result of the subtle interplay
between π –π interactions of PF segments and interac-
tions of PEO segments with the substrate. Combined
with the molecular modeling calculations, a sketch

substrate

(b)

Figure 7. Sketch of the stacking of PF-block–PEO chains into

nanoribbons. The conjugated chains are π-stacking parallel to each
other, edge-on over the substrate, with the PEO chains alternating on
each side of the ribbon axis. (a) Top view, with the conjugated
segments perpendicular to the view; PF chains are in black, PEO in
grey. b) View in perspective. For the sake of clarity, the octyl
substituents are not represented. Reproduced by permission of
Wiley-VCH Verlag GmbH.137

for the proposed stacking of the chains is shown in

Fig. 7. This stacking configuration can minimize steric
Figure 5. The chemical structures of PF-based diblock and triblock hindrances between the conjugated backbones. These
copolymers reported in reference 136. fibrillar morphologies can only be attained when the

Polym Int 55:473–490 (2006) 479

DOI: 10.1002/pi
P Chen et al.

average volume ratio of PEO is lower than 0.3, beyond
which untextured polymer aggregates are formed upon
deposition. In addition, the solvent evaporation kinet-
ics and crystallographic symmetry of the substrate can
also affect the orientation of fibrillar supramolecular
structures.
Thanks to the creative work of synthetic chemists,
more functional materials with novel and well-defined
supramolecular architectures can be realized in the lab.
One of the striking examples is exemplified by atom
transfer radical polymerization (ATRP) methodology.
The ATRP method not only offers more facilities to
synthesize rod–coil copolymers under a facile reaction
condition with a wide range of comonomers,138 – 140
but also allows for a linear increase in the molecular
weight with conversion and quite low polydispersity
due to the activation–deactivation step, which is very
important as the segment with a longer conjugation

C6H13 C6H13 C6H13 C6H13 C6H13 C6H13

O CH3
O C CH CH2 C Cl
n
CH3 O C
O

OFPHM HO

C6H13 C6H13 C6H13 C6H13 C6H13 C6H13

O
O C CH CH2 CH Cl
n
CH3

(A) OFPS

5 µm 5 µm
9.62 nm 9.62 nm

0.00 nm 0.00 nm
2.5 µm 2.5 µm

(a) (b)

0 µm 0 µm
0 µm 2.5 µm 5 µm 0 µm 2.5 µm 5 µm

4.9 µm
5 µm
19 nm
11 nm

0.00 nm
0.00 nm
2.5 µm 2.45 µm

(c) (d)

0 µm 0 µm
(B) 0 µm 2.5 µm 5 µm 0 µm 2.45 µm 4.9 µm

Figure 8. (A) Chemical structures of two novel PF-based copolymers with HEMA and PS, respectively. (B) AFM micrographs (5 × 5 µm images) of
surface patterns formed by the OFPHM on mica substrates as a function of solution concentration: (a) island morphology, 0.025 wt %;
(b) string-like morphology, 0.125 wt %; (c) honeycomb morphology, 0.2 wt %; and (d) honeycomb morphology, 0.25 wt %. Reproduced by
permission of the American Chemical Society.122

480 Polym Int 55:473–490 (2006)

DOI: 10.1002/pi

length surrounded by short conjugation segments
could act as a trap for both holes and electrons. Galvin
et al. have shown that an increase of almost two orders
of magnitude is realized in device performance by
controlling polydispersity.141
Using ATRP techniques, a novel PF-based sample
(OFPHM, as shown in Fig. 8A), was prepared from
2-hydroxyethyl methacrylate (HEMA) with a low
polydispersity value of 1.33.122 Novel island, string and
honeycomb morphologies, which were different from
the foregoing fibrillar morphology, were accordingly
observed. Figure 8(B) shows the AFM image on mica
substrates as a function of concentration. By replacing
the HEMA coil part with PS to produce another novel
copolymer (OFPS, as shown in Fig. 8A), honeycomb-
like structures were still obtained, indicating that the
coil segments do not disturb the ability to self-organize
but only affect the size of the structure formed.
Microphase separation was also supported by thermal
analysis (e.g., differential scanning calorimetry). It was
worth noting that OFPHM in both solvents (THF,
EtOH 95%) displayed an emission peak at 535 nm,
indicating the occurrence of aggregates or excimers,
while OFPS can emit pure blue light. As mentioned
above, the emission behavior can only be attributed to
the organized supramolecular structure. Interestingly,
the emission characteristics of OFPHM in THF did
not change from solution to the solid state, in contrast
with a red shift of 10 nm in 95% EtOH solution.
Similar behavior was also observed in other novel
rod–coil di/tri-block copolymers based on terfluorene
segment coupling with PS and poly(tert-butyl acrylate)
(PtBA), respectively, by the ATRP method.142 Block
copolymers with molecular weights up to ca 21 000
and polydispersity indices less than 1.5 were obtained
in most cases. Phase separation occurred, but no
formation of ground-state aggregates or excimers was
observed in the solid state, even after annealing at
high temperatures. There seemed to be almost no
difference when changing from the solution to the
solid state, mainly because of the well-diluted PF
chromophores in the matrices. The flexible segments
were demonstrated to inhibit aggregate or excimer
formation and do not affect the luminescent properties
of the PF chromophores, so that the rod–coil
copolymers can emit pure blue light. As far as
these analyses were concerned, the coil blocks play
a significant role in the opto-electronic properties
of the rod–coil copolymers, further supporting that
constructing rod–coil block copolymer is a vigorous
modification technique to avoid the 535 nm green
emission peak and spectral shift.
More novel morphologies were observed by study-
ing PF-based block copolymers coupled with other
types of segments. Figure 9(A) shows the globu-
lar or spherical morphology observed from hybrid
block copolymers comprised of helical polypep-
tide sequences (poly(γ -benzyl-L-glutamate), PBLG)
and rigid PF sequences at a trifluoroacetic acid
(TFA)/chloroform (CHCl3 ) ratio of 30/70 (v/v).143
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi
Optimization of opto-electronic property of polyfluorenes
500
(A)
250
0
0 250 500
nm
(B)
PBLG
PHF
Figure 9. (A) AFM amplitude image of PF-b–PBLG block copolymer
cast from TFA/CHCl3 (30/70, v/v) and then annealed in the solvent
vapor. (B) Possible packing scheme of the block copolymer in thin
film. Reproduced by permission of the American Chemical Society.143
The morphology is thought to be produced by
π -stacking of PF blocks and the repulsive interactions
of protonated PBLG blocks. However, parallel fib-
rillar textures appeared when changing TFA/CHCl3
from 30/70 to 3/97 (v/v) (as shown in Fig. 10A).
These self-assembled nanostructures were quite dif-
ferent from those of conventional rod–coil block
copolymers containing π -conjugated polymer blocks.
Figures 9(B) and 10(B) further depict their possible
self-organization patterns, respectively, to elucidate
the morphological differences. It was proved that the
presence of the polypeptide blocks did not impede
charge injection, charge transport or photophysical
processes in EL devices. In addition, branched cylin-
drical morphology (‘nanoworms’) was also observed
for PF-b-PANI block copolymers, as shown in Fig. 11
by microscopy.144,145
Alternating copolymers: tailoring molecular
structures
For applications in LEDs, one major problem is the
imbalance of the injection and transport of holes
and electrons. Most semiconducting polymers have
a higher hole mobility than electron mobility due
to low quantum efficiency and degradation as a
result of Joule heating. One approach to solve such
problems is to exploit the alternating copolymers by
incorporating comonomer with high-electron-affinity
481
P Chen et al.
(A)
(B)
Figure 10. (A) AFM amplitude image of PF-b–PBLG block copolymer
cast from TFA/CHCl3 (3/97, v/v) and then annealed in the solvent
vapor. (B) Possible packing scheme of the block copolymer in thin
film. Reproduced by permission of the American Chemical Society.143
Figure 11. TEM image of a spin-coated film (with thickness of ca
100 nm) of the PF-b–PANI block copolymer (with permission from
reference 144).
moieties. Just as Aviram and Ratner suggested,146
one D-A alternating molecule should behave as an
elementary diode, the effect of which is associated with
the existence of a low-barrier charge-separated D+ A−
state.146,147 The copolymer with alternating donor and
482
acceptor units can lower the barrier for the balanced
D-A charge injection. In addition, the D-A polar HJ
destroys the electron hole symmetry and disturbs the
formation of long-lived charge-transfer intermediates.
Therefore, the formation of the emissive singlet exciton
is accelerated. Huang et al. proposed the concept
of p–n HJ alternating structure, in which typical p-
dopable and n-dopable segments are incorporated
into one backbone of conjugated polymer in order
to adjust the HOMO and LUMO levels of the
resulting conjugated polymers, thus matching the
Fermi energy levels of the electrodes.148 – 153 The
designed polymers usually possess good charge
injection and charge transport properties for both holes
and electrons. Consequently, the approach avoids
the technical problems originating from the high
reactivity of metals with low work functions as the
cathodes as well as the introduction of additional
electron-transporting/injecting layers when fabricating
devices.
Electronic and physical properties, redox behavior
and emission color of the alternating copolymers can
be fine tuned by tailoring the molecular structures,
including attaching different functional groups onto
the comonomers, changing the steric configuration
in n-dope type segments or by controlling the repeat
number of comonomers in one alternating unit. Huang
et al. investigated a series of PF-based copolymers
alternated with various structural units.154 Figure 12
shows the studied compounds and synthetic route.
Most of these copolymers exhibit partial reversibility
in both n-doping and p-doping processes. The
experiments revealed that modifications on the main
chain and related side chain lead to the tuning of
HOMO and LUMO energy levels in the range of
0.4–0.5 eV. The attachment of electron-withdrawing
ester groups leads to an obvious blue shift in the
absorption spectrum, thus enhancing the displacement
of the equilibrium geometry of the polymer at the
excited states from its ground state but strongly
reducing the fluorescence quantum yields, while the
attachment of electron-donating alkoxy groups on the
phenylene ring causes a red shift. The introduction
of carbazole species also causes a spectral blue shift
with increased HOMO and decreased LUMO energy
levels. In addition, the heterocyclic comonomers can
offer some protection against electrically induced
oxidation,155 projecting a possible increase in device
efficiency.
It has been documented that tailoring the molecular
structures of alternating copolymers are a kind of
robust molecular design to tune the color across
the entire spectrum. It is facile to achieve the
goal of full-color display only by easily modify-
ing the comonomers. Successful color tuning relies
on effective energy transfer from the high-band-
gap fluorene units to the low-energy n-type moi-
eties. Therefore, a variety of aromatic heterocycles
containing N, S or O atoms with narrow band
gaps was easily introduced, for example, containing
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi

O O
B B
O O
H13C6 C6H13
11
Ar =
H13C6 C6H13
1 2
CN
EtOOC
5 6
N N
8 9
Figure 12. Chemical structures and synthetic route for PF-based alternating copolymers. Reagents and conditions: (PPh3 )4 Pd(0) (1.0 mol %)
toluene/2 M K2 CO3 (3:2), reflux. Reproduced by permission of the American Chemical Society.154
benzothiadiazole, pyridine, thiophene, oxadiazole or
phenothiazine.155 – 170 The pure red emission (CIE
coordinate values x = 0.66, y = 0.33) was shown
for alternating copolymers containing thiophene and
cyano groups, which is almost identical to the standard
red (x = 0.66, y = 0.34) designated by the National
Television System Committee.167 Organosilicon and
organotin units with aromatic or aliphatic groups were
also incorporated into π -conjugated systems to pro-
duce novel alternating copolymers. Such π -conjugated
systems displayed blue color with relatively high lumi-
nescence efficiencies at a low operating voltage of less
than 10 V, due to the participation of the d-orbitals
of silicon or tin atoms and the decrease in LUMO
level.169,170 Additionally, oligofluorene-type moieties
have been incorporated as part of the ligand framework
of iridium tris-complexes to avoid crystallization.171,172
There has been great success in fabricating high-
efficiency LEDs with alternating copolymers contain-
ing fluorene moieties. For instance, a high external
quantum efficiency (EQE) of 2.54% with luminous
efficiency of 1.45 cd A−1 was reported for saturated red
poly emitter using alternating copolymers containing
benzothiadiazole.168
In essence, the approach of alternating copolymers
can be attributed to conjugation confinement, which
limits π -stacking along the backbone by inserting
inert non-conjugated moieties into the polymer chain.
Polym Int 55:473–490 (2006)
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Optimization of opto-electronic property of polyfluorenes
+ Br Ar Br Ar
H13C6 C6H13
1-10 P1-10
C6H13 OC6H13
H13C6 H13C6O
3 4
COOEt H21C10 C10H21
S
7
10
Although shortening of the conjugated segments may
hinder energy transfer to lower-energy-gap chro-
mophores originating from some defects and thus
enhance the EL capacities because of lesser non-
radiative processes and the reduced interchain inter-
actions, a larger ratio of interruption of π -conjugation
may lead to a decrease in carrier mobility. More-
over, the incorporation of flexible units into the rigid
backbone will, in turn, impose constraints on molec-
ular size, reduce the extent of rigidity and coplanarity
in molecular geometry and affect the microscopically
molecular order of the polymer. As a result, it becomes
more difficult to form morphologically stable and uni-
form amorphous thin films. Ultimately, higher turn-on
and operating voltages are usually a result. Therefore,
there should exist an optimal structure for the choice
of fabrication of LED devices.2,173
The incorporation of fluorene derivatives into
polyesters produces another type of alternating
copolymers,174 – 177 which also shows promising optical
and electrical properties for LED applications. Under
the right conditions, this type of alternating copolymer
does not exhibit any excimer formation or variation
after thermal treatment. It belongs to the reversible
p–n dopable polymers.174 Durocher et al. synthesized
a series of fluorene-based polyesters, and proved that
the oligofluorene units are well isolated in the polyester
chain, with almost no changes in the conformations
483
P Chen et al.
and spectral properties of polyesters.175 – 177 The
luminescence intensity of polyesters remains intense,
and the fluorescence spectra show better vibronic
resolution and sharper peak but significantly red-
shifted bands, indicating a narrower distribution of
conformers in the first excited singlet state. The length
of the oligomer chains and addition of carbonyl groups
do not significantly affect molecular conformation of
the ground state.
BLENDING (DOPING): IMPROVING DEVICE
EFFICIENCY BY OPTIMIZING MORPHOLOGIES
A significant achievement of OLED development
would be to break through the statistical limit of
25% with reference to spin-orbit coupling with a
heavy metal atom and subsequently triplet exci-
ton harvesting by doping the phosphorescent dyes
into semiconducting host materials.178 – 181 An EQE
of 15.4 ± 0.2% and luminous power efficiency of
40 ± 2 lm W−1 were achieved by doping phosphores-
cence dyes.182 Internal quantum efficiencies of 32%
and a peak luminance of 100 000 cd m−2 for tris(2-
phenylpyridine) iridium in dicarbazole biphenyl were
also demonstrated.183,184 Moreover, doping fluores-
cent or phosphorescent dyes into conjugated polymer
hosts has been demonstrated to be very useful to
tune color and emit full color as an alternative
approach for designing alternating copolymers.76,184
Berggren et al. have shown that emission color can
vary as a function of applied voltage by blending
polymers with different emission and charge trans-
port characteristics.33,185 In such host–guest systems,
the energy of excitons formed in the host is trans-
ferred to the luminescent dyes by a combination of
Förster and Dexter energy transfer. Figure 13 sketches
the energy transfer pathways between dyes and host
materials.186,187 Figure 13(a) shows the singlet-to-
singlet transfer responsible for fluorescence in most
doped organic EL devices, and Förster transfer domi-
nates at low fluorescent dye concentrations because of
its long-range nature. Figure 13(b) depicts the possibly
slower, triplet–triplet Dexter transfer from the host.
Figure 13(c) presents singlet–singlet transfer between
the host and the phosphor, and Förster transfer is
still the dominant process in this case. Figure 13(d)
represents direct Dexter transfer between triplet states
in the host and phosphor dopants. However, the dop-
ing method may lead to energy loss due to transfer
to low-lying triplet state or triplet–triplet annihila-
tion, and the efficiency may be limited by phase
separation and aggregation of dopants even at low
blending concentrations.188 Besides, the utilization of
polymers as host materials for LED applications is
still a challenge; thus non-doped phosphorescent host
emitters have been developed to avoid the doping
process.189
On the other hand, the history of the develop-
ment of PLEDs has seen that improvement in EL
efficiencies has successfully been made by blending
484
Energy transfer to fluorescent dyes
(a) host singlet dye singlet
host guest energy transfer
(b) host triplet dye triplet
Energy transfer to phosphorescent dyes
(c) host singlet dye singlet dye triplet
ISC
(d) host triplet dye triplet
Figure 13. Proposed energy transfer mechanisms in films doped with
a fluorescene dye and films doped with a phosphorescent dye. For
each molecule the figure shows the ground-state energy level S0 , the
excited singlet level S1 , and the excited-state triplet level T1 .
Reproduced with permission from Baldo MA, O’ Brien DF, Thompson
ME and Forrest SR, Phys Rev B 60: 14422 (1999). Copyright  1999
by the American Physical Societ. http://prb.aps.org/.186
conjugated polymers. The earlier work of Nishino,
Salaneck, Shim, Sainova, and Inganas and their
coworkers should be highlighted.2 There are two
reasons that together account for the improvement
in device efficiencies. One is that dispersive emitters
within the polymer matrix alleviate the formation of
aggregation or excimers due to dilution. The other is
that efficient Förster energy transfer from the donor
to the acceptor, as well as spatial confinement of
the excitons in the acceptor polymers, leads to a
decrease in exciton quenching and excimeric emission
via a non-radiative process. Moreover, electron hole
recombination preferentially takes place at the domain
boundaries of two phases.190 Ho et al. demonstrated
that devices fabricated from an active layer consist-
ing of PFO blended with poly(dioctylfluorene-alt-
benzothiadiazole) (F8BT) have an external forward
efficiency of 6.0% at a luminance of 1600 cd m−2 at
5 V, exhibiting nearly balanced injection, near-perfect
recombination and greatly reduced pre-turn-on leak-
age currents.191 Yang et al. suggested that the PL
and EL efficiency of MEH-PPV-based PLEDs could
be dramatically enhanced by blending with PFO,
and their results showed that EL efficiency is sig-
nificantly increased from about 0.5 cd A−1 for pure
poly[2,5-bis(cheolestranoxy)-1,4-phenylene vinylene]
(BCHA) to nearly 3.0 cd A−1 for the blend of BCHA
Polym Int 55:473–490 (2006)
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and PFO, and the absence of interchain species was
revealed in the blends.192 Jenekhe et al. reported that
the spectrally stable blue EL is obtained for LEDs
fabricated from binary blends of PFO with either
poly(vinyldiphenylquinoline) (PVQ) or PS as a result
of higher thermal stability of the blends on account
of higher Tg of both PVQ and PS relative to that
of PFO.193 Meanwhile, brightness and EL efficiency
were improved by a factor of 5–14 compared to PFO
homopolymer devices.
The PF-based blends open a new approach to
understanding some principal issues from LED appli-
cations, including the basic processes of exciton
dynamics. Regarding the usually observed black spots
(non-emissive areas) in the period of device operation
that lead to complete device degradation within a few
hours, Kim et al. investigated PLEDs fabricated from
F8BT blended with poly(9,9 -dioctylfluorene-co-N-
(4-butylphenyl)diphenylamine (TFB) as the emissive
layer by using in situ micro-Raman spectroscopy, and
proposed that the black spots are not responsible for
the reduction in EL efficiency with device operation,
but only effectively cause a reduction of the device
active areas and the concomitant loss of total lumi-
nance output.194 Concerning the fact that the singlet
generation fractions of conjugated polymers do not
obey to the limit of 25%,178,195 Greenham et al. stud-
ied blends of PFO and F8BT, and thought that the
singlet:triplet ratio relies on the chemical structures
of the polymers. Moreover, the singlet yield could be
unexpectedly high; that is to say, triplet formation is
not an obstacle to high-efficiency device operation.196
Regarding the difficulties of charge injections, Gross
et al. showed that doping π -conjugated polymer layers
in PF-based systems is conducive to improving the
injection of holes in OLEDs, and the barrier to hole
injection can be continuously reduced by increasing
the doping level of conjugated polymers.197 In respect
of energy transfer in blends, Byun et al. blended a
series of polyfluorenes with poly(N-vinylcarbazole),
and demonstrated that the D–A distance, which
affects the efficiency of energy transfer, was altered
by the side-chain length of fluorene rather than the
spectral overlap integral.198 For example, blends con-
taining PFs with longer and bulkier substitutions at
C-9 atoms have a greater distance between donor and
acceptor and thus the rate and efficiency of energy
transfer decrease. Referring to device structure and
performance, Morteani et al. reported that production
of high-efficiency LEDs with green emission at 2.1 V
and a luminance of 100 cd m−2 was achieved from
de-mixed blends of PFs by fabricating ‘distributed HJ’
structures when investigating the properties of two dif-
ferent blend systems: blends of TFB and F8BT, and
blends of poly(9,9 -dioctylfluorene-co-bis-N,N  -(4-
butylphenyl)-bis-N,N  -phenyl-1,4-phenyldiamine
(PFB) and F8BT.199 The ‘reverse photo-induced
charge transfer’ state was proposed to explain the very
low operating voltage, where electron hole capture is
a barrier-free process to form the exciplex, which has
Polym Int 55:473–490 (2006)
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Optimization of opto-electronic property of polyfluorenes
significant charge transfer character and is lower than
the charge-separated state in energy.
Beyond all doubt, device performance is very
sensitive to blend morphology. Spherical or cylindrical
morphologies are believed to be favorable for LED
applications.122 Vertically and laterally segregated
structures have also been observed in PF-based blends.
However, it has been proved that the external quantum
efficiencies of LEDs made with vertically segregated
structures are more efficient than those of laterally
segregated LEDs, between 25% and 100%.200 Recent
studies reporting on spin-cast thin-film morphology
of blends can support this. X-ray photoelectron
spectroscopy (XPS) and AFM experiments further
revealed that lateral phase-separated domains are not
pure at the submicron length scale, and vertical phase
segregation at the nanoscale occurs in blend films.190
Processing conditions also have some influence on
device efficiency. For instance, a pre-heated device
was shown to exhibit an increase in efficiency while a
post-heated device did not.201
Conjugated polymer blends are used not only in
LEDs but also in PVs. For applications in PVs,
blends consisting of donor and acceptor polymers
are commonly employed to increase efficiency. An
interpenetrating network of spatially distributed D–A
HJs are constructed.202 Because of the large surface
areas of dispersed interfaces between phase-separated
components, exciton dissociation into polarons is
effectively promoted. As a matter of fact, higher
device efficiency can be achieved by increasing diverse
interfacial areas between mesoscale phases. Besides,
the charges generated close to the phase-separated
interfaces are more readily collected owing to the
ease in percolating into their preferred phases. Friend
et al. further studied a device involving a blend of
PFB and F8BT, and suggested that effective charge
collection only occurs for charges generated close to
the corresponding electrode,203 and charge transport
rather than charge generation is the limiting factor in
device performance. Also, owing to the direct paths
from cathode to anode within either separated phase,
the open-circuit voltage of a blended layer is lower than
that of a bilayer device comprising distinct layers of
donor and acceptor materials.203,204 A major problem
with blends is that a possible partial discontinuity of
the donor and/or acceptor phases may occur. Besides,
increased energy level disorder in both phases may
lead to an increase in charge trap density and a
reduction in electron and/or hole mobility. Therefore,
a degradation in overall device performance could be
expected.126,205
The efficiency of photovoltaic blends strongly
relies on both blend morphology and compositional
microstructure like that of LEDs. For example, bicon-
tinuous structures are considered to be pivotal for
high-efficiency PVs since they are crucial for the
transport of holes and electrons to the respective elec-
trodes without recombination.205,206 With regard to
phase-separated morphology of the blend, Stevenson
485
P Chen et al.
found that micro-scale phases penetrate substantially
through the film and contain significant volumes of
both constituents.207 Lidzey et al. further investigated
the structures of the blend of PFO and F8BT by
scanning near-field optical microscopy, scanning force
microscopy and nuclear reaction analysis, and pro-
posed that one of the polymers may preferentially
wet the surface and form a partially crystallized wet-
ting layer.206 However, enhanced residual emission
still may come from the regions beneath the contin-
uous surface layer and a relative depletion in the
concentration of F8BT acceptor molecules at the
edge of PFO-rich domains. Additionally, a hierar-
chy of micro- and nanoscale morphology probably
emerges.187 In addition, the preparation method of
the blend film, for example the solvent, solvent evap-
oration rate, substrate temperature and saturation of
the ambient atmosphere during film preparation, all
play important roles in controlling phase-separated
morphologies and ultimately PV performance.33,208
For instance, PVs using PFB/F8BT prepared from
xylene solution show an EQE of merely 1.8%, whereas
devices from chloroform solution exhibit an EQE of
4% at 3.2 eV.33
As mentioned above, the dimension of phase
separation should be controlled in the range of
the exciton diffusion length equal to a few tens
of nanometers. Thus, the overall layer thickness
should not greatly exceed the penetration depth
of the incident light.206 Moreover, an increase in
PV efficiency occurs together with a decrease in
feature size. For a columnar, segregated or three-
dimensional interpenetrating network structure in the
blend film, a linear or super-linear dependence of
PV efficiency on length scale might be expected.187
However, the blends in the conventional way are
difficult to realize, although the characteristic phase-
separated length scales vary with conditions such as
the solvent, substrate temperature or saturation of the
atmosphere over the transforming film. Luckily, the
micro-emulsion method was successfully applied in
polymer blends to precisely manipulate the dimension
of phase separation from 30 to 500 nm.206,207,209 The
solvent used in the micro-emulsion process does not
affect the efficiency of PVs, indicating that not the
kinetics of particle formation but rather the particle
size and composition control the device performance.
Two kinds of blends prepared in this way were studied
(as shown in Fig. 14). An EQE of ca 4% is attained
for a device made from polymer blend nanoparticles
containing PFB:F8BT at a weight ratio of 1:2 in
each individual nanosphere, which is among the
highest values reported so far for PVs. Further studies
revealed the influence of the layer composition on PV
efficiency.209 In addition, the micro-emulsion method
has already been applied to the fabrication of OLEDs
to improve their opto-electronic characteristics by
producing semiconducting polymer nanospheres.210
Moreover, PF-based polymer blends also show great
promise in other fields. The maximum luminance
486
Blend of two
different dispersions
Two different polymers in
individual particles
Figure 14. Strategies to prepare binary polymer blends using
polymer nanospheres. Phase-separated structures at the nanometer
scale can be prepared either by coating a layer from a dispersion
containing nanoparticles of two different polymers, or by using
dispersions that contain both polymers in each individual
nanoparticle. Reproduced by permission from Macmillan Publishers
Ltd: Nature Mater 2: 408 (2003).205
of white polymer light-emitting diodes comprised of
polyfluorene doped with a ‘twistancene’ can exceed
20 000 cd m−2 . A maximum luminous efficiency
of 3.55 cd A−1 at 4228 cd m−2 was achieved with
a maximum power efficiency of 1.6 lm W−1 at
310 cd m−2 , while device emission color is not a
function of bias currents.211 Polymer blends are
attractive for lasers as they can form four-level systems,
thereby impeding self-absorption and reducing the
threshold for amplified spontaneous emission due to
the highly efficient host–guest Förster energy transfer.
However, Edman demonstrated that the ‘defect
polymer’ exhibits more advantages than polymer
blends in light of PF-based studies for optically
pumped lasers.212
CONCLUSIONS AND OUTLOOK
There is no doubt that PFs are one of the
most promising materials for opto-electronic devices,
especially PLEDs and PVs. As demonstrated by this
review, their opto-electronic properties and device
performance can be greatly enhanced by subtly
copolymerizing or blending with other molecules. A
mass of novel organic materials has been created, and
the great improvement benefits from the optimization
of molecular structures, supramolecular orders and
morphologies. For PLED applications, color purity
and stability in long-term operations remain a
challenge, while efficiency has met the requirements of
commercialization. Solving such problems correlates
with progress on knowing the origin of the unwanted
greenish emission band. Understanding the electronic
properties of polyfluorenes and mechanisms of exciton
dynamics is momentous for LED development. In
the long term, as Kohler et al. predicted,35 the
focus of LED development will be to optimize
the out-coupling of light from the device instead
of the emission efficiency. On the other hand, for
applications of PFs in PVs, it is crucial to effectively
manipulate the length from donors to acceptors
in the nanometer regime of the exciton diffusion
range. Hence, the concepts of ultra-fast photo-induced
energy and electron transfer between donor and
acceptor units, D-A bulk HJ and polymer blends of
Polym Int 55:473–490 (2006)
DOI: 10.1002/pi

donor and acceptor have been proposed to promote
efficient exciton dissociation and balanced transport.
Recently, Forrest et al. proved that efficiency could
be much increased by designing a smart device
structure. They demonstrated a hybrid planar-mixed
molecular HJ photovoltaic cell consisting of a mixed
layer of donor and acceptor molecules sandwiched
between homogeneous layers of donor and acceptor
materials,213 and then the maximum power conversion
efficiency of (5.0 ± 0.3) % was first realized.
Although much progress has been made in the fields
of PLEDs and PVs, the relationship between their
structure, morphology and photophysical properties
has not been quite clear, and the different hierarchies of
organization from molecules to devices remain a chal-
lenge. As a result, nanoscience and nanotechnology are
logically merged and consequently facilitate in-depth
studies. The development of synthetic methodology,
especially controlled radical polymerization methods,
opens new avenues to precisely control structures and
morphologies. For electronic devices comprised of
π -conjugated polymers, the role of inter-/intra-chain
electronic coupling has not yet been well understood.
Thus, one of the elementary but key subjects is to
form a picture of quantum mechanical processes of
exciton dynamics. Nevertheless, valuable production
can successfully proceed under the guidance of such
processes. For instance, Klimov et al. showed a sim-
ple but elegant, high-efficiency device structure by
exploiting the non-radiative Förster energy transfer
process.214,215 Their significant work can lead to a
new generation of ultra-high-efficiency light sources
ranging from nano-optics to city blocks. In a word, the
ongoing efforts on materials designing, device archi-
tecture and processing technologies will advance the
development of polyfluorenes in organic electronics
and ultimately boost the commercialization of devices
such as LEDs and PVs.
ACKNOWLEDGEMENTS
This work was financially supported by the National
Natural Science Foundation of China under Grant
50403012, the ‘Program for New Century Excellent
Talents (NCET) in University’, and the ‘Shanghai
Rising-Star Program’ under grant 04QMX1403.
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