Molecular and Polymer Semiconductors,
(1948), who observed the conductivity and photo-
Conductors, and Superconductors:
Overview
Conducting and semiconducting polymers have
emerged as efficient materials for electronic appli-
cations and have helped to open up the era of plastic
electronics. This was recognized in 2000, twenty years
after their discovery, by the award of the Nobel Prize
for Chemistry to their inventors, Heeger, McDiarmid,
and Shirakawa. In contrast to saturated polymers,
conducting polymers find their electrical and optical
activity in the conjugation of π-electrons along the
polymeric carbon backbone. What makes electrically
active polymers and other organic solids attractive for
a wide range of applications is the unique combination
of the electronic properties of metals and semi-
conductors and the mechanical plasticity of con-
ventional polymers. ‘‘Metallic’’ conducting polymers
can be used, for example, as protective coatings against
metal corrosion or as electromagnetic interference
shieldings: semiconducting polymers find applications
in light-emitting diodes, field-effect transistors, and
photovoltaic solar cells. Finally, superconductivity
has been observed at relatively ‘‘high’’ temperatures
in some organic charge transfer salts.
1. Brief History
The story of inventions is paved with milestones, some
of which are seen as essential breakthroughs while
others remain forgotten. A good example is provided
by microelectronics, one of the today’s major tech-
nologies. Almost everyone involved in this field recog-
nizes the invention of the transistor in 1947 as the
starting point; this was acknowledged by the award of
the Nobel Prize to its inventors. But the transistor
would probably not have been conceived without the
disclosure of the triode by Lee de Forrest 50 years
earlier. However, apart from a handful of specialists,
who remembers Lee de Forrest today?
Electrically conducting polymers provide a similar
story. Their discovery dates back to the synthesis of
polyacetylene (PA) by Shirakawa et al. (1977) and
their observation that chemical doping allowed it to
conduct electricity almost as well as a metal, with
conductivities as high as 10& S cm−". This was the start
of the contemporary generation of conducting ‘‘plas-
tics’’. A conducting polymer is now used as an
antistatic coating in photographic films, while poly( p-
phenylenevinylene) (PPV) is used to fabricate light-
emitting diodes (a second commercial application of
conjugated polymers). But again, evidence of electrical
conduction in organic solids and polymers can be
traced back several decades to when a number of
molecular and polymeric conductors were identified.
The first molecular conductor was described by Eley
conductivity of copper phthalocyanine. Two groups
of compounds emerged in the 1950s and 1960s, namely
covalent conjugated polymers (such as substituted
polyacetylenes) and low molecular charge transfer
complexes (e.g., derivatives of tetracyanoquinodi-
methane [TCNQ]). A number of monographs and
reviews that appeared in the 1960s testify to this
early but intense activity (Kallmann and Silver 1961,
Rembaum et al. 1965, Katon 1968).
The lesson from both stories is that materials are the
key factor in most technological breakthroughs. The
transistor had to wait until highly pure, single crystals
of germanium, and then silicon, were produced.
Similarly, organic light-emitting diodes could not be
developed before good quality, conjugated polymers
had been synthesized.
This brief historical introduction would not be
complete without mentioning that, as early as 1964,
the theoretical possibility of superconductivity in
polymers had been evaluated (Little 1964). A model
consisting of a polyene chain with cyanine dye substit-
uents was suggested and it was even inferred that
superconduction could occur at room temperature.
Although superconductivity in polymers has not yet
been observed, the first organic superconductor was
discovered in 1980 on a charge transfer salt (Je! ro# me et
al. 1980. These salts and others such as alkali-metal
doped fullerenes and transition metal complexes of the
type M(dmit) (where dmit l isotrithionedithiolate
and M l Ni, # Pd, Pt) can be superconducting at
relatively high temperatures (up to Tc l 10 K). Or-
ganic superconductors have been reviewed by Kresin
and Little (1990) and Williams et al. (1992).
Conducting polymers in their doped form are now
targeted for bulk applications such as antistatic
coatings, shielding materials against electromagnetic
interference (EMI), materials for rechargeable bat-
teries, capacitors and supercapacitors, electrochromic
devices (‘‘smart windows’’), and a variety of elec-
trochemical sensors. Semiconducting polymers and
oligomers can be used in more ‘‘high-tech’’ devices
such as light-emitting diodes (LEDs), field-effect tran-
sistors FETs (see Field Effect Transistors with Semi-
conducting Polymers and Thin-film Transistors From
Organic Semiconducting Materials, Processing Tech-
nologies for), photovoltaic solar cells (PhotoŠoltaic
DeŠices from Organic Semiconductors), and solid state
injection lasers (Molecular Organic Semiconducting
Single Crystals: Fundamental Properties and Appli-
cations). Organic LEDs can find applications in
display technologies (Light Emitting Diodes from
Molecular and Polymer Semiconductors) and organic
FETs in low-end data storage such as identification
tags, smart cards and complementary logic circuits
(Thin-film Transistors From Organic Semiconducting
Materials, Processing Technologies for).
1
Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
Semiconductors
Figure 1
Comparative electrical conductivities of conjugated polymers and other materials.
2. Electrically Conducting Polymers
The electrical properties of materials are determined
by their electronic structure. The comparative con-
ductivities of conjugated polymers and various other
materials are shown in Fig. 1. Note that the con-
ductivity of polymers (including molecular ‘‘conduc-
tors’’) span the metallic and semiconducting ranges.
The metallic conductivity of conjugated polymers is
due to the delocalization of π-electrons along the
carbon backbone. The molecular structures of some
important conducting polymers are shown in Fig. 2.
These linear and planar polymers are constituted by a
number of sp# carbon atoms covalently linked to each
other by alternating single and double bonds; the
classic example being PA, i.e., (CH)n. Three electrons
on each carbon atom are in σ-bonding orbitals, while
the fourth one resides in a delocalized pz-orbital. The
pz-orbitals of neighboring carbons overlap to form π-
bands extending all along the linear polymer chains—
thus providing a one-dimensional delocalized system.
The highest occupied molecular orbitals (HOMO)
constitute the (filled) π-bands, while the lowest un-
occupied molecular orbitals (LUMO) constitute the
(empty) π*-bands. The energy difference between the π-
and π*-bands is called the band gap energy, Eg.
2.1 Doping
However, in their neutral form, conjugated polymers
are semiconducting (see Sect. 3). The cis conformation
of neutral PA is a copper-colored flexible film with a
conductivity of 1.7i10−( S m−". This turns to a silvery
trans form with a conductivity of 4.4i10−$ S m−" upon
heating above 150 mC. To confer metallic conduction,
it is necessary to oxidize or reduce them; a chemical
process called ‘‘doping’’ by analogy with inorganic
semiconductors. At low doping levels, partial band
filling induces conductivity, while sufficiently high
doping levels lead to a transition from insulator to
metal. For example, Shirakawa et al. (1977) showed
that after chemical oxidation (or p-doping) of PA by
2
Metallic conductors
Graphite
bromine or iodine vapors (Eqn. (1)) its conductivity
increases by nine orders of magnitude up to 10& S m−".
In comparison, the conductivity of copper is 10) S m−",
while that of silicon is 10−$ S m−" and that of Teflon is
10−"' S m−". Reductive doping (n-doping) of PA by an
alkali metal like sodium is also possible (Eqn. (2)), and
also leads to metallic conduction:
(CH)nj3x\2 I (CH)x+ jxI− (1)
# n $
(CH)njxNa (CH)x−n
jxNa+ (2)
However, although chemical doping is an efficient and
straightforward charge transfer process, it is difficult
to control and inhomogeneous doping often results.
Electrochemical doping allows precise control of the
doping level by the applied voltage and leads to an
homogeneous distribution of dopants in the bulk. In
electrochemical doping, the working electrode supplies
the redox charge to the polymer while ions contained
in the electrolyte diffuse inside the polymer to com-
pensate the charge. Equation (3) shows the electro-
chemical p-doping of polythiophene (PT) by lithium
tetrafluoroborate (LiBF ):
%
PTjn (Li+, BF−) (PTn+, nBF−)jnLi! (3)
% %
Doping, i.e., introduction of a certain amount of
positive or negative charge on the polymer chains,
results in a profound modification of their electronic
structure. Besides the changes in electrical conductivity,
the optical absorption spectrum is spectacularly modi-
fied upon doping. As can be seen in Fig. 3, doping of
trans-PA induces the emergence of a new band at low
energy (0.7 eV) and an intensity decrease of the π–π*
band at 1.7 eV. This can be explained by the formation
of localized states within the band gap due to the
addition to or removal of electrons from the polymer
by the dopant. If, for example, an electron is removed
from the valence band of PA on oxidative doping by
iodine, the resulting ‘‘hole’’ can be compared to a
radical cation associated with a local deformation of the
neutral chain’s geometry. This so-called ‘‘polaron’’
 Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
Figure 2
Chemical structures of some important conducting polymers.
can then migrate along the chain with a high mobility,
which is reduced by Coulomb interactions with the
counterion. Doping of conjugated polymers can create
a variety of charged or neutral defects responsible
for conductivity and other modifications (polarons,
bipolarons, solitons).
All these observations about doping show that the
description of conjugated polymers in simple terms of
energy bands is incomplete. They imply that the
electron–lattice and electron–electron interactions
must be included for an accurate treatment of the
electronic structure of these macromolecular systems.
Disorder in particular is responsible for localization
of electronic states and broadening of the optical
transitions. On the other hand, conjugated polymers
are characterized by a strong coupling between elec-
tronic and chemical structures, leading to lattice
relaxation around electrons and holes. Finally, the
Coulomb attraction between electrons and holes in the
π and π*-bands causes the formation of ‘‘excitons,’’
3
Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
trans –(CH) x
E (eV)
Figure 3
Absorption spectra of neutral and lightly doped trans-
polyacetylene (CH)n showing the emergence of the soliton
band at 0.7 eV and the concomitant decrease of the
fundamental absorption in the visible absorption.
(Reproduced by permission of American Physical Society
from Phys. ReŠ. Lett., 1980, 45, 1209.)
which are neutral bound electron–hole pairs. The
nature and fate of these excitons are of primary
importance in understanding the fundamental physics
of conjugated polymers. Among the many questions
still under intense debate is that of the magnitude of
the exciton binding energy and the role of excitons in
photoconductivity (see Excitonic Model Šersus Band
Gap Model in Organic Materials: Theory).
Doping, i.e., the introduction of charges on the
polymer chains, can also be achieved by photo-
excitation through the creation of an electron–hole
pair and separation into free carriers of both signs.
Consequently, photoconductivity is not permanent (as
is chemical or electrochemical doping) and only lasts
the time of decay back to the ground state. Finally,
electrons and holes can also be injected from metallic
contacts (electrodes) into the π- and π*-bands of
conjugated polymers, respectively. In this doping
process, injected charges are not compensated by
charges of the opposite sign, in other words there are
no counterions. Again, doping is transient and persists
as long as the biasing voltage is applied.
2.2 Structural Anisotropy
Another important feature of conducting polymers is
their structural anisotropy. Unlike diamond, which
contains only sigma bonds and is therefore insulating,
conjugated polymers are constituted of (quasi) one-
dimensional chains with highly anisotropic properties.
4
(a)
(b)
Figure 4
Two examples of functional conducting polymers.
However, if these chains are randomly distributed in a
highly disordered material, conductivity is isotropic. If
the chains are aligned at the macroscopic level (by
mechanical or stretching orientation), conductivity
turns out to be highly anisotropic. In the case of a
polyaniline film, for example, conductivity increases in
the stretching direction while it decreases in the
perpendicular direction. Anisotropies of a few tens are
typically obtained for a stretching of 300–500%
(Travers 2000).
2.3 Functional Polymers
In addition to electrical conductivity, it is possible to
functionalize conducting polymers by introducing a
covalently bound functional group to their conjugated
backbone. Functional conducting polymers thus open
the way to various technological applications such as
energy storage, electrochromism, electrocatalysis, and
chemical sensors for various chemical species from
ions to biomolecules (see Chemical and Biological
Sensors from Conducting and Semiconducting Poly-
mers). Figure 4 shows two examples of functional
conducting polymers.
The main synthetic strategy consists of preparing a
functional monomer, i.e., a monomer bearing a
chemical function (on a free position) which is then
polymerized either chemically or electrochemically.
Electrochemical polymerization is often used as it
offers several advantages over chemical methods
(Roncali 1999). Electropolymerization is a simple and
 Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
Figure 5
Two well-known molecular organic semiconductors.
straightforward technique for preparing modified
electrodes in which the conductivity of the conjugated
polymer is associated with the specific property of the
functional group. As well as simple alkyl or alkoxy
chains (to induce solubility), a large number of more
complex functional groups have been grafted on
conjugated polymers, e.g., crown ethers, chromo-
phores and fluorophores (see Conjugated Oligomers
and Polymers, Synthesis of), metal-containing groups,
C fullerenes, tetrathiafulvalenes (TTF) (Bryce 2000),
'! nucleobases or oligonucleotides (see Chemical and
and
Biological Sensors from Conducting and Semi-
conducting Polymers).
Parallel to the molecular design of new functional
polymers, the past few years have seen an intense
activity in the quest for low band gap conjugated
polymers. Reduction of the band gap would indeed
lead to true ‘‘organic metals’’ that showed intrinsic
conductivity without having to be doped.
2.4 Processability and Applications
Conducting polymers show a remarkably wide range
of electronic phenomena and can consequently be
used in a large number of specific applications. For
most of these applications, the key property is proces-
sability. Early conducting polymers were intractable
(insoluble and infusible), but also chemically unstable
in open air conditions (dedoping, decomposition),
rendering them inappropriate for applications. Vari-
ous routes have been tested to induce solubility in
common organic solvents and water. One of the most
successful approaches consists of grafting long and
flexible aliphatic chains onto the conjugated polymer
backbone. Two examples based on poly(3-hexylthio-
phene) and poly(2,5-alkoxy)-p-phenylenevinylene
(MEH-PPV) are shown in Fig. 5. Introduction of
bulky substituents may, nevertheless, be detrimental
to conductivity due to the loss of planarity and
subsequent decrease of π-conjugation.
The main interest in using solution-processible
conducting polymers is in low-cost manufacturing.
Thin-film coatings can easily and rapidly be prepared
by casting from solution or electrochemically. Appli-
cations can then be found in large-area coatings and
also in microelectronics, where integrated circuits or
display devices can be manufactured using simple
inkjet printing techniques.
For example, acid-doped poly(3,4-ethylenedioxy-
thiophene-2,5-diyl) (PEDOT) has been used to produce
transparent, abrasion-resistant and noncorrosive
antistatic coatings for photographic films. Conduct-
ing PEDOT is now used commercially and also
serves as a hole-injecting material in polymer-based
light-emitting diodes (see Sect. 3.1). PEDOT can also
be used to fabricate (multicolor) electrochromic
devices (‘‘smart windows’’ absorbing sunlight and
turning transparent in cloudy weather), where the
polymer switches between two forms that have dif-
ferent colors. Doped polyaniline is used for electro-
magnetic shielding of electronic circuits and as a
corrosion inhibitor. Polypyrrole (PPy) is considered
suitable as a microwave-absorbing material for
‘‘stealth’’ screen coatings. A number of conducting
polymers—mainly PT and PPy derivatives—are used
in various chemical and biological sensors (see
McQuade et al. 2000, Chemical and Biological Sensors
from Conducting and Semiconducting Polymers, and
Chemical Sensors for Mine Detection from Conducting
and Semiconducting Polymers). Other potential appli-
cations include resists, recording materials, fabri-
cation of patterns, and materials for rechargeable
batteries (see Organic Electrolytes and Electrodes
for Batteries), supercapacitors (essentially as power
storage devices), and electrolytic capacitors.
Generally, the combination of electrical conduc-
tivity and mechanical flexibility with low-cost manu-
facturing should, in a near future, lead to conjugated
polymers invading our daily life. Antistatic textiles
and paintings, smart windows, large electrostatic
loudspeakers, antennas for satellites reception, and
domestic sensors are just a few examples of what
conducting polymers could do in our homes.
3. Molecular and Polymeric Semiconductors
The discovery that doping PA raised its electrical
conductivity to a magnitude close to that of a metal
has remained the prominent property of conjugated
polymers. Hence their most popular name—‘‘con-
ducting’’ polymers. However, in 1990 it was found
that ‘‘undoped’’ (more accurately, non-intentionally
doped) conjugated polymers, which are semiconduct-
ing rather than conducting, could be used as the active
component in electronic devices such as LEDs (see
Light Emitting Diodes from Molecular and Polymer
Semiconductors), FETs (see Thin-film Transistors
5
Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
Figure 6
Operating mode of an organic light-emitting diode.
From Organic Semiconducting Materials, Processing
Technologies for and Field Effect Transistors with
Semiconducting Polymers). At present, ‘‘organic
electronics’’ is probably the major research topic
involving semiconducting polymers (Hadziioannou
and Van Hutten 2000). This research area also includes
conjugated oligomers and other small conjugated
molecules (Mu$ llen and Wegner 1998, Fichou 1999).
This suggests that the popular terminology ‘‘plastic
electronics’’ should sometimes be avoided.
3.1 Light-emitting Diodes
Electroluminescence (EL) in organic materials was
first discovered by Helfrich and Schneider (1965)
in anthracene single crystals. The origin of light
electrogeneration in organic semiconductors is under
discussion. However, the most accepted mechanism
remains the one developed at that time.
As shown in Fig. 6, an organic light-emitting diode
(OLED) consists of a luminescent organic layer
sandwiched between an electron-injecting cathode and
a hole-injecting anode. The anode and cathode are
made of high work function and low work function
conductors, respectively. Two important features dif-
ferentiate organic compounds from their conventional
inorganic counterparts. First, because doping levels
are very low in organic materials, a double injection of
electrons and holes is required (only minority carriers
need to be injected in inorganic devices). Second, the
recombination of electrons and holes does not directly
lead to light emission. Instead it gives birth to an
exciton (an excited molecule), which in turn may emit
light while deactivating to the ground state. The
exciton is characterized by its binding energy. The
higher the binding energy, the more the exciton is
localized. The magnitude of the exciton binding energy
is at the core of controversies on EL mechanisms in
organic LEDs (Sariciftci 1997). The ‘‘molecular’’
school claims a binding energy of around 0.5 eV,
which corresponds to an exciton localized on a single
6
molecule (a so-called ‘‘Frenkel’’ exciton). The ‘‘semi-
conductor’’ school opts for a significantly lower
binding energy, leading to a more ‘‘delocalized’’
(‘‘Wannier-Mott’’) exciton; a picture that puts organic
semiconductors close to their inorganic counterparts.
The Frenkel exciton model gives rise to an important
characteristic of organic LEDs. Because the spin of
injected charges is randomly distributed, the ratio of
generated excitons should be three triplets to one
singlet. As the ground state of most organic molecules
is singlet, the deactivation of triplet excitons is spin-
forbidden. Triplet excitons therefore have a long life
and are more likely to deactivate nonradiatively rather
than emit light. Accordingly, the quantum yield of
OLEDs (that is, the ratio of emitted photons to
injected charges) is expected to be limited to 25%.
Reports on organic devices with quantum yields in
excess of this theoretical limit have been taken as
evidence for a mechanism of direct recombination of
electrons and holes, as in conventional inorganic
semiconductors. However, quantum chemistry calcu-
lations show that, unlike the prediction from a simple
statistical picture, the recombination cross-section
tends to favor the formation of singlet excitons (see
Quantum Mechanical Simulations of Organic Mate-
rials).
As OLEDs are made of very thin layers (their total
thickness is around 100 nm), high carrier mobility is
not necessarily required. However, a balance between
electron and hole flux is desired for efficient electron–
hole recombination. It is recognized that electron
injection is the main limiting step in the sequence of
events that leads to electroluminescence. Tang and
Van Slyke (1987) showed that the performance of
OLEDs could be significantly improved by using a
double-layer device made of an electron-transporting
layer (ETL) next to the cathode and a hole-transport-
ing layer (HTL) next to the anode. Current OLEDs,
particularly those made with small molecules, may
include up to four different organic layers.
Finally it should be noted that two transistors built
on either sides of a lamellar pentacene single crystal
have allowed the first ever organic solid state injection
laser to be achieved (see Molecular and Polymer
Semiconductors, Conductors, and Superconductors:
OŠerŠiew). This breakthrough comes after optically-
driven amplified spontaneous emission and lasing have
been demonstrated in various conjugated polymers and
oligomers (see Laser DeŠices from Molecular and
Polymer Semiconductors).
3.2 Field-effect Transistors
Organic field effect transistors (OFETs) emerged in
the late 1980s (Burroughes et al. 1988, Horowitz et al.
1989) almost simultaneously with OLEDs. Owing to
their limited performance, OFETs are far from com-
peting with silicon-based microelectronics. However,
 Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview

Figure 7
Schematic diagram of a thin-film transistor. Figure 8
Molecules typically used for deposition.
single crystalline silicon is an expensive and brittle
deposition and increasing the temperature of the
material. Commercial applications of OFETs can
substrate. Current mobility in vacuum-evaporated
therefore be envisioned in fields where low cost is
OFETs ranges between 0.1 cm# V−" s−" and
crucial, e.g., smart cards and electronic bar codes. In
1 cm# V−" s−". This makes the devices competitive with
addition, organic electronics will probably find their
amorphous silicon transistors. Even higher mobility
way into devices built on soft polymeric substrates.
has been measured in OFETs built on individual
For example, applications like soft displays or an
organic single crystals such as pentacene (see Mole-
‘‘electronic book’’ made of rewritable pages would
cular Organic Semiconducting Single Crystals: Fund-
constitute an attractive alternative to current com-
amental Properties and Applications) and sexithio-
puter displays.
phene (see Field Effect Transistors with Semiconducting
Organic transistors are built according to a thin-film
Polymers). The impact of the structural order of
architecture (a schematic view is shown in Fig. 7). A
oligothiophenes on the performances of transistors
field effect transistor is essentially a capacitor where
(and other optoelectronic devices) is reviewed by
one of the plates has been replaced by a semi-
Fichou (2000). A model developed for polycrystalline-
conducting layer. The other plate constitutes the gate
evaporated devices showed that charge transport in
electrode. The semiconducting film is equipped with
most OFETs is actually limited by carrier hopping
two electrodes—the source and the drain—separated
between grains (Horowitz and Hajlaoui 2000). The
by a distance, L, wherein lies the conducting channel
model predicts that carrier mobility should improve
of the device. When a bias is applied between the
with increasing grain size, a behavior that has indeed
source and the gate, an equal amount of charge of
been observed in evaporated pentacene (Nelson et al.
opposite sign is induced at either side of the insulating
1998). For large grains, the mobility in polycrystalline
layer. The charge induced at the insulator–semiconduc-
pentacene may approach that of the single crystal.
tor interface can be driven by a second bias applied
However, low cost is not compatible with vacuum
between the source and the drain. In practice, the field
evaporation, which is a rather expensive technique.
effect transistor behaves as an variable resistance, the
Solution processing, such as spin-coating, appears
magnitude of which can be adjusted through the gate
much more appropriate. This technique requires the
voltage. As such, it constitutes the elemental backbone
use of soluble polymers, such as poly(alkyl-thio-
of logic circuits.
phene)s. Good ordering of the semiconductor layer is
To be efficient, the transistor must offer the lowest
achieved by using regio-regular derivatives. Encour-
possible ‘‘off’’ current and the highest possible ‘‘on’’
agingly, a mobility as high as 0.1 cm# V−" s−" has been
current. The magnitude of the latter is dictated by the
reported by Sirringhaus et al. (2000).
carrier mobility of the semiconductor. This measures
Until now, most of the organic semiconductors used
the ratio of the carrier mean velocity to the applied
in OFETs are p-type (i.e., most carriers are positive
electric field, which in turn is proportional to the
holes). n-Type compounds are highly desirable be-
applied voltage. In single crystalline silicon, mobility is
cause they could allow the design of circuits using
of the order of 1000 cm# V−" s−". Typical values of the
a complementary architecture, which would give
mobility in early OFETs were in the range of
numerous advantages. Unfortunately, most n-type
10−% cm# V−" s−" or even lower. Much effort was then
organic semiconductor are very sensitive to oxygen,
devoted to improve mobility. As the mobile charges
which makes the fabrication of devices possible only
induced in the conducting channel are located very
under strict control of the ambient environment.
close to the insulator–semiconductor interface, it was
Efforts have therefore been made to synthesize air-
soon recognized that purity and good ordering of the
stable n-type organic semiconductors. Perfluorinated
organic layer in that region were crucial. These
compounds are claimed to meet this requirement
characteristics largely depend on the deposition tech-
(Katz et al. 2000).
nique. Small molecules such as oligothiophenes and
pentacene (Fig. 8) are most often deposited by
vacuum evaporation. In this case the films are poly-
3.3 PhotoŠoltaic Solar Cells
crystalline, so mobility mostly depends on the orien-
tation and size of the crystal grains (Dodabalapur et Solar energy conversion was probably the first
al. 1995). Both are improved by a low rate of application thought of for organic semiconductors

7
Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
Figure 9
Flexible organic solar cell fabricated on a plastic sheet
(courtesy of Professor N. S. Sariciftci, Linz University,
Austria).
when the photovoltaic effect in laminated organic
systems was first reported by Kearns and Calvin
(1958). However, the power yield of organic photo-
voltaic cells remained well below 1% for many years.
A bilayer structure that delivered a power efficiency
slightly over 1% was reported by Tang (1986), but the
device used very thin layers thus making it difficult to
avoid short circuits when increasing the area of the
device.
An important step toward efficient organic solar
cells was the model developed by Ghosh and Feng
(1978), which postulated that, unlike their inorganic
counterparts, the limiting step in organic solar cells is
exciton diffusion rather than charge transport. The
structure of an organic photovoltaic cell is very similar
of that of an OLED and the mechanism of light
conversion to electricity is the reverse of that of light
emission depicted in Fig. 6. The energy of an impinging
photon is absorbed by a molecule, which generates an
exciton. Then comes the bottleneck, namely the
breaking of the exciton into a pair of separate charges.
It is generally recognized that charge separation of a
Frenkel exciton occurs through an Onsager process
(see Excitonic Model Šersus Band Gap Model in
Organic Materials: Theory and Molecular and Polymer
Semiconductors, Transport Properties of), the quantum
yield of which is very low unless the electric field is very
high. Unfortunately, the latter is limited in a phot-
ovoltaic cell because the voltage drop through the
device cannot exceed the work function difference
between both electrodes, that is, 1.5 V at most.
One idea consists of using two materials between
which photoinduced charge transfer is ultrafast (see
8
Figure 10
Molecular structures of tetrathiafulvalene and
tetracyanoquinodimethane.
PhotoŠoltaic DeŠices from Organic Semiconductors),
thus avoiding any other exciton relaxation mechanism.
The initial separation of charges may then take place
with quantum efficiency close to unity. Interesting
results have been reported with devices made of the
combination of a conjugated polymer together with
fullerene C . An alternative approach to ‘‘interpene-
'! networks’’ consists of doping penta-
trated polymer
cene with a small amount of iodine or bromine.
Heterojunction devices based on ZnO and bromine-
doped pentacene crystals allow solar-energy conver-
sion efficiencies up to 4.5% for standard AM1.5
illumination. Efficiencies as high as 2.2% have even
been achieved by this approach using thin-film devices
grown on plastic substrates by organic vapor phase
deposition. These breakthroughs in the field of organic
photovoltaics could finally open the road toward
low-cost, large-area and flexible organic solar cells
(Fig. 9).
4. Organic Superconductors
Interest in conducting charge transfer salts has been
propelled by three turning points—one theoretical
idea and two experimental breakthroughs. The theor-
etical idea was the proposal of a possible excitonic
pairing of electrons and holes in conjugated (unsatu-
rated) organic materials. Because this theory predicted
an attractive interaction of the Cooper pair in an
energy range extending up to the Fermi energy instead
of the limited range imposed by the phonon energy in
the conventional BCS (superconductivity) theory, it
would have led to high-temperature superconductivity.
However, numerous physical problems were over-
looked and the mechanism has never actually been
observed. Nevertheless, the unsuccessful search for
a high-temperature organic superconductor led to two
important discoveries: the synthesis of the first highly
conductive charge transfer salt and the observation of
superconductivity in organic ‘‘Bechgaard’’ salts.
The first ‘‘organic metal,’’ tetrathiafulvalene–tetra-
cyanoquinodimethane (TTF–TCNQ), is a quasi-one-
dimensional metal made up of TTF and TCNQ (Fig.
10). At high temperatures, the conductivity of TTF–
TCNQ increases as the temperature decreases, with
σ(T ) ` T−#.$. However, TTF–TCNQ undergoes a so-
called Peierls transition at 53 K, below which it
becomes electrically insulating. The Peierls transition
is related to the one-dimensional instabilities that
originate from the fact that one-dimensional regular
 Molecular and Polymer Semiconductors, Conductors, and Superconductors: Overview
chains of atoms (or molecules) are thermodynamically
unstable. This instability leads to a structural dis-
tortion of the chain driven by electron–phonon in-
teraction. The transition takes place at the Peierls
temperature, TP. Below TP, a dimerization into two
sets with unequal intersite distance occurs. This
dimerization opens up an energy gap in the half-filled
conduction band and the metal becomes an electrical
insulator. Diffuse x-ray and neutron scattering
measurements have confirmed the presence of struc-
tural changes accompanying the metal insulator tran-
sition.The crystal structure of TTF–TCNQ is shown in
Fig. 11. It corresponds to the most favorable structure
for high conductivity in charge transfer salts, where
electron donors, D, (TTF) and acceptors, A, (TCNQ)
stack in segregated parallel columns. A mixed stacking
of D–A–D–A, which leads to electrical insulators, is
the most common packing mode in charge transfer
salts.
Superconductivity was discovered by Je! ro# me et al.
(1980), when the donor tetramethyltetraselenafulva-
lene (TMTSF) was combined with the octahedral
acceptor anion phosphorus hexafluoride (PF−) using
electrocrystallization. The compound became' super-
conducting at a temperature of 0.9 K and a pressure of
10 kbar. In this compound, the lateral Se–Se inter-
actions make the crystal two-dimensional, thus defeat-
ing the Peierls dimerization. Superconductivity was
subsequently achieved at ambient pressure by replac-
Figure 11
Crystal structure of the TTF–TCNQ complex.
ing the acceptor with perchlorate (ClO−). Several tens
of superconducting organic charge transfer% salts have
so far been isolated. Most of them are quasi-two-
dimensional compounds—a feature necessary to avoid
the Peierls transition. A complete list of superconduct-
ing charge transfer salts can be found in the review by
Metzger (1999).
5. Conclusion and Perspectives
Organic conductors and semiconductors have
emerged as new materials for information technology.
Chemistry and solid state physics combine elegantly
to provide the basis for fundamental science as well as
device applications. Molecules and polymers can be
tailored ‘‘on demand’’ by means of chemistry to afford
complex systems capable of performing various opto-
electronic functions.
Today’s microelectronics are based on silicon, a
material composed of a large number of atoms ordered
over long distances of at least several nanometers. In
sharp contrast to silicon, organic conductors and
semiconductors are built with a limited number of
atoms (mainly C, O, N, and H) according to a precise
three-dimensional architecture with dimensions of
only a few angstro$ ms. Each molecule can then behave
as an individual device that can in turn be connected
by conducting polymer wires to form molecular
arrays. The possibility of fabricating electronic circuits
with dimensions of a few angstro$ ms (instead of less
than 1 µm) could significantly increase the size and
performances of computers, thus realizing the dream
of ‘‘molecular electronics.’’
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