Professional Documents
Culture Documents
0 Introduction
1
II.3.a Overview over basic phenomena
II.3.b Bipolar carrier injection
III.4.c Exciton formation
2
0 Introduction
3
I.1 Chemistry of Carbon (C)
For our context, the key difference between
organic and inorganic solid matter is that
excitations in inorganic matter are delocalised
and best described by a wave vector k, while in
organic matter, excitations usually are localised
and k is not a good quantum number. To understand
organic semiconductors (and, maybe synthetic
metals?), we have to understand how something
like a ‘bandgap’ can arise within a single
molecule. The key to this understanding lies in
the chemistry of carbon.
12
The most common carbon isotope is C (nucleus has
6 neutrons, 6 protons), but there is a natural
13
abundance of 1.2% the C isotope with 7 neutrons,
6 protons. This has a nuclear magnetic momentum,
which is used in NMR. In atomic carbon, the 6
electrons occupy the following orbitals, table
I.1:
Table I.1
4
I.1.a Hybrid orbitals
Carbon, like most chemical elements, forms
covalent bonds. The driving force for chemical
reaction is the desire to share electrons between
different atoms to complete electronic shells.
Thus, usually,
5
sp3 hybrid orbitals have 4 ‘fingers’ pointing
into space ‘symmetrically’, i.e. into the corners
of a tetraeder. The angle between the ‘fingers’
o
is 109.5 . In this form, C can form 4 bonds, e.g.
by sharing electrons with Hydrogen’s 1s shell:
CH4 (methane), or with other sp3 carbon (e.g. H3C-
CH3, ethane). The C-C bond in ethane is called a
σ bond. σ bonds are very strong: Diamond consists
of carbon held together by σ bonds entirely.
6
molecule overlap to form two π bonds (carbon
triple bond). This is Ethene (acetylene), HC≡CH.
Or
7
delocalized to form a ‘cloud’ that spans the
entire molecule.
= 1 / 2
8
throughout the entire molecule and are relatively
loosely bound.
9
The last pair of electrons (one for each spin
state) to be ‘filled’ into the molecule occupies
a molecular orbital that is called ‘highest
occupied molecular orbital’ (HOMO). Note that a
half-filled HOMO would imply an unpaired spin,
i.e. the molecule would be a radical. Since the
completion of electronic shells is the driving
force behind chemical reactions, radicals usually
appear at intermediate stages of chemical
reactions, but not as end product. The next
molecular orbital beyond the HOMO is called
‘lowest unoccupied molecular orbital’ (LUMO).
HOMO and LUMO together are also referred to as
frontier orbitals.
10
Here follows a reference list of conjugated
molecules and polymers, which are of importance
in the field of organic semiconductors, together
with acronyms by which they will be referred to
throughout this text. The sheer length of this
(hopelessly incomplete!) list underscores one of
the key assets of organic semiconductors: The
practically unlimited diversity of synthetic
organic chemistry allows tailoring materials with
a large property portfolio.
Table I.2
S S S
S S S
6T
11
Pentacene
Perylene
N N
H3C CH3
TPD
N
N
O
PBD
C60
12
N O
N
O Al
O
N
Alq3
N
N Pt N
N
PtOEP
N O
Ir
O
S
2
btpacac
13
N O
Eu
N O 3
ADS053RE
N
C7H15O
S SC12H25
7O-PBT-S12
C6H13 C6H13
S S
C6H13 S S C6H13
S S
C6H13 C6H13
HHTT
ABTo O
S ABTo
O
O
HO N O
N N
HO
N
Ru N
N Ru N S
N
N N
HO N S S N
O S
ABTo
O
ABTo O
N3 Black dye
14
O
O2N NO2
O2N
TNF
*
n *
PPV
MEH-PPV
N
C
n CN-PPV
* n *
PPE
15
* n *
PPP
C10H21
H3C
* *
H3C
C10H 21
MeLPPP
S
* n
*
R PAT
S n *
S
PTV
PTAA
16
* n *
R R PF
* n *
N N
C8H17 C8H17 S
F8BT
S
* n *
S
C8H17 C8H17
F8T2
*
n *
N
PVK
17
N
N N
ST 638
sQP
O
O
O O
(H2C)nO O(CH2)n
N N
oxTPD
18
N
NDSB Dendron
(G2)
*
* n
PA
n *
*
PDA
19
NH N
N
NH
PAni
* S
n *
O O
PEDOT
20
semiconductors, which are known for their fast
hole mobilities and are often used in organic
transistors. PBD (2-(biphenyl-4-yl)-5-(4-tert-
butylphenyl)-1,3,4-oxadiazole) is an electron
conductor. Both TPD and PBD have been used as
carrier injection layers in multilayer device
architectures. C60 is a material with very high
electron affinity, and C60 derivatives have been
used as electron acceptors in organic
photovoltaic devices. However, electron transport
in C60 is very sensitive to even traces of oxygen,
which limits its practical potential. Alq3
(tris(8-quinolinolato)aluminum(III)) is an
organometallic Al chelate complex with efficient
green electroluminescence and remarkable
stability. Alq3 was used as the emissive material
in the first double layer organic light- emitting
device. PtOEP is a red phosphorescent porphyrine
derivative. The central Pt atom facilitates spin-
orbit coupling that allows light emission from
triplet excitons. btp2Ir(acac) (bis(2-(2'-
benzothienyl)-pyridinato-N,C-3')
iridiumacetylacetonate) is a representative of a
family of highly efficient phosphors that have
been used successfully as triplet- harvesting
emitters in efficient electrophosphorescent
devices. ADS053 RE is a trade name for the red-
emitting organolanthanide
Tris(dinapthoylmethane)mono (phenanthroline)-
europium(III). Organolanthanides transfer both
singlet- and triplet excitons to an excited
atomic state of the central lanthanide, resulting
in very narrow emission lines, i.e. spectrally
21
pure colours (here, the 612 nm red line of
Europium). 7O-PBT-S12 and HHTT are hole-
transporting calamitic and discotic liquid
crystals, respectively. Due to the stacking of
conjugated cores in smectic (7O-PBT-S12) and some
discotic (HHTT) liquid crystalline phases, both
can display rather high charge carrier
mobilities. ‘N3’ and ‘black dye’ are
organometallic dyes with broad absorption spectra
spanning the red and near infrared, which are
often used for the harvesting of solar photons in
dye- sensitized photovoltaic cells (‘Grätzel
cells’). Trinitrofluorenone (TNF) is often used
as electron acceptor for the formation of charge
transfer complexes with conjugated molecules.
22
and low ionisation potentials, which qualifies
them for use in organic field effect transistors.
However, thiophene- containing materials are
generally sensitive to oxygen, which for
practical organic transistor applications can not
be excluded. Instead, variations of
poly(triarylamine) (PTAA) are being developed for
hole- transporting transistors. Polyfluorene (PF)
is a blue emitter that has recently competed
successfully with PPV as organic light emitting
material. Typically, PF is copolymerized rather
than sidechain- substituted to modify its
properties. F8BT is an electron transporter and
efficient green emitter. F8T2 is a hole
transporter that works well in transistors. PF,
F8BT, and F8T2 also display interesting liquid
crystalline phases.
23
phenyl-amino)-triphenylamine. This is a low
molecular weight material, but due to its
sterically hindred ‘starburst’ architecture it
has a very high glass transition temperature and
does typically not crystallise when spincast from
solution, but forms a glassy film, like many
polymers. The glassy morphology has considerable
advantages for device applications; a tendency to
crystallise is a major problem with hole
transporting small molecules such as TPD. The
same structural theme was employed for the design
of electron transporting starburst- type
phenylquinoxalines (not shown here). Another
structural theme that can be used to suppress
crystallisation in non- polymeric materials is
the use of spiro- links between two (or more)
para-phenylene units, here exemplified by a
spiro- linked pair of quaterphenyls (sQP). Note
the cross- shaped 3- dimensional architecture of
spiro compounds that is difficult to sketch on
paper. oxTPD is clearly a low- molecular weight
compound, but via the oxetane functions that are
attached with flexible spacers it can be
crosslinked in- situ with the help of a suitable
(photo)initiator. The result is a highly
crosslinked, inert hole transporting film with no
crystallisation tendency that has been used
successfully in multilayer devices. NDSB Dendron
(G2) is a second generation, nitrogen- cored
distyryl benzene dendrimer. The core displays
visible absorption and emission, the meta- linked
dendronic sidegroups have a bandgap in the UV and
24
for the purposes of charge injection, transport,
and light emission can be considered as inert.
25
show very different performance in devices.
Device performance can be very sensitive to low
levels of impurities and/or chemical defects, and
often, different chemical routes that lead to the
same material introduce different levels and
types of defects and/or impurities. Experience
shows that the Gilch route is superior to Wittig,
Horner, and Stille coupling for high quality
poly(arylenevinylene)s, while Suzuki coupling is
to be preferred over Yamamoto or Kovacic coupling
for poly(arylene)s. The highest regioregularity
in poly(alkylthiophene)s are achieved with the
help of Rieke Zinc. Companies or research groups
that are able to provide conjugated materials in
the quality required for practical devices are
few and far between. Even if chemistry is
‘ideal’, the same material can still display very
different properties when prepared in different
ways. The solvent and casting method used for
solution processing, or deposition rate, type and
temperature of substrate for evaporated films,
thermal treatment cycles, and the presence or
absence of even trace amounts of oxygen and/or
water can have a decisive impact on the resulting
device.
26
be mobile. In I.2, we will discuss the
fundamental properties of these excitations. In
I.3, we will see how excitations are generated
practically, and how they migrate.
27
illustrates that in the format of a chemical
reaction:
→ D+ + e −
I
D
p
Eq. I.1:
A + e− → A−
a E
28
As a practically important example for an organic
radical ion, a neutral and a positively charged
polythiophene segment are sketched in Fig. I.3.
Note how the missing electron (hole) leads to a
redistribution of the π-bonds and hence, to
different bond lengths, bond angles, and nuclear
positions.
S S S S
S S S S S
Hole
injection
(oxidation)
S S S S
S S S S S
29
from the combination of a hole- and an electron
polaron.
Excitation
30
The ‘size’ of the exciton is about 3 repeat
units, or 10 nm, and the exciton has clearly
intramolecular, one- dimensional character. This
makes organic excitons Frenkel excitons, while in
inorganic semiconductors, excitons typically are
more delocalised Wannier excitons. Due to the
mutual attraction of electron and hole in the
exciton, and structural relaxation of the
molecule, the energy difference between the
excitonic state and the ground state is lower
than the difference between Ip and Ea suggests
(which in turn is lower than the difference
between HOMO and LUMO). This energy difference is
known as exciton binding energy Eb. Eb is larger
in Frenkel than in Wannier excitons; typical
organic (Frenkel) exciton binding energies are in
the range 0.2 to 0.5 eV. Note how considerable
ambiguity arises in the term ‘bandgap’ when
applied to organic semiconductors, which can mean
either the energy difference between LUMO and
HOMO, or Ip - Ea, or (Ip – Ea) – Eb.
31
LUMO
Ground state
HOMO
Hole Electron
polaron polaron
Singlet
Triplet exciton
exciton
32
rules of quantum mechanics, in particular the
Pauli principle. There is three ways in which
hole and electron spin can combine so that the
resulting overall spin part of the wavefunction
is symmetric under particle exchange, and has
total spin S = 1 - namely ↑↑>,↓↓>, and 1/√2(↑↓>
+ ↓↑>). Excitons with that property are called
triplet excitons. One combination of spins,
namely 1/√2(↑↓> - ↓↑>), results in a spin part
of the wavefunction that is antisymmetric under
particle exchange, and total spin S = 0. This
combination is called a singlet exciton. The
properties of excitons are summarised in table
I.3:
Table I.3
↑↑> 1 1 +
↓↓> 1 -1 +
1/√2(↑↓> +↓↑>) 1 0 +
1/√2(↑↓> -↓↑>) 0 0 -
33
symmetry property under particle exchange.
Excitons with a spin ket symmetric under particle
exchange are triplet excitons, excitons with spin
ket antisymmetric under particle exchange are
singlet excitons.
34
being the bond length. Bond length is longer for
the excited state due to the presence of
π
*
antibonding orbitals. The horizontal lines
represent the vibrational states of the bonds.
Nuclear distances oscillate around the
equilibrium bond length within the limits of the
intersection of the horizontal line with the
potential curve. Vibrational levels are quantised
with a vibronic spacing in the order 0.1 eV ≅
1100 K; consequently, at room temperature, almost
all bonds are in the lowest vibronic level of the
ground state. From there, they may be lifted into
the first excited state by absorption of a
photon.
E
S1
S0
r
R0 R1
35
The absorption process is governed by the Franck-
Condon principle: Electronic transitions are much
faster than nuclear rearrangement. Hence,
transitions always occur ‘vertically’ in the
diagram, from ground state equilibrium position
to the turning point of a vibrational mode of the
excited state that is close to the ground state
equilibrium distance. Transitions from the 0
vibronic level of the ground state into the 0 / 1
/ 2 /… vibronic level of the first excited state
are known as 0-0 / 0-1 / 0-2 /… transitions. The
relative intensity of these is controlled by the
overlap integral between the electronic ground
state / vibronic ground state (0 vibronic state)
wavefunction and excited state / vibronic state
0, 1, 2,… wavefunctions. The overlap integral can
be separated into an electronic and a vibronic
integral; the square of the vibronic integral is
known as the Franck-Condon factor of the
transition. A detailed discussion is in [T6, Ch.
17]. If the equilibrium bond lengths in the
ground- and first excited state were equal, the
0-0 transition would have unit Franck-Condon
factor, and all higher vibronic transitions would
have Franck-Condon factor zero, i.e. they would
be forbidden. In reality, bond lengths for
excited states are longer than for the ground
state, and higher vibronic transitions become
allowed, the so- called vibronic satellites.
Usually, however, the 0-0 transition will be the
most intense.
36
normalised fluorescence (x)
1 1
0.6 0.6
0.4 0.4
0.2 0.2
0 0
300 350 400 450 500 550 600
Wavelength [nm]
37
shorter wavelengths (higher energies), emission
spectra on the right (lower energies). When
represented against an energy or wavenumber
scale, the situation is reversed.
38
In organic light emitting devices, light is
generated not by the absorption of a photon, but
by the combination of an electron- and a hole
polaron: An electron in the LUMO and an electron
vacancy (hole) in the HOMO can combine to form an
exciton. The fluorescence emitted from an
electrically generated exciton is called
electroluminescence (EL). However, there is a
fundamental difference between the formation of
excitons by absorption of light, and by
combination of polarons.
st
to singlet 1 excited state). Since the photon
carries a unit h of orbital angular momentum L,
0 1
S and S have orbital angular momentum quantum
numbers l differing by 1 (one). Inversely, the
S ÅS
0 1
fluorescence transition does fulfil the
selection rule ∆l = 1. The photon’s orbital
angular momentum provides the required angular
S ÆS
0 1
momentum for the transition; conversely,
the S ÅS transition provides the orbital angular
0 1
39
0
corresponding to the T state. This is simply
because there is 3 ways to combine 2 spins into a
triplet state and only one way to combine them as
0 0
a singlet. Both S and T have the same angular
momentum quantum number l, hence ∆l = 0 for the
S ÅT
0 0
transition: The triplet- to- singlet
transition is dipole forbidden. Triplets can not
emit fluorescent light, because the necessary
angular momentum h can not be supplied from the
orbital angular momentum difference between
excited and ground state. Obviously, it is bad
news for organic electroluminescence that
apparently only 1 in 4 electrically generated
excitons can emit light.
0
However, T does carry angular momentum in its
spin: Remember triplet excitons have total spin S
= 1, singlets 0. In some molecules, triplet spin
angular momentum can be transferred to a photon’s
orbital angular momentum. The conversion of spin
into orbital angular momentum is facilitated by
the interaction of the magnetic fields that both
electron spin and orbital angular momentum
generate. These fields interact with each other,
and interaction is proportional to the product of
orbital and spin angular momentum, L.S. This
interaction is therefore known as spin- orbit or
0
LS coupling. The emission of light from T via LS
coupling is known as phosphorescence. To have
strong LS coupling, we need to incorporate atoms
into our molecules that have filled atomic shells
with high orbital quantum number l. This will
40
generally be ‘heavy’ atoms (i.e., heavier than
carbon). Phosphorus may work – the clue is in the
name – but modern phosphors used in organic EL
are heavy metal organometallic complexes using
e.g. Iridium.
41
When π orbital overlap is improved by forcing
rings into a coplanar arrangement by chemical
bonds, bandgap will be reduced. Example:
Oligomers of para-phenylene (PPP), fluorene
(PFO), and methylated ladder-type poly(para-
phenylene) (mLPPP):
Table I.4
Number of Oligo-PP Oligofluore Oligo-mLPP
Benzene [eV] ne [eV]
Rings [eV]
3 4.44 3.70
4 4.25
5 4.15 3.18
6 4.03 3.56
7 3.00
8 3.43
9
10 3.35
42
It is evident that at a given number of rings,
the more planarized the backbone, the lower the
bandgap.
43
gives MEH- PPV the photophysical properties of a
homopolymer, but crystallisation is suppressed as
in a random copolymer. As crystallisation often
is detrimental to fluorescence efficiency, this
was a welcome step forward in the development of
conjugated polymers. The alkoxy- linkage of MEH-
PPVs sidechains to the phenyl backbone ring also
changes the electronic structure of the backbone.
Alkoxy links have a tendency to donate electrons
to the backbone, which changes the shape and
location of the HOMO. As a result, emission is
redshifted compared to PPV, from green to orange.
44
type of sidechain attached. Note that sidechains
are attached pairwise at a position which itself
is not part of the conjugated backbone, and these
pairs are widely spaced, so that there is neither
steric nor electronic impact of the sidechains on
the backbone properties. However, strictly
alternating copolymers of fluorenes with
comonomers with different electronic properties
have been prepared, such as F8BT (alternating
copolymer between dioctyl fluorene with
benzothiadiazole) and F8T2 (alternating copolymer
of dioctyl fluorene with two thiophenes). For
both F8BT and F8T2, the resulting bandgap is
reduced, and they both emit in the green- yellow
region. The reduction of the bandgap has
different reasons: In the case of F8BT, the
benzothiadiazole comonomer has a higher electron
affinity Ea than fluorene, thus leading to a
polymer with higher Ea. In the case of F8T2, the
two thiophene groups have a lower ionization
potential Ip than fluorene, thus leading to a
polymer with lower Ip. Copolymerization thus does
not only allow control of the bandgap, but of
both Ip and Ea in a predictable manner, and a
large number of fluorene copolymers have been
synthesized and studied. For a review, see [R13].
Both polymers have found interesting
applications: Some of the most efficient organic
EL devices have been built from blends of a
minority amount of F8BT as electron injecting /
transporting material in hole injecting /
transporting polyfluorene host material. F8T2, on
45
the other hand, is an excellent material for p-
type OFETs.
46
Location Location
V a c u u m
0 level
Vacuum te
level
Ea
2.5 Cathode
2.8
Ca
4.2
Al
4.7 Ip
ITO 5.2 ITO
PPV
Energy [eV] th
47
functions, ionisation potential, and electron
affinity – are the same at the metal- organic
semiconductor interface as they are in the
isolated metal, or bulk semiconductor. Note that
due to the molecular nature of organic
semiconductors, there are no surface ‘dangling
bonds’ which do usually distort bulk energy
levels in inorganic semiconductors. However, in
metal- organic semiconductor contacts, interface
dipole moments often are present (sometimes,
deliberately engineered) which will modify
barriers. Also, the work function of a metal
coated with an organic semiconductor can be
different from that of the same metal with
respect to vacuum. An example is the gold-
pentacene interface, which displays a
surprisingly large energy barrier. These issues
are discussed e.g. in [N Koch, A Elschner, J
Schwartz, A Kahn, Appl. Phys. Lett. 82, 2281
(2003)]. In the presence of such effects, levels
in Fig. I.13 have to be re- drawn at a different
energy.
48
injection barrier, here of 0.5 eV for holes from
ITO into PPV. Electron injection from Ca or Al
into PPV needs to overcome a barrier of 0.3 or
1.7 eV for electron, respectively. On the other
hand, for electron injection from ITO, there
would be a large barrier of 2.2 eV. Thus, the use
of electrodes made from unlike metals defines a
forward and reverse bias for the OLED. To
minimise barriers, a high workfunction anode and
a low workfunction cathode are required. Table
I.7 lists the work functions of some metals, as
well as the highly doped semiconductor ITO, and
the synthetic metal PEDOT/PSS.
Table I.7
Cs 1.81
Ca 2.8
Mg 3.64
Al 4.25
Ag 4.3
Au 4.7
Cu 4.4
ITO ≈ 4.7
PEDOT/PSS ≈ 5.0…5.2
49
Table I.7: The work function of a number of
metals, most data from [T4, Table 18.1, Ch. 18].
High work function metals are known as ‘noble’
metals. Low work function metals are highly
reactive and usually need to be protected from
ambient atmosphere to avoid oxidation.
3/ 2
(eq.I.4.1) C ( Vbias )2 exp[−B d∆V
j FN = ∆V ]
d Vbias
*
with B = 8π√(2m )/(2.96eh) with an effective
electron mass m*. For a detailed discussion, see
e.g. [T1, Ch. 12]. Note that jFN depends on
applied voltage Vbias and film thickness d only in
50
the combination Vbias/d, i.e. jFN scales with the
applied field E. Thermally activated or
thermionic injection is described by the
Richardson- Schottky (R-S) equation:
2
(eq. I.4.2) j RS = AT exp[−(∆V − Vm (E)) /kT ]
2 3
with A = 4πemkb /h , and Vm(E) describing the
field- dependend lowering of the injection
barrier by the attraction of the injected carrier
to its mirror charge; Vm(E) = √(eE/4πεε0).
51
charge carriers across the film. Carrier
transport is characterised by charge carrier
mobility µ, which plays a crucial role for
organic transistors. Practically, a contact can
be considered ohmic whenever carrier transport is
a more restrictive limit on current density than
carrier injection.
52
II.1 Synthetic Metals
According to a general theorem proven by Peierls,
there cannot be a one- dimensional metal (Peierls
transition). This seems to exclude the
possibility of metallic polymers.
53
introduced into a host crystal lattice. In
synthetic metals, doping is by a chemical
reaction between semiconducting polymer and
dopant. Both redox- and acid/base reactions
between semiconductor and dopant have been used
successfully; typical examples are PA oxidation
with chloride or iodine, and acid doping of PAni
with camphorsulfonic acid, PPy with phosphoric
acid, and PEDOT with poly(styrene sulfonic acid)
(PSS). Quite high dopant concentrations of (1 to
50)% are typically used. Iodine oxidises
polyacetylene, thus removing π electrons from the
HOMO. This opens up mobile vacancies (holes) in
the previously completely full HOMO (‘valence
band’). Conductivity will depend on doping level;
for the highest doping levels PA can be as
5
conductive as Platinum (≈10 S/cm at room
temperature). Generally, synthetic metals become
more metal- like in their behaviour as dopant
concentration is increased. Above a critical
dopant level, most synthetic metals remain
conductive in the limit T Æ 0, and display NTC
behaviour at room temperature. Fig. II.1
summarises the behaviour of a number of synthetic
metals. Multiple entries for the same material
correspond to samples with different dopant
levels.
54
Fig. II.1: Room- temperature conductivity and
temperature behaviour of conductivity for several
synthetic metals at different temperatures. SWCN
= single- wall carbon nanotubes. Full squares:
NTC at RT and σ > 0 at T Æ 0 (‘proper metal’);
hollow squares: NTC at RT, but σ Æ 0 at T Æ 0;
full circles: PTC at RT but σ > 0 at T Æ 0;
hollow circles: PTC at RT and σ Æ 0 at T Æ 0
(‘proper semiconductor’). From A B Kaiser, Adv.
Mater. 13, 927 (2001).
55
II.2.a Water- based synthetic metals
Nowadays, mainly PANi and PEDOT are used as
synthetic metals. This is because both of them
are available as aqueous dispersions for
spincoating or ink jet printing. This makes them
easy to process into coatings, or for multilayer
film applications in conjunction with organic
semiconductors: Soluble organic semiconductors
are usually processed from organic solvents, in
which the water- based synthetic metals are not
soluble. The advent of water- based synthetic
metals can be seen as a second breakthrough in
addition to the initial discovery of metallic
polyacetylene. Soluble synthetic metals have
considerably larger potential for applications
than insoluble polyacetylene.
56
Na 2 S 2 O 8
O O
H 2O
S n
SO 3 H
* n
*
SO 3 - SO 3 H SO 3 H SO 3 H SO 3 - SO 3 H
O
O O O O O
* S S S *
C S n
+ S S C +
O O O O O
O
57
- A net positive charge on the PEDOT chain that
will strongly attract the negative charge left on
the acid. Since this happens at many points along
the chain, PEDOT and PSS become closely
intertwined and float as a fine dispersion or
colloid in the aqueous solution, rather than
precipitate. They can not separate, and will not
dissolve in organic solvents.
58
8 2
sufficient. Today, > 10 m of photographic film
is coated with PEDOT/PSS every year.
59
Recently, flexible and transparent PEDOT/PSS-
coated polyester sheets with sheet resistance in
the order 1kΩ/square have become available under
TM
the tradename ‘Agfa Orgacon ’. These sheets can
be patterned by an etching procedure which is
performed in a very similar way to conventional
photoresist patterning, although the chemistry is
rather different. This is the substrate onto
which future organic electronics and displays
will be prepared.
60
II.2 Organic field effect transistors
The transistor is the mainstay of solid state
electronics, and represents one of the seminal
inventions of the 20th century. All transistors
have three terminals. A current between two of
these three terminals can be controlled by the
input of the third terminal. Transistors can be
categorised into two ‘families’ according to how
this control is exercised: Those where the
control is through a current at the third
terminal, and those where the control is through
a voltage at the third terminal.
61
Voltage- controlled transistors are also known as
field effect transistors (FETs). The three
terminals are called source (S), drain (D), and
gate (G). A voltage at G controls the S- D
current. The basic principle of the field effect
transistor dates back to 1930 [J E Lilienfeldt,
US Patent 1745175, 1930]. FETs are simpler in
design than bipolar transistors, require only one
type of carrier transport material (n or p), and
as we will see, not necessarily need to be doped
at all. Field effect transistors can be
manufactured in high integration densities and
are typically applied for logic gates in digital
electronics.
62
overcome. Also, higher added- value applications
are envisaged in combination with light emitting
organic semiconductors. Active- matrix addressed
display screens require two FETs and a capacitor
to address each pixel in a screen. Ultimately,
organic semiconductor technology aims to make the
transistors as well as the light emitting
material from organics.
63
Vd
Substrate
Vg
64
thus gets doped by applying VG. However, other
than in chemical doping, this is quickly
reversible: Switching VG off will switch the
doping off. Hence, VG can switch the channel
conductivity. This behaviour is quantified by the
so- called on / off ratio, which in some cases
6
can be as high as 10 . Accordingly, ID at a given
VD will change with VG: The FET is an electronic
switch. The accumulation layer in an OFET is
generally very thin, about 5 nm or less [M A
Alam, A Dodabalapur, M R Pinto, IEEE Transactions
on Electron Devices, 44, 1332 (1997)]. This is
much thinner than the typical thickness of the
semiconducting film.
65
The output characteristic of a FET is the family
of curves ID vs VD with VG fixed during every
single VD scan (‘drain sweep’).
66
make contact to the channel semiconductor without
contact resistance or injection barrier, the
semiconductor shall be trap- free and undoped,
and carrier mobility shall be independent of
gate- and drain voltages. Note that in reality,
few if any of these assumptions will be met!
Then, the following equation applies [T1, Ch.
14.2.2.1.2]:
Z
(eq.II.2.1.a) ID = Ciµ(VG − VT )VD for VD << VG ≥ VT
L
Z 2 for VD ≥ VG
(eq.II.2.1.b) ID = ISat = Ciµ(VG − VT )
2L
67
electric field and DG the gate electric
displacement. DG has the dimensions of charge /
area, and corresponds to a surface charge density
QS of equal magnitude – this is the accumulation
layer. From this consideration, we see it is the
electric displacement DG that switches the
transistor on, not the gate voltage or gate
electric field directly.
68
II.3. At VD = VG, the accumulation layer becomes
triangular and is on average half as ‘strong’ as
for VD Æ 0; this explains the factor 1/2 in eq.
II.2.1.b. When VD exceeds VG, the pinch- off point
moves away from the drain into the transistor
channel, and the carrier- depleted part of the
channel between pinch- off point and drain will
display very high resistance. Consequently, the
transistor displays drain current saturation for
VD ≥ VG, with ID,sat ∝ VG . The only way to increase
2
69
VG applied, VD ≈ 2VG. The accumulation layer
pinches off in the middle of the channel.
70
II.4.b
1.2
|ID |1/2 [(microAmp) 1/2 ]
1
0.8
0.6
0.4
0.2
0
0 10 20 30 40 50 60 70
|V G | [V]
71
Charge carrier mobility can be determined from
experimental characteristics with the help of
eq.s II.2.1. A very robust method of doing so is
to plot I D vs. VG , with ID in the saturation
72
V that corresponds to the voltage available in
the respective application, and Voff the gate
voltage that minimises the drain current; usually
Voff ≈ 0. On / off ratios typically are large
3 7
numbers roughly in the region 10 …10 , and can be
extracted most conveniently from a saturated
transfer characteristic when this is plotted with
the ID axis on a logarithmic scale.
∂I ZC
(eq. II.2.3) gm = D = i µVD
∂VG V <<V L
D G
73
We had seen that short channel length L will
result in higher drain currents, but L is even
more important for switching speed. The maximum
speed at which a transistor circuit can operate
is limited by the time τ it takes carriers to
cross the FET channel. That is the time the
accumulation layer takes to be emptied of charges
through the drain after VG has been switched off.
At frequencies f > f0 = 1/τ, the output signal
(ID) drifts out of phase with the input signal
(VG), and switching amplitude decreases. τ is
given by eq.II.2.4:
(eq.II.2.4) 1 = f 0 ≈ µVD
τ L2
74
electronics has to compete on price rather than
performance.
75
NOT NOT
NOT
76
that uses a pentacene- based organic ring
oscillator with a frequency of about 200 Hz [P F
Baude, D A Ender, M A Haase, T W Kelley, D V
Muyres, S D Theiss, Appl. Phys. Lett. 82, 3964
(2003)]. The rf ID tag has an antenna (LC
circuit) that absorbs an incoming radio signal
(frequency 13.6 MHz), and re- emits a signal of
the same frequency, but with an amplitude
modulation. The amplitude modulation is
facilitated by the ring oscillator periodically
shorting / re- engaging the antenna circuit.
77
processed organics!) or any other current
leakage, and should have a high dielectric
constant.
78
section, we will discuss several aspects of
charge carrier mobility in organic
semiconductors.
Table III.1
+ -
Materia Morphology µ h /e
l 2
[cm /Vs]
+
Pentace Large single crystal, 400 h
ne vapour deposited, c-axis,
low T
+
Pentace spincoated 0.001 h
ne
+
Pentace Evaporated onto 0.002…0. h
ne substrate, substrate at 03
room temperature (differe
79
nt
studies)
+
Pentace Evaporated onto 0.62…5 h
ne substrate, substrate at
120 C
+
F8T2 Aligned liquid crystal h
Parallel to alignment 0.01…0.0
Orthogonal to alignment 2
≈ 0.0015
-7 -4 +
PPV Several 10 …10 h
morphologies/methods
+
PAT Regioregular, face-on 0.001 h
substrate
+
PAT Regioregular, edge-on 0.1 h
substrate
+
6T polycrystalline 0.02 h
+
6T Single crystal 0.1 h
+
DH6T 6T with (α,ω)-dihexyl 0.05 h
endchains
-5 -
C60 Under air < 10 e
-
C60 In ultrahigh vacuum 0.08 e
-
F8BT Spincast from toluene ≈10 e
-3
80
We first note that typical organic mobilities are
much lower than the mobilities of carriers in
crystalline inorganic semiconductors. In
crystalline inorganic semiconductors, transport
is coherent or band- like with carrier mobilities
in the region of several hundred or even thousand
µ
2
cm /Vs (typically higher for Also, will
decrease with increasing temperature. This is the
hallmark of band- like transport, which in
exceptional cases can be observed in single
crystals of organic semiconductors at low
temperatures, as well – e.g., Karl et al. found µ
≈ 400 cm /Vs in Pentacene at low temperature [N
2
81
temperature. Amorphous organic semiconductors
will display hopping- type transport at all
temperatures. A detailed discussion of mobility
limits is in [C D Dimitrakopoulos, D J Mascaro,
IBM J. Res. & Dev. 45, 11 (2001)].
82
Low molecular weight (vapour- deposited)
thiophenes are less susceptible to oxygen doping,
however, their performance is now eclipsed by
pentacene that has been prepared with room-
2
temperature mobility of 5 cm /Vs [T W Kelley, D V
Muyres, P F Baude, T P Smith, T D Jones, Mat.
Res. Soc. Symp. Proc. 71, L6.5.1 (2003)]. This is
a mobility as good as that of amorphous silicon,
and is believed to be close to the theoretical
limit for hopping- type transport.
83
standard deviation of the assumed Gaussian
density of transport states). Higher σ
2
leads to
reduced mobility, it is thus paramount to
minimise energetic disorder by designing
molecules to have little scatter in their HOMO
levels. Disorder is introduced by conformational
degrees of freedom, such as possible rotations
around single bonds; and molecular dipoles. Note
that pentacene has no dipoles and no degree of
freedom in its molecular architecture, which goes
some way towards explaining its record hopping
mobility. Also, evaporated pentacene is
crystalline, thus further reducing energetic and
positional disorder. For some reason, in the case
of pentacene, the inevitable grain boundaries do
not seem to compromise transport.
84
complexity in device manufacture, which means a
high price.
85
In fluorescence, excitons are created by the
absorption of light, while in EL excitons are
created by electron and hole polaron ‘capture’.
Polarons first have to be injected from the
electrodes, and migrate towards each other. They
then form an exciton that sometimes can decay
under the emission of light. Fig. II.6 shows the
basic architecture of an organic light emitting
device (OLED). The variety of electrical and
photophysical processes involved are summarized
in the chart Fig. II.7.
86
Electric drive circuit
Cathode Organic
Semiconductor
Anode
Substrate
Light out
Anode Cathode
Hole Electron
Electron injection injection Hole
leakage leakage
current current
Coulomb Capture
exciton formation
"1/4" "3/4"
Intersystem crossing
Singlet Triplet
S=0 S=1
Triplet- triplet
annihilation
Radiative
decay (allowed) Radiative
non- decay
radiative non-
radiative (weakly
decay allowed)
decay
Ground state
Fig. II.7: A chart describing the formation and
decay of excitons in organic EL devices. Adapted
87
from [D D C Bradley, Current Opinion in Solid
State & Materials Research 1, 789 (1996)]].
88
make full colour displays. Materials chemistry
alone cannot overcome this hurdle.
89
Vacuum level
0
2.7
3.2
3.7
2.5 eV
Mg
2.5 eV
4.7
ITO
5.2
5.7
Energy [eV]
90
In addition to the injection barrier, both holes
and electrons will encounter an internal barrier
at the HTL/ETL interface, which is also called a
heterojunction. Note, however, that
heterojunctions in organic devices are quite
different from those in inorganic devices due to
the lack of (deliberate) doping. The internal
barrier is not detrimental to device performance.
Instead, it can help to improve the balance
between electron- and hole currents. Assuming a
slightly smaller injection barrier for holes than
for electrons, or higher hole- than electron
mobility, even in a bilayer device we would
expect a carrier imbalance with a larger hole-
than electron current. However, since holes will
encounter an internal barrier, they will not
simply cross the device and leave at the cathode
as a ‘blind’ leakage current. Instead, they will
accumulate at the interface, where they represent
a positive space charge. The effect of the field
resulting from that space charge is to improve
charge carrier balance: Firstly, it will impede
the further injection of majority carriers
(holes) from the anode, and secondly, it will
enhance the injection of minority carriers
(electrons) from the cathode. Also, excitons will
form at the internal interface, far away from the
electrodes. Cathodes in particular have been
associated with exciton ‘quenching’ (i.e.,
radiationless exciton decay); this is avoided by
placing exciton formation in the centre of the
device rather than close to the cathode.
91
As Tang and van Slyke used small molecules,
bilayers could readily be manufactured by
subsequent evaporation. This approach has been
extended to sophisticated multilayer
architectures, e.g. by the group of Kido in
Yamagata. They have demonstrated some of the
brightest and most efficient OLEDs to date
2
(140,000 Cd/m and 7.1% external quantum
efficiency) [J Kido, T Matsumoto, Appl. Phys.
Lett. 73, 2866 (1998)]. An interesting approach
to highly efficient, low- voltage operated
devices is the use of doped charge- injection
layers, that transform the characteristic of
carrier injection from a tunneling junction
(‘metal- insulator contact’) to a Schottky
junction (‘metal- semiconductor contact’). Often,
thin layers of LiF are evaporated as n- dopant
between the electron transporting organic
semiconductor and the metal cathode. An example
where both hole- and electron injection into an
OLED are aided by dopants is in [J Blochwitz, M
Pfeiffer, M Hofmann, K Leo, Synth. Met. 127, 169
(2002)]. A concept closely related is that of the
light- emitting electrochemical cell, where
mobile carriers are introduced in the form of a
salt that dissociates into mobile ions.
92
spincasting than with vapour deposition, because
of the need for ‘orthogonal’ solubilities. To
sidestep solubility problems, in principle a
precursor route may be employed, where the first
layer is prepared from a soluble precursor
polymer that then is converted in- situ into a
conjugated, and completely insoluble polymer.
This has been successfully employed for hole-
transporting PPV / electron transporting CN- PPV
double layer polymer OLEDs [H Becker, S E Burns,
R H Friend, Phys. Rev. B 55, 1 (1997)]. However,
the precursor route requires lengthy in- situ
thermal conversion under high vacuum and has
generally fallen out of favour with the advent of
soluble conjugated polymers.
93
research, mainly with a view to photovoltaic
applications of organic semiconductors [J J
Dittmer, E A Marseglia, R H Friend, Adv. Mater.
12, 1270 (2000)]. Holes are injected and
transported into the (majority component) PFO,
but can be transferred easily to F8BT, as it has
similar ionisation potential. However, F8BT has
poor hole mobility due to hole- specific traps.
Instead, it has rather high electron affinity and
displays comparatively good (albeit dispersive)
electron transport [A J Campbell, D D C Bradley,
H Antoniadis, Appl. Phys. Lett. 79, 2133 (2001)].
Thus electrons are mobile on the F8BT chain until
they encounter a trapped hole. With some further
device improvements, highly efficient (4.1 cd/A)
and low onset voltage (≈ 3V) OLEDs have been
prepared from such blends [J Morgado, R H Friend,
F Cacialli, Appl. Phys. Lett. 80, 2436 (2002)].
94
semiconductors generally display exciton binding
energies Eb of a few tenths of an eV [J L Bredas,
J Cornil, A J Heeger, Adv. Mater. 8, 447 (1996)].
When a carrier has to overcome an internal
barrier to form an exciton, this may require a
certain amount of energy; however, on exciton
formation, Eb is instantly ‘refunded’ –
effectively, the internal barrier is reduced by
Eb. Thus, majority carriers remain stuck at an
internal barrier and redistribute the internal
field in the favourable way discussed above,
until a minority carrier arrives at the
interface. As soon as a minority carrier is
available, exciton formation is then helped by
the effective barrier reduction Eb. High Eb also
stabilizes excitons against dissociation and non-
radiative decay. In ‘bulk heterojunction’ blends,
one carrier has to transfer from one chain to
another to form an exciton. This will be the type
of carrier for which the energy level offset of
either the ionisation potentials (|∆Ip|) or the
electron affinities (|∆Ea|) is smaller. The
smaller of the two offsets (min (|∆Ip|, |∆Ea|))
defines the energetic cost of carrier transfer.
Two very different scenarios emerge for the case
min (|∆Ip|, |∆Ea|) < Eb as opposed to min
(|∆Ip|, |∆Ea|) > Eb. In the former case,
formation of excitons from polarons will be
favoured, while in the latter case, the
dissociation of existing excitons into polarons
will be preferred. In the case of F8 / F8BT
blends, that had been introduced previously,
95
exciton formation is clearly favoured, and such
blends are useful for OLED applications. In other
hole / electron transport material blends,
exciton dissociation is favoured, which makes
such blends attractive for use in photovoltaic
devices. Examples include blends of F8BT with a
poly(fluorene-alt-triarylamine) [J J M Halls, A C
Arias, J D MacKenzie, W Wu, M Inbasekaran, E P
Woo, R H Friend, Adv. Mater. 12, 498 (2000)], and
blends of poly(alkyl thiophene) and perylene
tetracarboxyl diimide, [J J Dittmer, E A
Marseglia, R H Friend, Adv. Mater. 12, 1270
(2000)].
96
luminescence quantum yield. However, the
formation of normally non- emissive triplet
excitons presents an unwanted limit on OLED
efficiency, and several approaches to overcome
this have been explored.
σS σT
(eq. III.4.1) ηEL = η
σ S σ T + 3 PL
97
directly rather than inferring them from EL / PL
efficiencies, Vardeny et al. [M Wohlgenannt, K
Tandon, S Mazumdar, S Ramasesha, Z V Vardeny,
Nature 409 (6819), 494 (2001)] carried out a
systematic magnetic resonance study on a number
of organic semiconductors with bandgaps in the
visible. They found that σS/σT was indeed
generally larger than 1, namely between 2 and 5
for different materials. σS/σT ≈ (2 … 5)
corresponds to ηEL ≈ (0.4 … 0.6) ηPL, instead of
0.25 ηPL. Vardeny et al. then studied an oligomer
series [M Wohlgenannt, X M Jiang, Z V Vardeny, R
A J Janssen, Phys. Rev. Lett. 88, art. no. 197401
(2002)], finding σS/σT to increase with
conjugation length. This implies larger σS/σT for
polymeric than for low molecular weight organic
semiconductors – a finding that potentially can
influence the future direction of an entire
industry.
98
coherence over one conjugation length;
consequently polarons can ‘sense’ each others’
spin from a relatively long distance. Thus, if
singlet formation is preferred over triplet
formation, polymers have a chance of avoiding
triplet formation while electron and hole are
still widely separated, i.e. only weakly bound
electrostatically. In small molecules, quantum
coherence ends at the end of a molecule. Once a
hole and an electron are on the same molecule, it
is too late to avoid exciton formation,
regardless of spin statistics.
Electrophosphorescence
As alternative to the enhanced singlet formation
cross- section in polymers, in particular the
low- molecular weight OLED community has
developed the concept of ‘harvesting’ triplets
for light emission by using phosphorescence.
99
bandgap host, electrophosphorescence with > 80%
internal quantum efficiency and 60 lm/W is
observed [C Adachi, M A Baldo, M E Thompson, S R
Forrest, J. Appl. Phys. 90, 5048]. Using pure
btp2Ir(acac) without host matrix had resulted in
less efficient devices due to triplet- triplet
annihilation [C Adachi, M A Baldo, S R Forrest, S
Lamansky, M E Thompson, R C Kwong, Appl. Phys.
Lett. 78, 1622 (2001)]. In particular in the red,
electrophosphorescence is an attractive approach.
Due to the response characteristics of the human
eye, red dyes must show very narrow emission
peaks, otherwise colour purity will be
compromised. Iridium- based phosphors display
considerably narrower emission bands than typical
fluorescent dyes, and are thus particularly
useful as red emitters. These phosphors also
display relatively short triplet lifetimes (4µs),
which means they are fit for use in video rate
display systems, and do avoid problems associated
with triplet- triplet annihilation at high
brightness, which had been encountered with
longer lifetime phosphors.
100
sophisticated multilayer architectures, exciton
diffusion may be used to achieve efficient white
emission [B W D'Andrade, M E Thompson, S R
Forrest, Adv. Mater. 14, 147 (2002)]. However,
the manufacture of such devices is highly
complex.
101
covalently bound heavy metal catalyst residue;
namely Palladium at about 80 ppm. This highlights
firstly, that extremely low impurity
concentrations can have profound effects on the
properties of organic semiconductors, and
secondly, that such effects in some cases may
lead to favourable behaviour, as well – in this
case, triplet harvesting.
102
References – Textbooks [T] and review papers [R]
103
Either of R7-R9 will serve you nicely as an introduction
into organic field effect transistors.
104