PROGRESS REPORT

Advanced Materials Progress Report on

Liquid Crystals for Charge Transport,

Luminescence, and Photonics**
By Mary O'Neill* and Stephen M. Kelly
Ordered molecular materials are increasingly used in active electronic and photonic
organic devices. In this progress report we discuss whether the self-assembling properties and supramolecular structures of liquid crystals can be tailored to improve such
devices. Recent developments in charge-transporting and luminescent liquid crystals
are discussed in the context of material requirements for organic light-emitting devices, photovoltaics, and thin film
transistors. We identify high carrier mobility, polarized emission, and enhanced output-coupling as the key advantages of nematic and smectic liquid crystals for electroluminescence. The formation of anisotropic polymer networks gives the added benefits of multilayer capability and photopatternability. The anisotropic transport and high
carrier mobilities of columnar liquid crystals make them promising candidates for photovoltaics and transistors.
We also outline some of the issues in material design and processing that these applications demand. The photonic
properties of chiral liquid crystals and their use as mirror-less lasers are also discussed.

1. Introduction
Over many years the liquid-crystal display (LCD) industry
has stimulated an enormous research effort in the development of new liquid crystals (LCs).[1] These are mostly required to be transparent and highly insulating, as well as easily
and very quickly reoriented in an electric field. A wide range
of chemically, photochemically, and electrochemically stable
liquid crystals and additives have been developed to fit these
criteria. However, the continued dominance of LCDs in the
area of flat panel displays is now being challenged by rapid
improvements in organic light-emitting diodes (OLEDs), an
emissive and potentially more efficient display technology recently introduced to the market.[2,3] The wide viewing angle,
high brightness, video-rate addressing, and low power consumption of OLEDs compare well with the capability of current LCDs. Unsurprisingly, OLEDs have a different spectrum
of material requirements: e.g., some must be highly conjugated for light emission; molecular energies must be engineered

[*] Dr. M. O'Neill

Department of Physics
University of Hull
Cottingham Road, Hull, HU6 7RX (UK)
E-mail: M.ONeill@hull.ac.uk
Dr. S. M. Kelly
Department of Chemistry
University of Hull
Cottingham Road, Hull, HU6 7RX (UK)

[**] The authors thank A. E. A. Contoret for Figures 8 and 9.

Adv. Mater. 2003, 15, No. 14, July 17

DOI: 10.1002/adma.200300009

for electronic injection and transport. A high viscosity is an

advantage for these applications as the organic materials
should not move in the electric fields present and indeed an
extremely high viscosity can lead to the formation of an amorphous glass required for stable OLEDs. These commercially
important developments in OLEDs are occurring concurrently with a renaissance in active organic materials in the
areas of photovoltaics,[4] transistors,[5] and solid-state lasers.[6]
Therefore, a question of immediate scientific interest is: can
the LCD know-how and understanding of the self-assembling
properties and various supramolecular structures (phases) of
liquid crystals be used to advantage in OLEDs and in other
devices such as organic solar cells, organic thin film transistors, and lasers? If the answer is positive then further issues to
be resolved include the nature of the liquid-crystalline state of
most use. Possibilities include the nematic and smectic states
of calamitic (rod-like) molecules or the various columnar (discotic) phases produced by phasmidic or disk-shaped molecules (see Figs. 1,2).
The literature suggests that different phases are required
for different physical effects and device configurations. For
example discotic liquid crystals orient in columns and are effectively molecular wires with a high hole mobility, greater
than 0.1 cm2 V1 s1, along the columns. Very promising photovoltaic performance has been recently obtained by making
use of this high hole mobility.[7]
Luminescent and charge-transporting LC polymer networks
formed from nematic liquid-crystal monomers provide a low-

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Fig. 1. A) Schematic of a nematic phase with orientational order. B) Schematic

of a smectic phase with positional and orientational order.

transporting and light-emission properties of LCs are outlined

in Sections 3 and 4, respectively. Device-processing issues and
current device performance are investigated in the following
two sections. Then, in Section 7, the photonic properties of
chiral LCs are discussed with emphasis on their use in distributed feedback lasers. The review concludes with an overview
of the discussion.

2. Material Requirements for OLEDS,

Photovoltaics, and Transistors

Fig. 2. Schematic of a discotic (columnar) phase with A) homogeneous and

B) tilted homeotropic orientation.

cost option to fabricate multilayer OLEDS with the added advantage of being photolithographically patternable.[8,9] The
photonic band-structure of (optically active) chiral nematic
LCs, well known for producing vivid colors in reflection, has
recently been used to provide feedback for mirror-less, solidstate organic lasers.[10]
This Progress Report discusses the potential role of liquid
crystals in luminescence, electronic transport, and photonics.
In Section 2 we discuss the material properties and device
configurations of OLEDs, photovoltaics, and transistors, to
provide a context for subsequent discussion. The charge-

We need a clear appreciation of the material requirements

of OLEDs, photovoltaics and transistors in order to assess the
potential of LCs for these devices. Figure 3 shows a schematic
of the simplest type of OLED where light is generated by
electrical excitation. A thin film of an organic emitter is sandwiched between a transparent anode and a metallic cathode.
Electrons and holes, which are injected into the lowest unoccupied molecular orbital (LUMO) and highest occupied
molecular orbital (HOMO) respectively, drift through the orcathode
emitter
anode

substrate

light
Fig. 3. Schematic of a single layer OLED.

Mary O'Neill was born in Ireland and received her PhD in Physics from the University of Strathclyde. After a postdoctoral fellowship in Integrated Optics at the University of Glasgow and a
short spell in industry, she joined the Physics Department of the University of Hull. She is joint
leader of an interdisciplinary team investigating new photonic and optoelectronic applications
for liquid crystals. Other research interests include the photoalignment of liquid crystals and
hybrid inorganicorganic optoelectronic devices.

Steve Kelly has spent over 27 years involved in the synthesis of many different kinds of liquid
crystals for use in LCDs and about 10 years designing new reactive mesogens for various electrooptical applications including OLEDs and new photovoltaic devices. He is only the third chemist
to report the synthesis of over 3000 liquid crystals. Some of these are to be found in many types
of commercial LCDs. He has worked with G. W. Gray and E. P. Raynes at Hull, T. J. Scheffer
and J. Nehring at ABB and M. Schadt and J. Fnfschilling at Roche. He is now joint head with
Mary O'Neill of the Organophotonics Research Group at Hull, where the use of light-emitting
and charge-transporting liquid crystals in OLEDs has been pioneered.
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Adv. Mater. 2003, 15, No. 14, July 17

ganic film under the influence of the applied electric field (see
Fig. 4). The coulombic attraction between an electron and
hole at the same chromophore site results in the formation of
an exciton, a bound electronhole pair, which recombines to
vacuum level
EA

anode

LUMO

cathode
Ee

pounds is expensive and not easily scaleable. The deposition

of multiple polymer layers using conventional spin-coating
can prove problematic, because layers may mix when solvents
used for spin-coating subsequent layers dissolve the underlying film deposited previously. The problem has been alleviated to some extent by the use of blends, the latest of which
have some vertical segregation.[17] Thermal crosslinking has
also been used to fabricate graded hole-transporting polymer
layers.[18]

IP

SC12H25

S
C7H15O
N

Eh

HOMO
anode

emitter

7O-PBT-S12: Cr 90 C, SmA 100 C, I [117]

cathode

Fig. 4. Energy level diagram of single-layer OLED under forward bias. Ucathode
and Uanode refer to the work functions of the cathode and anode, respectively.
DEe and DEh refer to the barriers for electron and hole injection, respectively.

produce luminescence. More sophisticated devices have multiple layers with the luminescent layer sandwiched between
hole- and electron-injection/transport layers. Efficient devices
require the matching of energy levels to minimize the barriers
for carrier injection and to trap both electrons and holes in
the luminescent region.
A high carrier mobility (l), defined as the electron or hole
velocity per unit electric field, is required and it is important
to balance the injection of electron and holes. The luminescent material must have high quantum efficiency. The optical
mode pattern and recombination zone must be matched for
efficient out-coupling of the light. New OLED configurations
are being investigated to enhance output coupling by reducing
the fraction of light trapped in the device by total internal reflection. Finally the materials must be photochemically, thermally, and electrochemically stable to maintain long-term operation. There are many excellent review articles giving
detailed examinations of these issues for the two classes of organic materials that are normally used: small molecules and
main-chain conjugated polymers both stabilized in the glassy
state.[1114] The first system to be developed was the thermal
evaporation of materials of low molecular weight, which form
thermally stable glasses. Discrete thin films of different materials of low molecular weight are sublimed in sequence to optimize the device configuration. This multilayer approach has
proved very successful and has resulted in the best OLED
performance reported to date: a power efficiency of 60 lm W1
and an external quantum efficiency of 19 %.[15] Alternatively,
cheaper and scaleable deposition methods, such as spin-casting and ink-jet printing, are used to form electroluminescent
(EL) and charge-transporting films of main-chain conjugated
polymers. These thin polymer films are also stabilized in the
glassy state below the glass-transition temperature. A power
efficiency of 20 lm W1 has been obtained.[16]
With two very well established and commercially viable
technologies it is not immediately obvious that organic EL
requires a third approach involving liquid crystals. However,
the physical vapor deposition of low-molar-mass organic comAdv. Mater. 2003, 15, No. 14, July 17

http://www.advmat.de

7O-PBT-S12 is a typical example of the kind of low-mass calamitic (rod-like) LCs applicable to OLEDs.[19] The aromatic
core forms the chromophore, and, in a similar way to non-liquid-crystalline chromophores, electron-donating and electronaccepting groups can be incorporated within the core to facilitate hole or electron transport, or to control the luminescence
energy. However, the length and shape of the aromatic core
and aliphatic end-chains, as well as the presence of lateral substituents, must be balanced to obtain a LC phase at an appropriate temperature. Can we justify adding this complexity to
the range of properties required for OLEDs? We believe that
the intrinsic advantages of high charge mobility, low-cost multilayer fabrication, lithographic photopatternability, polarized
emission, and enhanced output-coupling make LC polymer
networks formed by the polymerization of LC monomers (reactive mesogens) viable organic materials for OLEDs.
There are many recent reviews on organic photovoltaics.[2022] Figure 5 illustrates the energy level diagram of a
photovoltaic blended device under short-circuit conditions.
The photovoltaic effect requires i) absorption of solar radiation and the photogeneration of electrons and holes and
ii) charge separation, and the transport of electrons and holes
for collection at the cathode and anode, respectively. Each of
these individual processes should be highly efficient and there
should also be a minimum of charge recombination. Absorption is via exciton formation. Charge separation is achieved
by ionization of the exciton at either a single hetero-interface[23] or over a distributed interface between electron-donating and electron-accepting species. The separated carriers
drift to the external electrodes in the built-in field introduced
by dissimilar electrodes. Distributed interfaces can be formed
eLUMO
anode

HOMO

LUMO
cathode
HOMO

h+
donor

acceptor

Fig. 5. Energy level diagram showing charge separation and transport in a blend
consisting of an electron donor and acceptor placed between a dissimilar anode
and cathode, which provide a built-in field.

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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either by phase separation of main-chain polymers having different electron affinities and ionization potentials[24] or, for
example, by dispersing a C60 electron-acceptor in a mainchain polymer.[25] Another option is the dispersal of a holetransporting organic in a mesaporous dye-sensitized TiO2
layer.[26] Power efficiencies above 2 % are obtained in many
configurations.[2426] It has recently been noted that charge
transport is a greater limitation on the efficiency of blended
polymer photovoltaics than charge generation.[27] This suggests a role for high-mobility LC materials.
The widespread interest in organic field-effect transistors
(OFETs) is based on their large-area coverage, structural
flexibility, and low-cost processing.[28] A typical OFET configuration is shown in Figure 6. For a p-type semiconductor,
conduction of charge between the source and drain electrodes is governed by the gate voltage. When the gate is posisource

drain
semiconductor

insulator

gate

insulator

substrate

A convincing demonstration that liquid crystallinity enhances carrier transport was provided by studying the 9,9dioctyl polyfluorene PFO as a uniformly aligned nematic
glass.[33] An exceptionally large room-temperature hole mobility of 9 103 cm2 V1 s1 was obtained, which compares
with a hole mobility of 4 104 cm2 V1 s1 when the same
polymer is deposited as an isotropic film.[34]
C8H17 C8H17

n
PFO: Cr ~ 170 C, N ~ 270280 C, I

The orientational order in the nematic state facilitates the

formation of a two-dimensional (2D) conductor. Discotic LCs
self-organize in one dimensional (1D) columns and smectic
LCs form 2D layers, as illustrated in Figures 1,2. Both of these
configurations have also been shown to promote anisotropic
carrier transport arising from the increased overlap of aromatic cores.[3537] A range of asymmetrical triphenylene
(HAT) materials such as those shown below with glassy or
plastic columnar phases were developed during the 1990s.[38,39]

Fig. 6. Typical configuration of an OFET.

OC5H11

tive with respect to the source, the semiconductor is depleted

of carriers. When the gate is biased negatively, carriers accumulate in the channel between source and drain. The drain
current is then proportional to the material mobility. Solution processed polythiophene OFETs attain a hole mobility
of 0.1 cm2 V1 s1,[5,29] whilst vapor-deposited pentacene has a
mobility of 1.5 cm2 V1 s1.[30] Carrier transport takes places
by hopping between localized states and the latter value is
close to the limit for molecular materials at room temperature. Very high molecular order without trapping at grain
boundaries is required to reach these high values of mobility.
Hence, the self-assembly properties of LCs, in combination
with their ability to provide anisotropic carrier transport
along the channel, makes them viable candidates for OFETs.

3. Recent Developments in Charge-Transporting

LCs
One of the major disadvantages of amorphous organic materials is their low mobility, which is limited by disorder. With
recent improvements resulting from molecular design, amorphous molecular materials are now available with hole and electron mobilties greater than 103 cm2 V1 s1 and 104 cm2 V1 s1,
respectively.[31] Polyphenylene vinylene (PPV), the standard
polymer for OLEDs, has a mobility of 105 cm2 V1 s1.[32]

n
PPV: intractable

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O
C5H11O

C5H11O
OC5H11
OC5H11

R=

R=

R=

CN

R=

Discotic LCs of higher molecular mass usually have LC

phases at elevated temperatures and a recent important advance is the development of hexacoronene materials with
room-temperature columnar phases. This has been achieved
in two ways: either by using a phenylene group as the coupling
agent between the core and the aliphatic side-chains to form
HBCPhC12,[40] or by attaching six multi-branched aliphatic
side-chains to a hexa-peri-hexabenzocoronene to form HBC
C416.[41] In the latter case, the high degree of chain branching
results in the formation of a low-melting hexagonal columnar
phase with an extraordinary phase range. These developments
are particularly exciting because of the large size of the hexacoronene core and the empirical observation that the maximum mobility obtainable for discotic LCs increases with the
size of the aromatic core.[42] Indeed a room-temperature mohttp://www.advmat.de

Adv. Mater. 2003, 15, No. 14, July 17

bility of 0.22 cm2 V1 s1 was obtained in the LC phase of

HBCPhC12.
R

gated, e.g., the terthiophene, 8-TTP-8, shows hole and electron mobilites above 1 102 cm2 V1 s1 in the smectic G
phase at elevated temperatures.[37]
S

C8H17

C8H17

8-TTP-8: SmG 72 C, SmF 88 C, SmC 91 C, I

Phenylnaphthalene LCs such as 8-PNP-012 show a variety

of smectic phases with temperature-independent hole mobilities within the individual phases. Polaron hopping models and
Monte Carlo simulations are applied to fit the data.[53,54]

OC12H25
C8H17

R=

8-PNP-012: Cr 79 C, SmB 101 C, SmA 121 C, I

HBCC416: Cr 36 C, Colho 231 C, I
R = C6H4C12H25
HBCPhC12: Col1 18 C, Col2 83 C, Col3

The transport properties of HAT have improved substantially on incorporation of a stoichiometric amount of a substituted phenyltriphenylene (PTP), which interleaves the triphenylene in the columnar stacks, thus increasing the order
and stability of the columnar mesophases. A glass is formed
on cooling to room temperature retaining a high hole mobility
of 1.6 102 cm2 V1 s1.[43] There have also been some developments in electron-transporting discotic materials. A perylene diimide having high-temperature discotic and smectic
ordering shows mobilities > 0.1 cm2 V1 s1 in the LC phase.[44]
An electron-deficient columnar plastic crystal at room temperature has recently been synthesized.[45]
C2H5O2C

CO2C2H5

C2H5O2C

CO2C2H5

However, these materials are crystals at room temperature

and, consequently, not suitable for practical applications. A
recent attempt to solve this problem involves the use of a
polymer-stabilized smectic gel containing the phenylnaphthalene LC8-PNP-012. Indeed the gel was found to retain the
high hole mobility values, > 103 cm2 V1 s1, of the unstabilized LC at elevated temperatures.[55] The diene 1 (see structure below) was the first compound to exhibit a smectic C
phase at room temperature with an electron mobility of
1.5 105 cm2 V1 s1. It is also a reactive mesogen, which can
be photopolymerized to form a polymer network.[56] This is a
more attractive approach for practical applications as LC
polymer networks retain the original order and some other
physical properties of the monomer up until the (very high)
decomposition temperature. Polymer networks are also insoluble and intractable, which facilitates the fabrication of multilayer devices by spin coating.
O

Diene 1: Cr 25 C, SmC 124 C, I

A variety of approaches have been used to examine the

mechanism of hole transport in discotic LCs. The relatively low
values of mobility (< 1 cm2 V1 s1) mean that incoherent hopping transport rather than coherent (band-like) models are
mainly used. A range of approaches have been used to explain
the low temperature dependence of mobility and confirming
the 1D nature of the transport.[4650] Quantum mechanics is also
used to study hole transport in discotic LCs.[51] A coherent theory is used to investigate why a high hole mobility is obtained
in mixed HAT/PTP systems where the high ionization potential
of the interleaving PTP may present
an energy barrier to hole tunneling between the HAT molecules along the
O
stack.[52]
C5H10O
The transport properties of the
O
smectic and nematic phases of nonpolymeric LCs have also been investiAdv. Mater. 2003, 15, No. 14, July 17

OC5H10

Perylene diimide: Cr 244 C, Col 313 C, I

N
C5H10O

http://www.advmat.de

Electronic rather than ionic transport in low-mass nematic

LCs was first observed in the glassy LC phase at room temperature.[57] Hole mobilities of up to 4 104 cm2 V1 s1 were reported and recent unpublished results show hole mobilities
> 1 103 cm2 V1 s1 using different aromatic cores.[58] The
hole mobility of a photopolymerizable nematic glass, diene 2,
is doubled on formation of the polymer network.[57] The mobility has a large temperature and a small field variation. This
is explained using a static disorder model that includes spatial
correlations in the carrier energies.
H7C3 C3H7
S

S
OC5H10

Diene 2: Cr 92 C, N 108 C, I [Tg 39 C])

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M. O'Neill, S. M. Kelly/Liquid Crystals for Charge Transport, Luminescence,

4. Light-Emitting LCs
The luminescent material in OLEDs must have a high
quantum efficiency of photoluminescence (PL). This can be a
formidable task since many molecular emitters, which are
highly efficient in solution, are dim in the solid-state. In solution, PL originates from singlet excitons and vibronic peaks
are observed. The PL spectrum red-shifts and broadens when
aggregates or excimers are formed and intensity is quenched
in the solid state. Various molecular strategies are used to
maintain exciton emission in the solid-state and to avoid
quenching configurations.[12] The aliphatic side-chains of polyfluorenes, many of which are liquid-crystalline, act as spacers
reducing intermolecular forces of attraction due to steric effects. This can result in high solid-state PL quantum efficiencies; up to 60 %. PL quenching can also be avoided by energy
and charge transfer from a host to fluorescent or phosphorescent dopants. In this section we discuss linear and circular
polarized emission and show how liquid crystallinity can improve the output-coupling of OLEDs to improve the observed
brightness.
The luminescence properties of polyfluorenes have been recently reviewed by Neher.[59] He discusses strategies, e.g., endcapping of chains, for eliminating the unwanted excimer emission resulting from molecular rearrangements during OLED
operation. Many low-molar-mass LCs are luminescent,[37,6063]
but there has been very little effort to quantify their PL quantum efficiency. Time-resolved PL shows that the quantum efficiency of the fluorene-based reactive mesogen, diene 2, is limited not by aggregation or excimer formation, but by spatial
diffusion to traps.[64]
The polarization properties of the luminescence from LCs
have been more widely studied with the aim of maximizing
the linear or circular polarization ratio. Linear polarized emission requires uniform alignment and this is discussed in Section 5.2. Polarized EL is discussed in Section 6.1. The anisotropy of PL is given by Ipara/Iperp, where Ipara and Iperp are the
PL intensities parallel and perpendicular to the orientation direction, respectively. It depends on second, P2, and fourth,
P4, rank components of is the orientational order parameter.[65] Small molecules have a maximum P2 value of 0.7.
The elongated molecule diene 2 shows a PL anisotropy of
0.72.[66] Polymers, on the other hand, can have very high orientational order parameters, but the PL polarization ratio depends on the chain conformation. The recently developed oligomeric approach, which combines the high order parameters
of polymers with the monodispersity and solubility of small
molecules, presents an alternative, but chemically more challenging approach.[67,68] High orientation order parameters are
possible without the high-temperature LC phases or the coiled
conformations of polymers. Fluorene oligomers, for example
F(MB)10F(EH)2, show anisotropies of up to 18:1 in PL.[68] A
microcavity containing an aligned PFO samples is used to
spectrally separate the cavity modes for PL polarized parallel
and perpendicular to the alignment direction.[69] A polarization ratio > 300:1 is obtained for the most intense mode.
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F(MB)10F(EH)2: Tg123 C, LC > 375 C, I

Circularly polarized emission is characterized by the circular dissymmetry factor denoted by ge = 2(ILIR)/(IL+IR) where
IR(L) is the right-hand (left-hand) circularly polarized luminescence. There are two approaches to obtain circularly polarized
light from chiral nematic LCs. One exploits the photonic band
structure of chiral nematic LCs and will be discussed in Section 7. The other relies on coupling between the electric and
magnetic transition dipole moments. Normally the vectors are
orthogonal so no coupling can occur. Polyfluorene adopts a
helical configuration and intra-chain coupling between
twisted monomer units rotates the magnetic transition dipole
moment giving rise to partially circularly polarized emission.[70] The ge factor of 0.28 is low, but substantially greater
than that obtained by inter-chain coupling of PPV with chiral
side-groups.[71]
The external quantum efficiency of OLEDs is limited by total internal reflection which traps photons emitted at large angles to the normal of the device within the organic thin films
and substrate.[72] The total intensity coupled out of the device
increases by a factor of 1.6 when the emitters are aligned in
the plane compared with an isotropic orientation. This is a significant improvement in terms of device efficiency. Many lowmolar-mass calamitic LCs spontaneously adopt in-plane alignment in the nematic or smectic state and so can promote this
enhanced output coupling. The orientational order of calamitic LCs provides another advantage in guest-host systems
based on Frster energy transfer. This involves a dipoledipole interaction between an excited donor and ground-state
acceptor so that excitation is spatially transferred to the latter.
The rate of energy transfer is proportional to the orientational
factor for dipoledipole interaction. This is six times larger for
perfect parallel alignment of the donor and acceptor compared with a random alignment.[73] Calamitic LCs adopt a
roughly parallel configuration and should exhibit an enhanced
Frster transfer rate. Efficient energy transfer in a LC polymer guesthost system results in an extremely low threshold
fluence of 3 nJ cm2 per pulse for optically pumped lasing.[74]
A microcavity was used to provide feedback in the device.

5. Processing Issues for LC Thin Film Devices

Traditional liquid-crystal devices (LCDs) require materials,
which retain their fluid, low-viscosity liquid-crystalline phases
over a broad temperature range (e.g., from 35 C to 90 C).
The material is sandwiched in a thin cell, e.g., 5 lm, formed

http://www.advmat.de

Adv. Mater. 2003, 15, No. 14, July 17

between two supporting glass plates. OLEDs, photovoltaics,

and OFETs require alternative thin film device configuration,
such as those shown in Figures 3,6, with substantially thinner
active layers, < 100 nm. Solution processing to form organic
thin films is preferred because of its low-cost and compatibility with high through-put manufacturing processes. Long-term
device stability requires a solid thin film rather than a fluid
LC layer for robustness and to avoid liquid flow, inter-mixing
of layers and in-diffusion of the overlying electrode. Unfortunately, the presence of traps formed at crystal grain boundaries makes polycrystalline films impractical for such devices.
However, the processing of LCs is more complex than that of
amorphous glassy materials as additional uniform orientation
layers are also often required in order to take advantage of
their anisotropic transport and luminescence properties. We
now discuss how these issues are being resolved at the present
time.

from a crosslinked diene polymer network formed from the

reactive mesogen diene 2.[8,9] Figure 8 shows PL from a patterned polymer network.[77]

5.1. Towards Robust Room-Temperature Devices

The bright regions were selectively crosslinked by exposure

to UV radiation, the top pixel being only partially crosslinked.
The substrate was subsequently washed in chloroform to remove the non-irradiated material. The success of the photopolymerization approach requires minimal photodegradation of
the chromophores during crosslinking and no long-term damage from free radicals generated either by the initial irradiation or by subsequent breakdown of the photoinitiator. It is
too soon to evaluate but initial experiments on the diene polymer network, which was polymerized without the use of a
photoinitiator, show that the PL quantum efficiency is increased by crosslinking.[64] The hole mobility is doubled
following polymerization to a value of 3 105 cm2 V1 s1.[57]
Photopolymerized polymer networks have also been formed
from fluorene oligomers with acrylate end-groups.[67,9] Photocrosslinking does not require LC phases and a recent red
greenblue (RGB) EL device has been demonstrated based
on crosslinkable polymers.[78] However, calamitic LC phases
combine high mobility levels and polarized emission.
Temperature stability can also be achieved by designing a
liquid crystal glass with a high glass-transition temperature
(Tg). Glassy discotic phases and the related plastic columnar
phases have been obtained using polymeric triphenylenes,[38]
triphenylene dimers,[39] asymmetric triphenylenes, and intercalated triphenylenes.[43] Some unusual discotic thin film configurations have been considered. The hole mobility of a HAT
discotic is enhanced by gelation in a hydrogen-bonded fiber.
This is attributed to increased columnar order and suppression of the molecular fluctuations of LC by the gel. It is well
known that the EL threshold voltage of HAT glasses is reduced on annealing the devices.[38] This property is retained
with an improved surface morphology when they are dispersed in a polymer matrix.[79] Fluorene oligomers, for example F(MB)10F(EH)2, see above, which form a nematic glassy
phases with a high Tg, and a very high clearing point have also
recently been developed.[68]

The UV polymerization of small liquid crystalline molecules is a well-known technique to develop thermally stable
passive optical devices such as optical retarders,[75] and is an
extremely promising approach for OLEDs because it renders
the thin film insoluble so that multilayer devices are easily
formed and transport and recombination zones vertically defined. Figure 7 is an idealized illustration of an anisotropic
polymer network.

crosslink

spacer
chromaphore
spacer

Fig. 7. Schematic of a crosslinked polymer network.

Reactive mesogens are formed by attaching a polymerizable end-group via a flexible spacer to each end of a molecular core. Polymerization and crosslinking occur either by the
thermal or photoinduced generation of free radicals or by ionic photoinitation. Polymerizable acrylate end-groups were
added to a light-emitting phenylvinylene-containing molecule,
which was then aligned and thermally polymerized in the liquid-crystalline state by heating up to a temperature of
180 C.[76] Photopolymerization offers a further advantage of
pixellation by photolithography, and this approach was applied to OLEDs by the Hull group who demonstrated EL

Adv. Mater. 2003, 15, No. 14, July 17

http://www.advmat.de

Fig. 8. Photograph of blue PL from a patterned polymer network, irradiated

with UV light at 351 nm.

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PROGRESS REPORT

M. O'Neill, S. M. Kelly/Liquid Crystals for Charge Transport, Luminescence,

5.2. Uniform Alignment Techniques

Uniform alignment of LCs is required in many instances to
fully exploit the advantages of anisotropic transport properties and polarised luminescence. A variety of methods have
been used to achieve this. Rubbed alignment layers, e.g.,
doped polyimide[80] and partially converted PPV,[81] have been
used to obtain polarized EL. The performance of these devices is discussed in Section 6.1. However, the process of mechanical rubbing produces dust and scratching, which can be
expected to severely affect the performance of thin layer EL
devices. These problems are avoided completely when using
non-contact photoalignment techniques developed for LCDs
and adapted to OLEDs.[82] Illumination with polarized light
generates a surface anisotropy in the alignment layer and
hence a preferred in-plane orientation of the overlying LC
layer. An added advantage is that the polarization direction
of EL can be patterned photolithographically. Coumarin sidechain polymers, which undergo an anisotropic depletion by
2 + 2 cycloaddition on irradiation with polarized UV light,
were the first compounds to be used in a photoaligned polarized OLED.[8] They provide photochemically stable alignment
to reactive mesogens with strong azimuthal orientation. The
luminescent reactive mesogen, is deposited by spin-casting on
the already irradiated alignment layer and aligns parallel to
the polarization direction of the aligning UV light. Azobenzene polymers have also been used as photoalignment layers
and undergo anisotropic cistrans isomerization on irradiation
with polarized light. Normally the LC alignment is unstable
and the orientation direction can be reversed by subsequent
irradiation of the photoalignment polymer with orthogonally
polarized light. However, the original alignment direction of
an electroluminescent fluorene main-chain polymer is retained, albeit with a lower dichroic ratio, on reorientation of
the underlying alignment layer.[83] This implies that azobenzene polymers provide stable alignment for polymers with
high Tgs.
There has been a great effort made to achieve the uniform
orientation of discotic LCs. Homeotropic alignment is required for OLEDs and photovoltaic devices with the columnar discs parallel to the substrate so that the molecular wires
conduct between the top and bottom electrodes. Solution processing often give homogenous or tilted homeotropic alignment, as illustrated in Figure 2, with tilt disclinations between
the domains.[41] Annealing is used to improve molecular ordering and promote non-tilted homeotropic orientation. In
contrast OFET operation requires high in-plane mobilities
and recent developments in the uniaxial in-plane alignment of
discotic LCs predict promising developments in this application area. Oriented poly(tetrafluoroethylene) (PTFE) films
obtained by friction transfer can act as a template for expitaxial growth. Uniaxial orientation of a triphenylene-based discotic LC, which is a glass at room temperature, was obtained
by spin-coating onto an oriented PTFE film on glass.[84] Improved ordering was obtained by annealing above the Tg.

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Drop-casting with slow evaporation was used to uniaxially orient HBCPhC12, with a LC phase at room temperature, and
slow solvent evaporation in a sandwich cell enabled epitaxial
growth of a room-temperature crystalline hexabenzocoronene
on PTFE.[85] OFET mobilities of up to 1 103cm2 V1 s1 were
obtained from the latter, significantly smaller than typical values obtained using a microwave conductivity technique.[40] A
similar crystalline coronene was zone cast through a nozzle
onto a moving untreated glass substrate.[86] This allowed selfassembly of the molecules into uniaxially oriented columns
over large areas without using a PTFE layer.

6. Recent Developments in LC OLEDS,

Photovoltaics, and OFETs
6.1. OLEDs
There is a lot of interest in the use of OLEDs with linearly
polarized emission for use as backlights for brighter, more efficient LCDs. This would remove the need for polarizers and
color filters and so improve the power consumption of the display. The use of uniformly oriented LCs for polarized EL was
reviewed in 1999,[87] and we discuss only developments since
then. At that stage 15:1 was the best polarization ratio,
(D = Ipara:Iperp) obtained for EL.[80] This was achieved using a
LC polyfluorene aligned on a rubbed polyimide alignment
layer doped with a hole-transporting small molecule (triarylamine). Since then a higher ratio of 25:1 and a brightness of
250 cd m2 was obtained using a similar polyfluorene oriented
on a thin PPV substrate, which was rubbed when partially
converted from its precursor.[81] However, photoalignment
gives the additional option of spatially patterning the polarization direction as demonstrated by Sainova et al., who report Ipara:Iperp of 14:1 from uniformly oriented polyfluorene
on an azobenzene-based photoalignment layer.[83] An efficiency of 0.66 cd A1 was obtained at 8 V using an ultrathin
alignment layer, although with a lower polarization ratio.[88]
The disadvantage of the polymer approach is that high temperature annealing ( 200 C) is required to align the polymer
in the LC state before rapid quenching to prevent crystallization by forming the glassy state. Low-molar-mass LCs are potentially an attractive alternative to polymers due to the lower
processing temperatures and spontaneous alignment. Indeed
there are a few reports of polarized EL from small molecules.
An anisotropic polymer network formed by the photopolymerization of diene 2 on a doped photoalignment layer gives
an EL polarization ratio of 11:1, limited by the order parameter of small molecules.[8] Fluorene oligomers, such as the
fluorene pentamer shown below, which are liquid-crystalline
at room temperature, were aligned on a thin rubbed PPV
alignment layer and subsequently crosslinked to form a polymer network.[67] A D ratio of 22:1 is obtained for some of
these materials in EL but there is some broad excimer or exciplex emission.

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PROGRESS REPORT

M. O'Neill, S. M. Kelly/Liquid Crystals for Charge Transport, Luminescence,

H7C3 C3H7
OC6H12O2CCH=CH2
2

H2C=CHCO2C6H12O
2

Fluorene pentamer: tg 10 C, N 123 C, I

As discussed in Section 5.1, the formation of polymer networks allows the solution processing of multilayer devices.
Promising preliminary results have been obtained by Contoret et al. who compared the spectra of EL devices consisting of
a hole-transporting/luminescent polymer network with and
without an overlying electron-transporting polymer.[9,77] As
Figure 9 shows, the spectra are almost identical indicating that
EL comes from the same layer in each case. The small shifts
in the wavelength of the vibronic bands results from slightly
different environments in the two and three layer device.

EL Intensity

(b)

(a)

400

500

600

Wavelength (nm)
Fig. 9. Electroluminescence spectrum from a polymer network of diene 2,
a) without and b) with an overlying electron-transport layer.

Multilayer OLEDs based on columnar discotics deposited

by LangmuirBlodgett techniques were first reported in the
1990s.[89,90] An all-columnar bilayer light-emitting diode was
produced by sequential thermal evaporation of HAT and an
electron-deficient perylene-based discotic.[91] Both materials
have LC phases at elevated temperatures and a columnar
packing is retained in the crystalline phase at room temperature. Low luminance but promising lifetimes were shown.

respectively. External quantum efficiencies of up to 34 % and

power efficiencies of 2 % were obtained in photodiode configurations.

6.3. Transistors
The first application of LCs to OFETs exploits the high 1D
carrier transport properties of oriented liquid-crystalline polyfluorene block polymers.[93] The source and drain electrodes
are deposited onto a rubbed polyimide alignment layer. The
polyfluorene and gate electrode are then deposited in sequence. A FET mobility of up to 2 102 cm2 V1 s1 is obtained only when the quenched polyfluorene glass is oriented
along the transport direction between the source and drain.
This shows that the rate of intra-chain transport of holes is
very much greater than the hopping rate between chains:
aligning the chains along the channel minimizes the number
of inter-chain hops.

7. Chiral Nematic LCs for Distributed Feedback

Lasers
The vivid colors observed in reflection from uniform
aligned chiral nematic LCs result from their spontaneous selfassembly: the director is continuously rotated to form a helical
structure, as shown in Figure 10. The LC is birefringent so
that the formation of the helix gives a periodic modulation of
refractive index establishing a 1D photonic stop band. This

6.2. Photovoltaics

A recent breakthrough shows conclusively that discotics

make efficient photovoltaics. A 1:1 blend of the room-temperature discotic HBCPhC12 and a crystalline perylene dye was
deposited by spin-coating.[7,92] The components were vertically segregated by evaporation of the solvent to produce a
thin film with a perylene-rich surface layer overlying a coronene-rich layer. This spontaneous self-assembly gives a distributed interface which provides ideal conditions for separation of electrons and holes into the top and lower layers

Adv. Mater. 2003, 15, No. 14, July 17

http://www.advmat.de

n
n

pitch, p
n

Fig. 10. Helical structure formed from uniformly aligned chiral nematic LCs.

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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M. O'Neill, S. M. Kelly/Liquid Crystals for Charge Transport, Luminescence,

forbids the propagation, along the helical axis, of circularly

polarized light having the same handedness as the helix and
over the wavelength range DkR ~ DnkR/n. The stop band is
centered at kR = np, with the pitch, p, defined in Figure 10 Dn
is the birefringence and n, the average refractive index,
= ((n 02 + ne2)/2)1/2. Low-cost temperature sensors, in which p is
temperature-dependent, have been widely available for many
years. More recently the photonic properties of chiral LCs
have been applied to light-emitting materials where the PL
spectrum matches the stop band. Highly circularly polarized
PL has been obtained,[94] and low threshold mirrorless lasing
has been reported.[10] We discuss developments in both these
areas.
A quantitative description of luminescence in the stop band
spectral region has recently been given.[95] According to Fermi's Golden Rule, the rate of spontaneous emission is proportional to the density of photon states (DOS) in the medium.
For a very thick film with a right-handed helix, the DOS of
right-hand circularly polarized light is zero in the stop band
and diverges at the edges. Hence spontaneous emission in the
stop band is left-hand circularly polarized. For a thin film,
multiple reflections between the front and back interfaces of
the film result in FabryPerot-like peaks at resonant wavelengths near the stop band edge. At these resonant wavelengths the intensity of right-hand circularly polarized PL is
enhanced so that the sign of ge is reversed at the stop band
edge. The group velocity is inversely proportional to the DOS
so that these emitted photons have a long dwell time through
the film. This increases the probability of stimulated emission
so that the 1D photonic bandgap structure can be used as a
mirrorless laser resonator.
Chen et al. report circularly polarized PL from a dye doped
in the noncalamitic chiral nematic glass GLC.[94] A ge value
approaching 1.8 is obtained over a limited range of the emission spectrum. Commercially available chiral nematic mixtures were subsequently used to obtain circularly polarized
PL in a similar guesthost configuration.[96] A maximum ge
value of 1.3 was obtained from a luminescent chiral nematic
poly(para-phenylene).[97] In all the above cases the PL linewidth is greater than the spectral width of the stop band, and
the low average ge results from the reversal in the sign of ge at
the edges of the stop band.[10,96] Two alternative methods have
been used to improve the wavelength dependence of ge. A
chiral nematic film with a graded pitch was prepared to give a
stop band from about 370 nm to 580 nm and a maximum ge
value 1.4.[98] Alternatively PL from a dye with a narrow
spectral width gives a virtually wavelength-independent ge
with a maximum value of 1.27.[99]
Lasing in chiral nematic LCs was first proposed in 1973,[100]
and fifteen years later was demonstrated at the stop band
edge of a dye-doped chiral nematic LC.[10] Since then rapid
progress has been made in a wide range of systems, including
lyotropic and ferroelectric LCs.[101,102] The wavelength of laser
emission was tuned by mechanical deformation of a dyedoped elastomer.[103] Elsewhere an applied electric field was
used to shift the stop band edge in a chiral nematic LC and

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2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

hence tune the laser wavelength.[104] Improved temperature

stability was obtained using a photopolymerized chiral nematic polymer network,[105] which forms a solid film removable from the substrate.[106] The first observation of lasing in a
three dimensional (3D) photonic crystal was made in the blue
phase of a chiral-nematic LC.[107] All the above lasers use a
guesthost configuration in which the dye guest is directly excited by an optical pulse. Lasing, albeit with a high threshold,
is demonstrated in an undoped chiral nematic LC.[108] Frster
energy transfer is also used to indirectly excite a dye in a twodye-doped chiral nematic LC.[109,110]
Distributed feedback lasers fabricated from layered dielectrics have been well known for many years.[111] What advantages do chiral nematic resonator have apart from spontaneous self-assembly of the resonator structure? The electric
field of the resonator modes at the band-edges has the same
helicity as the chiral medium. This means that there is optimized coupling with the transition dipole moment of an anisotropic emitter whose orientation follows the helix.[112] It is difficult to compare the threshold fluence for the different
systems discussed above, since, in many cases, the excitation
beam size is not defined. However, all systems are pumped
with high-energy pulsed lasers. Kopp et al. propose a new
mode of operation for lasing.[113,114] The defect mode results
from a phase discontinuity at the interface between two chiral
helical structures, and results in lasing in the center of the
bandedge. Hence, it is analogous to the distributed Bragg reflection laser, well known in semiconductors. The threshold
fluence for lasing is substantially lower for this mode than for
the bandedge lasing.[115]
R2
R1
R1
O
R1 = CO2C2H4O
O

OCH3

H
N *

R1 = CO2C2H4O
O

CH3
O

GLC 1: Tg 77 C, N* 147 C, I

8. Discussion and Conclusions

The application of LCs to conducting optoelectronic and
photonic devices is a relatively new area of research so, although many exciting and potentially significant initial approaches have been described above, the full potential of
hybrid or fully LC devices is not yet fully realized. Although
many fundamental issues have yet to be investigated and under-

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Adv. Mater. 2003, 15, No. 14, July 17

stood, the major limiting factor in our judgement may be nonoptimal LC morphology. Here, we summarize what we believe
are the potential benefits and challenges of using different
classes of LCs in electronic devices other than LCDs. Discshaped LCs show high mobility resulting from enhanced molecular order when the discs self-organize into 1D columns. These
intrinsic advantages can be realized in real devices as demonstrated in very recent breakthroughs in photovoltaics and
OFETs. However, the materials used do not possess an optimal
morphology: they are either crystalline or liquid-crystalline at
room temperature. This leads to trapping at crystal grain boundaries and layer flow, respectively. A possible solution to improved performance is to use glassy, plastic or more sophisticated crosslinked columnar films. Increasing the size of the
crystalline grains is another option. Self-organized electronand hole-conducting channels remain a vision potentially to be
realized using new supramolecular dendritic structures.[116]
The in-plane spontaneous alignment of rod-like LCs gives
higher output-coupling efficiencies as well as anisotropic
transport for OLEDs. Their lower mobilities compared to discotics is not a major disadvantage for OLEDs, where the
balance of electrons and hole densities is more important. We
have shown that highly efficient OLEDs require multiple
layers or at least vertical segregation. The lithographic formation of nematic polymer networks is a promising approach for
this and has the added advantage of photopatternability for
pixel formation. Devices have been demonstrated, but more
research is required to improve the performance of these
OLEDs and to ascertain long-term photochemical stability.
New strategies in the molecular design of smectic LCs are required to lower the melting point and clearing point of the
smectic phases. Other challenges are to extend the color range
and efficiency of LC emitters. Improved alignment layers are
also essential components for many applications: alignment
layers with high hole mobility are required for more efficient
polarized EL; the formation of a well ordered interface for
OFETs requires an alternative to rubbed or friction-transferred alignment layers.
The application to mirrorless lasing of 1D photonic bandgap
structures using chiral LCs has intrigued many scientists and a
wide range of systems have been investigated. Many issues
must be resolved if the phenomenon is not to remain a laboratory curiosity. The threshold fluence for lasing remains high
but there is a lot of scope to reduce this, for example, by operating in the defect mode configuration. So far optical pumping
has been exclusively used and electrically pumped lasing in
chiral systems would indeed be a major breakthrough.

[1]
[2]
[3]
[4]
[5]

Received: February 7, 2003

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[117] The abbreviations used for the phases are defined in Table 1.

Table 1. Abbreviations used for phases describing the compounds presented as

structures.
Phase

Abbreviation

Columnar
(hexagonal ordered)
Crystalline
Isotropic
Liquid-crystalline
Nematic
Chiral nematic
Smectic A
Smectic B
Smectic C
Smectic F
Smectic G

Colho
Cr
I
LC
N
N*
SmA
SmB
SmC
SmF
SmG

______________________

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Adv. Mater. 2003, 15, No. 14, July 17